WO2008059986A1 - Encre pour impression jet d'encre - Google Patents

Encre pour impression jet d'encre Download PDF

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Publication number
WO2008059986A1
WO2008059986A1 PCT/JP2007/072488 JP2007072488W WO2008059986A1 WO 2008059986 A1 WO2008059986 A1 WO 2008059986A1 JP 2007072488 W JP2007072488 W JP 2007072488W WO 2008059986 A1 WO2008059986 A1 WO 2008059986A1
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WIPO (PCT)
Prior art keywords
ink
formula
ink jet
compound
group represented
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PCT/JP2007/072488
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English (en)
Japanese (ja)
Inventor
Satoshi Tanioka
Kaori Eguchi
Takashi Kikukawa
Hiroshi Anraku
Shinsuke Hanafusa
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Chisso Corporation
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Priority to JP2008544220A priority Critical patent/JPWO2008059986A1/ja
Publication of WO2008059986A1 publication Critical patent/WO2008059986A1/fr

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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
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

Definitions

  • the present invention relates to an ink jet ink, for example, an inkjet ink containing an alkenyl-substituted nadiimide compound (A) for forming an insulating film layer in the manufacture of electronic components, and a polyimide film formed by using the ink jet ink. Furthermore, the present invention relates to a film substrate on which a polyimide film is formed and a bright electronic component having the film substrate.
  • an ink jet ink for example, an inkjet ink containing an alkenyl-substituted nadiimide compound (A) for forming an insulating film layer in the manufacture of electronic components, and a polyimide film formed by using the ink jet ink.
  • the present invention relates to a film substrate on which a polyimide film is formed and a bright electronic component having the film substrate.
  • Polyimide is a material widely used in the field of electronic communication because of its excellent heat resistance and electrical insulation properties.
  • Patent Document 1 JP 2000-039714 A (Patent Document 1), JP 2003-238683 A (Patents) Reference 2) and Japanese Patent Application Laid-Open No. 2004-094118 (Patent Document 3)].
  • Polyimide is used as the desired pattern film: ⁇
  • ⁇ In the past, it was common to form a pattern using a etching polyimide, but in recent years, methods for forming the desired pattern film by inkjet have been studied. Has been.
  • Ink jet inks have been proposed [see, for example, Japanese Patent Application Laid-Open No. 2003-213165 (Patent Document 4) and Japanese Patent Application Laid-Open No. 2006-131730 (Patent Document 5)].
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2003-213165
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2006-131730
  • the proportion of polyamide in the ink is reduced by increasing the proportion of the solvent.
  • the thickness of the film obtained by one injection becomes thin.
  • a alkenyl-substituted nadiimide compound is a chemical compound that can be polymerized by heating under heat to become a solid product (polyimide) having an imide bond [for example, JP 59-080661 A (See Patent Document 6), Japanese Patent Application Laid-Open No. 60-124619 (Patent Document 7), Japanese Patent Application Laid-Open No. 61-018761 (Patent Document 8), Japanese Patent Application Laid-Open No. 05-301948 (Patent Document 9)] .
  • Thermosetting polyimides such as maleimide type, acetylene type, and nadic acid type are obtained by three-dimensional crosslinking of low molecular weight, low viscosity compounds having an unsaturated group at the end, so that conventional linear poly It is easier to process than mid. Since it exhibits good heat resistance and generates less voids and cracks when hard, it has excellent properties as a matrix resin for molding materials and laminated materials. It is a talented and low molecular weight imide monomer with a bulky structure, so it is soluble in almost all organic solvents except aliphatic hydrocarbons. It can be used stably without gelation.
  • liquid crystal aligning agent varnish in which a varkenino! ⁇ -Converted nadiimide compound is further added to a varnish containing polyamic acid, soluble polyimide and the like [for example, JP-A-2 004-341030 (Patent Document 11) )].
  • this technology is mainly based on polyimide polymer compounds such as polyamide acid and soluble polyimide, and a small amount of alkenyl-substituted josimide compound is used to improve the mechanical strength and resistance to rubbing of the polyimide alignment film. (In the examples, 0.6% of the liquid crystal aligning agent varnish and
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2000-039714
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-238683
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. 2004-094118
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2003-213165
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2006-131730
  • Patent Document 6 Japanese Patent Laid-Open No. 59-080661
  • Patent Document 7 Japanese Patent Laid-Open No. 60-124619
  • Patent Document 8 Japanese Patent Application Laid-Open No. 61-018761
  • Patent Document 9 JP 05-301948 A
  • Patent Document 10 Japanese Patent Application Laid-Open No. 09-325210
  • Patent Document 12 JP 07-053516 A Disclosure of the Invention
  • ink-jet ink that can form a relatively thick polyimide film (1 ⁇ m or more) by one jetting (discharge).
  • the present inventors have proposed an ink jet ink containing at least one alkenyl-substituted nadiimide compound (A), an ink jet ink further containing a polymer compound (B), and an ink jet containing a solvent (C). Found ink for use.
  • the present invention provides the following ink jet ink and the like.
  • An ink jet ink comprising at least one alkenino V®-converted nadimide compound (A).
  • the alkenyl-substituted nadiimide compound (A) is an alkenyl-substituted nadiimide compound obtained by reacting a monoamine, diamine, triamine, or tetraamine with an alkenyl-substituted nadic acid anhydride represented by the following formula (1,) Ink jet ink as described in item [1].
  • R 1 and R 2 are independently hydrogen, carbon number :! -12 alkyl, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, arylenole having 6 to 12 carbons, or benzenore.
  • a compound in which the self-carel-substituted nadiimide compound ( ⁇ ) is represented by the following formula (1) [1] above.
  • R 1 and R 2 are each independently hydrogen, carbon number:! To 12 alkyl, carbon number 3 to 6 alkyl, carbon number 5 to cycloalkyl, carbon number 6 to It can be either 12 reels or benzinore, n :! Is an integer of ⁇ 4,
  • R 3 is hydrogen, carbon number :! ⁇ 12 alkyl, C1-C12 hydroxyalkyl, C5-C8 cycloalkyl, C6-C12 aryl, benzyl, one ⁇ (C q H 2q ) O t (C r H 2r O) u C s H 2s X ⁇ (where q, r, and s are independently selected integers of 2 to 6, t is an integer of 0 or 1, u is an integer of 1 to 30, and X is a hydrogen or hydroxyl group.
  • R a -C 6 H 4 -R 4 (where a is an integer of 0 or 1, R is an alkylene having 1 to 4 carbon atoms, and R 4 is A group represented by hydrogen or carbon number;! Represents an alkyl of 4 to 4), C 6 H 4 — T— C 6 H 5 (where T is _CH 2 _, -C (CH 3 ) 2 — one CO-, one S- or single S_ ⁇ 2 - group in which a is ⁇ group represented by or from 1 to 3 hydrogen directly bonded to the aromatic ring of these groups, is replaced with a hydroxyl group,
  • R 3 is alkylene having 2 to 20 carbon atoms (any methylene in alkylene not adjacent to each other may be replaced by 1 O— or 1 CH ⁇ CH—, and any hydrogen is May be replaced by fluorine, ⁇ , cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, one (R) a -C 6 H 4 -R 5- (where a is 0 or 1 ::, R and R 5 are each independently an alkylene having 1 to 4 carbon atoms), one C 6 H 4 — ⁇ — C 6 H 4 —, one C 6 H 4 — T_C 6 H 4 — T_C 6 H 4 — or _C 6 H 4 — T, one C 6 H 4 — ⁇ — C 6 H 4 — T, one C 6 H 4 — ⁇ where T is a single bond, carbon number: !
  • An alkylene of ⁇ 6, 1 C (CH 3 ) 2 —, -C (CF 3 ) 2 —, 1 CO_, 1 0_, 1 S— or 1 S 2 —, and T, is 1 CH 2 — or 1 ⁇ —.
  • R is hydrogen, fluorine, chlorine, One ⁇ _H, _ ⁇ _CF 3, One OCF 2 H, one CF 3, _CF 2 H, _CFH 2, one OCF 2 CF 2 H, One OCF 2 CFHCF 3 , or alkyl having 1 to 10 carbon atoms
  • R 4 , R 5 , and R 6 are each independently a single bond, a transformer 1, 4 -Cyclohexylene, 1,3-dioxane-1,2,5-diyl, 1,4 monophenylene, 1,4 monophenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms
  • any methylene that is not adjacent to each other in the alkylene may be replaced with 1 O— or 1 CH ⁇ CH—, any hydrogen may be replaced with fluorine
  • n is 2 and R 3 is alkylene having 2 to 15 carbon atoms (any methylene which is not adjacent to each other in alkylene may be replaced by 1—0 or 1 CH ⁇ CH—) Any hydrogen may be replaced by fluorine ⁇ ,-(R) a -C 6 H 4 -R 5- (where a is an integer of 0 or 1, R and R 5 are each independently C 1 H 4 —T 1 C 6 H 4 —, -C 6 H 4 -TC 6 H 4 -TC 6 H 4 -or 1 C 6 H 4 — T, 1 C 6 H 4 — ⁇ 1 C 6 H 4 — ⁇ , 1 C 6 H 4 _ ⁇ where T is a single bond, 1 CH.
  • R is one CH 2 —, one CH 2 CH 2 —, one O—, one C (CH 3 ) 2 one, one C (CF 3 ) 2 —, one S ⁇
  • R 1 and R 2 are each independently hydrogen or carbon number :! Is an alkyl of ⁇ 6, n is 3, and R 3 is represented by formula (5-1), formula (5, 1), or formula (5, 1 2)
  • R is alkyl having 1 to 1 carbon atoms: I 0 or 1 OH.
  • R 4 , R 5 and R 6 are each independently 1 , 2-ethylene, 1,4-butylene [8]
  • R 1 and R 2 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 4, and R 3 is represented by the following formula (6-1): Ink for inkjet described in 1.
  • Solvent (C) Ethyl lactate, Ethanol, Ethylene glycol, Propylene glycol mono-ole, Glycerin, Diethylene glyco-no-resin methinoreate , Diethylene glycol nomonoethyl ethinoate etherate acetate, ethylene glycol nole mono pentenoate etherate, ethylene glycol monoethyl ether etherate, propylene darconol monomethyl ether acetate, methyl 3-methoxypropionate,
  • the inkjet ink according to item [14] which is one or more selected from the group consisting of 3-ethyl ethoxypropionate, cyclohexanone and ⁇ -ptyrolactone.
  • a polyimide film forming method including a step of forming a polyimide film.
  • Fig. 1 shows the IR spectrum of TrisA ITAEA obtained in Synthesis Example 12.
  • FIG. 2 is a 1H-NMR spectrum of TrisANITAEA obtained in Synthesis Example 12.
  • Fig. 3 shows the IR spectrum of TrisANITrisAM obtained in Synthesis Example 1-3.
  • FIG. 4 is a 1H-NMR spectrum of TrisANITrisAM obtained in Synthesis Example 13.
  • Fig. 5 shows the IR spectrum of TrisANIPARARO obtained in Synthesis Example 14.
  • FIG. 6 is a 1H-NMR spectrum of TrisANIPARARO obtained in Synthesis Example 14.
  • Figure 7 shows the IR spectrum of TetrakisA ITAM obtained in Synthesis Example 15.
  • FIG. 8 is a 1 H-NMR spectrum of Tetraki sANITAM obtained in Synthesis Example 15. BEST MODE FOR CARRYING OUT THE INVENTION
  • the present invention provides an ink-jet ink containing an alkenono V®-converted nadiimide compound (A), a method for forming a polyimide film using the ink, and the like.
  • the ink jet ink is an ink jet ink containing at least one alkenyl-substituted nadimide compound (A), an ink jet ink containing a polymer compound (B), or an ink jet ink further containing a solvent (C). .
  • the alkenino®-converted nadiimide compound (A) contained in the ink-jet ink of the present invention is a compound having at least one alkenyl-substituted nadiimide structure in the molecule, and preferably an alkenyl-substituted nadiimide represented by the following formula (1): Although a compound can be mentioned, it is not limited to this.
  • R 1 and R 2 are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 6 carbons. Either 12 aryl or benzinore, n is an integer from 1 to 4.
  • R 3 is hydrogen, carbon number :! ⁇ 12 alkyl, C 1-12 hydroxyalkyl, C 5-8 cycloalkyl, C 6-12 aryl, benzyl, 1 ⁇ (C q H 2q ) O t (C r H 2r O ) u C s H 2s X ⁇ '(where q, r and s are independently selected integers of 2 to 6, t is an integer of 0 or 1, u is an integer of 1 to 30, and X is hydrogen or (R) a -C 6 H 4 -R 4 (where a is an integer of 0 or 1, R is an alkylene having 1 to 4 carbon atoms, R 4 Represents hydrogen or alkyl having 1 to 4 carbon atoms), a group represented by: C 6 H 4 — T_C 6 H 5 , wherein T represents one CH 2 —, —C (CH 3 ) 2 _, 1 CO_, _S— or 1 S0 2 .
  • R 3 is alkylene having 2 to 20 carbon atoms (any methylene that is not adjacent to each other in alkylene may be replaced with 1 O— or 1 CH ⁇ CH—, and any hydrogen is May be replaced by fluorine ⁇ , cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, one (R) a -C 6 H 4 -R 5- (where a is 0 or 1 An integer, R and R 5 are each independently an alkylene having 1 to 4 carbon atoms), -C 6 H 4 _T—C 6 H 4 —, and one C 6 H 4 _T—C 6 H 4 — T— C 6 H 4 — or _C 6 H 4 — T, one C 6 H 4 — T— C 6 H 4 — T ′ — C 6 H 4 — ⁇ where T is a single bond, carbon number: !
  • ⁇ 6 alkylene 1 C (CH 3 ) 2 —, -C (CF 3 ) 2 _, 1 CO—, 1 0—, 1 S— or 1 S 2 —, and T ′ is 1 CH 2 — Or one O—.
  • ⁇ A group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced by a hydroxyl group, a group represented by formula (7), or a group represented by formula (8)
  • X is independently: ⁇ 6 and y :! It is an integer of ⁇ 70.
  • R 3 is a group represented by the following formula (5) or ') c
  • R is hydrogen, fluorine, chlorine, 1 OH, 1 OCF 3 , 10 CF 2 H, 1 CF, 1 CF 2 H, 1 CFH 2 , _OCF. CF 2 H, one OCF. CFHCF 3 or carbon number :!
  • R 4 , R 5 , and R 6 are each independently a single bond, trans 1,4-cyclohexylene, 1, 3 —Dioxane-1,5-diyl, 1,4-monophenylene, hydrogen replaced by fluorine;
  • TL may be 1,4-diphenylene, or an alkylene having 1 to 10 carbon atoms, alkylene
  • the adjacent methylenes in the! / Arbitrary methylene may be replaced with 1 O— or 1 CH ⁇ CH—, and any hydrogen may be replaced with fluorine.
  • R is the number of carbons! ⁇ 10 alkyl or 1 OH
  • the alkenyl-substituted nadiimide compound (A) includes an alkenoino! N-substituted nadiimide compound in which n is 1 (a 1: hereinafter sometimes simply referred to as “alkenyl-substituted nadiimide”), and 11 Is an alkenyl-substituted nadiimide compound (a 2 is simply referred to as “bisalkenino kg-substituted nadiimide” hereinafter), and an alkenyl-substituted nadiimide compound in which n is 3 (a 3 is hereinafter simply referred to as “trisarkenino-substituted nadiimide”). J), and alkenyl-substituted nadiimide compounds in which n is 4 (a4: hereinafter simply referred to as “tetrakisalkenino! ⁇ -Con
  • the ink jet ink of the present invention includes an alkenino-substituted nadiimide compound (A) in which n is 1, an alkenyl-substituted nadiimide compound (A) in which n is 2, an alkenyl-substituted nadiimide compound (A) in which n is 3 and n May contain at least two alkenyl-substituted nadiimide compounds (A) selected from the group consisting of alkenyl-substituted nadiimide compounds (A) having a power of 4.
  • the alkenyl-substituted nadiimide compound (A) is an alkell-substituted nadiimide compound obtained by reacting a monoamine, diamine, triamine, or tetraamine with an alkenyl-substituted nadic acid anhydride represented by the following formula (1,). Also good.
  • R 1 and R 2 are each independently hydrogen, alkyl having 1 to 12 carbons, alkyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 6 carbons. Either 12 ariel or benzyl.
  • R 1 and R 2 are each independently hydrogen or carbon number :! ⁇ Alkyl of 6 and R 3 is carbon number!
  • alkenyl-substituted nadiimide compound in which n is 1 used in the present invention include the following.
  • the substituted nadiimide (a l) may be used in worms or a mixture thereof.
  • alkenyl-substituted nadiimide (a 1) preferred are
  • N, N ' hexamethylene monobis (arylbicyclo [2. 2. 1] heptoh-5-en-1,2-dicarboximide),
  • bisalkenyl-substituted nadiimides (a 2) may be used as worms or as a mixture thereof.
  • Preferred as the bisalkenyl-substituted nadiimide (a 2) is
  • N N'-trimethylene bis (arylbicyclo [2. 2. 1] heptoe-5-en-2,3-dicarboximide), N, N, hexamethylene monobis (arylbicyclo [2. 2. 1] hept-1-ene 2,3-dicarboximide),
  • N, N, I —Xylylene bis (arylbicyclo [2.2.1] heptoe-5-en-2,3-dicarboxyimide),
  • Bis ⁇ 4_ (Arylmethinolebicyclo [2.2.1] heptoe-5_en-1,3-dicarboxy imide) phenyl ⁇ sulfone and the like. Also Bis ⁇ 4 -1 (metallinolebicyclo [2.2.1] hept- 1-5 _en- 2, 3- dicanolevoximid) phenol ⁇ sulfone and the like.
  • bisalkenyl-substituted nadiimide (a 2) more preferred are
  • the synthesis of the trisulfenino-substituted nadiimide compound having n of 3 used in the present invention is carried out by mixing 3.0 to 5.0 moles of alkenyl-substituted nadic acid anhydride with respect to 1.0 mole of triamine.
  • the above solvent is removed by drying under reduced pressure at 20 to 80 ° C. to obtain amic acid.
  • the above-mentioned amic acid is re-blacked in the solvent for 0.5 to 30 hours near the boiling point of the solvent, and the compound itself is heated at 160 ° C. to 200 ° C.
  • the target compound can be obtained by removing the solvent.
  • the target compound can be confirmed by NMR and IR. Specific examples of the trisanolokel-substituted nadiimide compound in which n is 3 used in the present invention include the following.
  • Tris ⁇ 4 -1 (Alilbicyclo [2. 2. 1] heptoe-5-en-1,2-dicarboxy imide) Triphenyl ⁇ Methane
  • Tris ⁇ 4 -1 (Aralbicyclo [2. 2. 1] Heptone 5-ene 2, 3-dicarboxy imide) Phenyl ⁇ Hydroxymethane Tris ⁇ 4 -1 (Aralbicyclo [2. 2. 1] Hepto 5_e Fig. 1 and Fig. 2 show the IR and 1 H-NMR spectra (400 MHz) of triethyl ⁇ amine (TrisANITAEA), respectively.
  • a tetrakisalkenyl-substituted nadiimide compound in which n is 4 used in the present invention is prepared by mixing 4.0 to 6.0 mol of alkenyl-substituted nadic acid anhydride with respect to 1.0 mol of tetraamine, and at room temperature, for example, Benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin, chlorophenol, trichlene, tetrachloroethylene, black benzene, dioxane, tetrahydrofuran, hexamethylene ether, anisole, acetone, methylethylketone, methylisobutylketone, acetophenone , N, N-dimethylolformamide, dimethyl sulfoxide, or any other solvent, or a mixture of two or more of them can be dissolved in a solution, and the reaction
  • the above solvent is removed by drying at 20-80 ° C for 3 ⁇ 4E to obtain amic acid.
  • the above amic acid is refluxed in the above solvent for 0.5 to 30 hours, near the boiling point of the solvent, or the compound itself is heated at 160 ° C to 200 ° C to ⁇ ring-close, and then the solvent
  • the desired compound can be obtained by drying.
  • the target compound can be confirmed by NMR and IR.
  • Specific examples of the tetrakisalkenino V®-converted nadiimide compound in which n is 4 used in the present invention include the following. W 200
  • the preferred alkeno-substituted nadiimide compound (A) of the present invention is a low molecular weight imide monomer having a bulky structure, it is soluble in most organic solvents and stored for a long period of time in a liquid state. However, it can be used stably without causing crystal precipitation or gelation. In addition, when heated, it forms a three-dimensional cross-linked polyimide, and the polyimide silicide exhibits good heat resistance, vigilance, electrical properties, and chemical resistance. 2 Polymer compound (B)
  • the polymer compound (B) that can be further contained in the ink-jet ink of the present invention is polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol, poly Although it is a high molecular compound such as oxyethylene, it is not limited to this.
  • it is a polyimide-based polymer compound such as polyamic acid or soluble polyimide.
  • polyamic acid or its imidized polymer described in Japanese Patent Application No. 2006-235336 can be preferably mentioned. This is not limited to this.
  • the polyamic acid comprises at least a compound (b 1) having two or more acid anhydride groups, a diamine (b 2), a monoamine (b 3), and a compound (b 4) having one acid anhydride group. It can be obtained by using, but is not limited to the polyamic acid obtained by the production method.
  • the compounds (b 1), diamine (b 2), monoamine (b 3), and acid anhydride groups having two or more acid anhydride groups that can be used to obtain the polymer compound (B) are described below. One compound (b 4) is explained.
  • Specific examples of the compound (b 1) having two or more acid anhydride groups used in the present invention include seven compounds such as styrene monomaleic anhydride copolymer and methyl methacrylate monomaleic anhydride copolymer. Examples thereof include a copolymer of a radically polymerizable monomer having a group and another radical polymerizable monomer such as tetracarboxylic dianhydride.
  • tetracarboxylic dianhydrides are 2, 2,, 3, 3, monobenzophenone tetracarboxylic dianhydride, 2, 3, 3 ', 4'-benzophenone tetracarboxylic dianhydride 2, 2,, 3, 3, Diphenylsulfonetetracarboxylic dianhydride, 2, 3, 3 ', 4, Diphenylsulfone tetracarboxylic dianhydride, 2, 2,, 3, 3 , 1-diphenyl ether tetra force sulfonic acid dianhydride, 2, 3, 3,, 4, — diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), ethane tetracarboxylic acid Dianhydride, 4- (2,5-dioxoterohydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-didecanoleic anhydride, 5-
  • styrene monomaleic anhydride copolymer formula bl-l, bl-5, bl-6, b 1-7, b 1-8, b 1
  • the compounds represented by -9, b 1-14, bl_18, and bl-20 are preferred because they have high solubility in a solvent and can prepare a high concentration of ink. In addition, high transparency is required depending on the application of the ink for ink jet.
  • Such ⁇ includes styrene-maleic anhydride copolymer, b 1-6, b 1-7, bl-8, b It is particularly preferable to use compounds represented by 1-9, bl-14, b1-18 and the like.
  • the compound having an acid anhydride group described above may be a single type or a combination of two or more types. May be used
  • the diamine (b 2) used in the present invention is not particularly limited as long as it has two amino groups, and examples thereof include compounds represented by the following general formulas (II) to (VIII).
  • ⁇ 1 is one (CH 2 ) p — (p is an integer from 1 to 12), ⁇ ⁇ (C q H 2q
  • a polyoxyalkylene which is of the formula (II
  • R is an organic group represented by 1 CH 3 or 1 (CH 3 ) 2 , and in formulas (IV) and (VI) to (VIII),
  • a 1 is a single bond, 1 O— , 1 S—, 1 S— S—, 1 S0 2 —, 1 CO—, — CONH—, — NHCO—, 1 C (CH 3 ) 2 —, — C (CF 3 ) 2 —, 1 (CH 2 ) m one, one O— (CH 2 ) m — O—, one S— (CH 2 ) m — S—, where m is an integer from 1 to 6,
  • a 2 is a single bond, — O—, 1 S—, 1 CO—, -C (CH 3 ) 2 —, 1 C (CF
  • diamines represented by general formula (II) include diamines represented by formulas (II-1) and (II-7).
  • diamines represented by general formula (IV) include, for example, formula (IV— 1)
  • Examples thereof include diamines represented by formulas (VI-1) to (VI-30).
  • Examples of diamines represented by general formula (VII) include, for example, formulas (VII _ :! to (VII-6).
  • Examples of diamines represented by general formula (VIII) include diamines represented by formulas (VIII-1) to (VIII-1 1).
  • diamine (b 2) represented by the general formulas (II) to (VIII), more preferably, the formula (V-1) to (V-5), the formula (VI-1) to (VI-12), Formula (VI-26), Formula (VI-27), Formula (VII-1), Formula (VII-2), Formula (VII-6), Formula (VIII-1) to (VIII 1), and more preferably a formula (V-6), a formula (V-7), a formula
  • Examples thereof include diamines represented by (VI-1) to (VI-12).
  • Examples of diamine (b 2) used in the present invention further include diamine represented by the general formula (IX).
  • a 3 is a single bond, 1 O—, 1 COO—, 1 OCO—, 1 CO_, 1 CONH— or 1 (CH 2 ) m ⁇ (where m is an integer from !! to 6) ,
  • the hydrogen bonded to the ring-forming carbon of the phenyl may be replaced with _F, 1 CH 3 , 1 OCH 3 , 1 OC H 2 F, 1 OCHF 2 or 1 OCF 3 .
  • a 4 and A 5 are each independently a single bond, 1 O—, 1 COO—, 1 OCO—, —C ONH—, 1 CH ⁇ CH— or alkylene having 1 to 12 carbon atoms,
  • R 7 and R 8 are each independently 1 F or 1 CH 3 ,
  • Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-1,2,5-diyl, pyrimidine-1,2,5-diyl, pyridine-1,2,5-dinole, naphthalene1,5 —Zinole, Naphthalene 1,7—Zill or Anthracene 9,10—Zill
  • a and b each independently represents an integer of 0 to 4,
  • c, d and e each independently represent S3 ⁇ 4 from 0 to 3, and when e is 2 or 3,
  • the number of rings s may be the same or different
  • f and g each independently represent an integer from 0 to 2
  • the two amino groups are bonded to the pheninocarbon.
  • the bonding position of the two amino groups is meta or para.
  • the two amino groups are preferably bonded to the 3rd and 5th positions or the 2nd and 5th positions, respectively, when the bonding position of “R 6 —A 3 —” is the 1st position.
  • Examples of the diamine represented by the general formula (IX) include diamines represented by the following formulas (IX-1) to (IX-1 1).
  • R 18 is an organic group having 2 to 30 carbon atoms, and among these, 3 to 12 carbon atoms. Or alkyl having 3 to 12 carbon atoms is preferable, and alkyl having 5 to 12 carbon atoms or alkoxy having 5 to 12 carbon atoms is more preferable.
  • R 19 is 1 H or an organic group having 1 to 30 carbon atoms. Preferred is alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, more preferably 3 to carbons: more preferably alkyl having 10 carbons or alkoxy having 3 to 10 carbons! /.
  • the diamines represented by the general formula (IX) include diamins represented by the following formulas (IX-12) to (IX 7).
  • R 20 is 1H or carbon number :! ⁇ 30 existence An alkyl group having 4 to 16 carbon atoms is preferable, and an alkyl having 6 to 16 carbon atoms is more preferable.
  • R 21 is 1H or an organic group having 1 to 30 carbon atoms, preferably alkyl having 6 to 20 carbon atoms, and having 8 to 20 carbon atoms. Alkyl is more preferred.
  • the diamine represented by the general formula (IX) for example, the following formulas (IX-18) to (IX-38)
  • R 22 is 1 H or an organic group having 1 to 30 carbon atoms, alkyl having 1 to 12 carbons, and alkyl having 1 to 12 carbons. Lucoxy is preferred, and alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons is more preferred.
  • R 23 is 1 H, 1 F, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, 1 CN, 1 O CH 2 F, 1 OCHF 2 or 1 OCF More preferred are alkyls having 3 to 12 carbon atoms or alkoxy having 3 to 12 carbon atoms.
  • a 9 is alkylene having 1 to 12 carbons. Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-39) to (IX-48).
  • diamines (b 2) represented by the general formula (IX) diamines represented by the formulas (IX-1) to (IX-11) are preferred, and the formulas (IX-2) and (IX-4) ), Formula (IX-5) and formula (IX-6) are more preferred.
  • Diamine (b 2) used in the present invention is a compound represented by the following general formulas (XI) and (XII)
  • R 1 Q is 1 H or 1 CH 3
  • Each R 11 independently represents 1 H or an alkyl or alkyl having 1 to 20 carbon atoms
  • R 13 and R 14 are each independently 1 H, alkyl having 1 to 20 carbon atoms, or phenyl.
  • each of the two amino groups is bonded to the phenyl ring carbon and bonded to the meta position or the para position with respect to the bonding position of A 6 .
  • diamines represented by the general formula (XI) include those represented by the formulas (XI-1) to (XI—4).
  • two “NH 2 — (R 1 4-) P h—A. One 0—” are each bonded to a phenyl ring carbon, but preferably a steroid nucleus is bonded. Bonded to carbon in meta or para position relative to carbon. The two amino groups are preferably bonded to the meta position or the para position with respect to the force A 6 bonded to the phenyl ring carbon.
  • Examples of diamine (b 2) used in the present invention further include compounds represented by general formulas (XIII) and (XIV).
  • R 15 is 1 H or alkyl having 1 to 20 carbon atoms, and any one CH 2 — of the alkyl having 2 to 20 carbon atoms is 1 O—, 1 CH ⁇ CH— or 1 C ⁇ C may be replaced by one,
  • Each A 7 is independently 1 O— or alkylene having 1 to 6 carbon atoms
  • a 8 represents a single bond or an alkylene carbon number 1-3
  • Ring T is 1,4 monophenylene or 1,4-cyclohexylene
  • h 0 or 1.
  • R 16 is alkyl having 6 to 22 carbon atoms
  • R 1 7 an H or the number of carbon atoms:! ⁇ 2 is alkyl of 2,
  • a 7 is independently 1 O— or carbon number :! ⁇ 6 alkylene.
  • the two amino groups are each bonded to the ring ring carbon, but preferably bonded to the meta position or para to A 7 .
  • Examples of the diamine represented by the general formula (XIII) include diamines represented by the formulas (XIII-1) to ( ⁇ -9).
  • R 25 is 1 H, carbon number :! Even more preferred are ⁇ 10 alkyl groups.
  • the two amino groups are each bonded to a phenyl ring carbon, but preferably bonded to the meta position or the para position with respect to A 7 .
  • Examples of the diamine represented by the general formula (XIV) include diamines represented by (XIV-1) (XIV-3).
  • R 2 6 is an organic group having 0 2-3 carbon atoms, preferably an alkyl group having a carbon number of 6-2 0 Of these, R 2 7 is It is an organic group having 2 to 30 carbon atoms. More preferred are ⁇ 10 alkynole groups.
  • diamine (b 2) used in the present invention for example, diamines represented by the general formulas (II) to (XIV) can be used, but diamines other than these diamines can also be used. it can.
  • a naphthalene-based diamine having a naphthalene structure, a funolite-based diamine having a fluorene structure, or a siloxane-based diamine having a siloxane bond can be used alone or mixed with another diamine.
  • the siloxane-based diamine is not particularly limited, but those represented by the following formula (XV) can be preferably used in the present invention.
  • R 3 and R 4 are independently carbon number :! ⁇ 3 alkyl or phenyl
  • R 5 is independently methylene, phenylene or alkyl-substituted phenyl
  • X is independently an integer from 1 to 6
  • y is 1 to 7 is an integer of 0.
  • y is more preferably 1 to 1 is an integer of 5.
  • the diamine (b 2) used in the present invention is represented by the following formula (11):
  • R 3 ° and R 3 1 are each independently an alkyl group having 3 to 20 carbon atoms.
  • the diamine (b 2) that can be used in the present invention is not limited to the diamine of the present specification, and various other forms of diamine can be used within the scope of achieving the object of the present invention. Can do.
  • the diamine (b 2) that can be used in the present invention can be used alone or in combination of two or more. That is, as the combination of two or more kinds, the above-mentioned jamins, the above-mentioned jamins and other jamins, or the other jamins other than the above-mentioned jamins can be used.
  • high transparency is required depending on the application of the ink-jet ink.
  • 3, 3, 1-diaminodiphenyl sulfone and an integer of y 1 to 15 in the general formula (XV) It is particularly preferred to use diamine which is 2.3 Monoamine (b 3)
  • the monoamine (b 3) used in the present invention is not particularly limited, but specific examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3 —Aminopropylmethyl ketoxysilane, 4-Aminoptyltrimethoxysilane, 4-Aminoptyltriethoxysilane, 4-Aminopynolemethylmethoxysilane, p-Aminophenoletrimethoxysilane, p -Aminophenol triethoxysilane, ⁇ -aminophenylmethyl ⁇ / dimethoxysilane, ⁇ -aminominomethylmethyloxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethylmethoxysilane, 2 —Aminobenzoic acid, 3-Aminobenzoic acid, 4-Amin
  • 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and p-aminophenyltrimethoxysilane are preferable because the resulting film has excellent durability.
  • Triethoxysilane is particularly preferred.
  • These monoamines can be used singly or in combination of two or more.
  • the compound (b 4) having one acid anhydride group used in the present invention is not particularly limited, but specific examples include p- (trimethoxysilinole) phenylsuccinic anhydride, p- (Triethoxysilinore) phenenoresuccinic anhydride, m— (trimethoxysilyl) phenylsuccinic anhydride, m_ (triethoxysilyl) phenylsuccinic anhydride, trimethoxysilyl repropinoresuccinic anhydride And trietoxysilylpropyl succinic anhydride.
  • trimethoxysilylpropyl succinic anhydride and triethoxysilyl-propyl succinic anhydride are particularly preferred from the standpoint of ink storage stability.
  • the polyamic acid that can be used in the present invention includes, for example, one or more selected from the group consisting of a monoamine (b 3) and a compound (b 4) having one acid anhydride group, and an acid anhydride group. It can be synthesized by reacting two or more compounds (b 1) with diamine (b 2). Using monoamine (b 3), diamine (b 2) 0.01 to 0.8 mol and monoamine (b 3) 0.4 per mol of compound (b 1) having two or more acid anhydride groups The compound having two or more acid anhydride groups (b 1) 1 monole, diamine (b 2) 0.15 to 0.25 mol and monoamine (b 3) 1 More preferred to use 5-1.7 mol.
  • the compound (b 1) having two or more acid anhydride groups per diamine (b 2) 1 monole (b 1) 0.01 to 0 Compound having 8 moles and one acid anhydride group (b 4) 0.4 to: 1. It is preferable to use 98 moles, and 2 moles of acid anhydride groups per mole of diamine (b 2) Compound (b 1) having 0.15 to 0.25 mol and one compound having one acid anhydride group (b 4) 1.5 to 1.7 mol is more preferably used.
  • At least polyamic acid is prepared using compound (b 1) having two or more acid anhydride groups, diamine (b 2), monoamine (b 3) and compound (b 4) having one acid anhydride group.
  • the solvent used for obtaining the compound is not particularly limited as long as the compound strength S can be synthesized.
  • jetylene glycol dimethinoleatenole diethylene glycol jetyl ether, jetylene glycol methylenoethyl / Leethenole
  • Jetylene glycol monoethyl etherate acetate Ethylene glycol monoethyl ether etherate, Propylene Daricol Monomethyl etherate acetate, Methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Hexanone for mouth-mouth, y petit rataton, N-methinoleyl 2-pyrrolidone, and N, N-di Chiruasetoamido, and the like.
  • reaction solvents can be used as war insects or as a mixed solvent of two or more. In addition to the reaction solvent, other solvents can be mixed and used.
  • the reaction solvent is a total of 100 weights of the compound (b 3) having two or more acid anhydride groups, diamine (b 2), monoamine (b 3), and compound (b 4) having one acid anhydride group. Using more than 100 parts by weight per part is preferable because the reaction proceeds smoothly! / ⁇ .
  • the reaction is preferably carried out at 0 ° C to 100 ° C for 0.2 to 20 hours.
  • the order of adding the reaction raw materials to the reaction system is not particularly limited. That is, the compound (b 1) having two or more acid anhydride groups, diamine (b 2), monoamine (b 3), and compound (b 4) having one acid anhydride group were simultaneously used as a reaction solvent.
  • compound (b 1) having two or more acid anhydride groups and diamine (b 2) are reacted in advance.
  • monoamine (b 3) is added to the copolymer. It is possible to have.
  • the polymer compound (B) having a weight average molecular weight of 1,000 to 20,000 is particularly excellent in solubility in a solvent and is preferred as an ink for a ink jet.
  • the weight average molecular weight is preferably from 1,000 to 10,000, 000 to 5,000 is more preferable.
  • the polymer compound (B) preferably has a weight average molecular weight of 1,000 to 2,000.
  • the polymer compound (B) having a weight average molecular weight of 1,000 or more does not evaporate by heat treatment, is stable in terms of chemicals and leakage, and has a weight average molecular weight of 2,000 or less. Since the polymer compound (B) having an improved solubility in a solvent, it is possible to increase the thickness of the resulting coating film, and as an inkjet ink. This is because it can be preferably used.
  • the weight average molecular weight of the polymer compound (B) can be measured by gel permeation chromatography (GPC) method. Specifically, the obtained polymer compound (B) was diluted to a concentration of about 1 weight 0/0 tetrahydrofuran (TH F), etc., Toso stock meeting force ram G 4 0 0 0 HX L, Using G 3 00 HX L, G 2 50 O HX L, and G 2 0 0 0 HX L, using TH F as a developing agent, measuring by gel permeation chromatography (GPC) method, and converting to polystyrene Can be sought.
  • GPC gel permeation chromatography
  • the inkjet ink of the present invention can be obtained, for example, by dissolving an alkenyl-substituted nadiimide compound (A) and, if necessary, a polymer compound (B) in a solvent (C). Therefore, the solvent contained in the ink jet ink of the present invention is not particularly limited as long as it can dissolve the alkenyl-substituted nadiimide compound (A) and, if necessary, the polymer compound (B). Even if the solvent alone does not dissolve the alkenyl-substituted nadiimide compound (A) and, if necessary, the polymer compound (B), the solvent (C) contained in the ink for ink jetting can be mixed with another solvent. Can be used.
  • solvent (C) contained in the ink-jet ink examples include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methinoreprolactam, N-methypropionamide, N, N-dimethylacetate.
  • the surface tension of the ink is 20 to 45 mN / m, preferably 27 to 42 mN / m, more preferably 3 Adjust to 0-4 O mNZm. If the surface tension is higher than 45 mN / m, the ink meniscus at the ink outlet may become unstable and ink may not be discharged. If the surface tension is lower than 20 mN / m, the applied droplet force S will spread out. The shape of the coating pattern is greatly deteriorated.
  • the solvent selection power S is important.
  • a kind of solvent whose surface is in the range of 20 to 45 mNZm can be used, but it has a high surface tension.
  • y-petit-mouth rataton 43 mN / m
  • a low surface tension solvent for example, diethyleneglycolenomethenoreethinoreethenole: 24 mN / m, or ethylene glycol monoptyl ether: 32 mN
  • a mixture of / because the surface 3 ⁇ 45 ⁇ can be finely adjusted by the solvent composition.
  • the solvent can be preferably used because it is a good solvent for alkenyl-substituted namidimide compounds ( ⁇ ) and polymer compounds ( ⁇ ), but on the other hand, the durability of the ink jet head is difficult and caution is required. It is.
  • the solvent (C) contained in the inkjet ink of the present invention does not contain any amide solvent, or at most 20% by weight or less based on the ⁇ ⁇ amount of the solvent (C). preferable.
  • solvents may be used alone or as a mixture of two or more.
  • the concentration of the alkenino-converted nadiimide compound (A) in the inkjet ink is not particularly limited, but is preferably 1 to 99% by weight, more preferably 10 to 80% by weight, and 2 2 to 2 More preferred is 70% by weight. These concentration ranges are preferable because the film thickness obtained by one ink jetting is optimal and the jetting accuracy is high.
  • the concentration of the polymer compound in the inkjet ink (B) is not particularly limited in the present invention, 0-5 is preferably 0 wt%, 0-2 5 weight 0/0 more preferably les. Within these concentration ranges, good characteristics can be imparted as an insulating film.
  • the ink-jet ink of the present invention can be obtained by mixing the alkenino-converted nadiimide compound (A), the polymer compound (B) if necessary, and the solvent (C) if necessary.
  • the inkjet ink of the present invention may be an epoxy curing agent such as an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, or trimellitic acid.
  • an epoxy curing agent such as an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, or trimellitic acid.
  • Amino silicon compounds, solvents, nmmi p-curing agents, preservatives, p-poisoning agents, antioxidants, anti-reduction agents, evaporation accelerators, chelating agents, water-soluble polymers, etc. Can be obtained by mixing and dissolving them uniformly.
  • the inkjet ink of the present invention may further contain an epoxy resin.
  • the epoxy resin contained in the ink jet ink is not particularly limited as long as it has oxysilane, but a compound having two or more oxysilanes is preferred.
  • the concentration of the epoxy resin in the ink jet ink is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 10 to 10% by weight. Within this concentration range, “excessive heat resistance, chemical resistance, and flatness formed from the ink for ink jet are good.
  • the epoxy resin examples include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy polymer, a polymer of a monomer having an oxysilane, and a copolymer of a monomer having an oxysilane and another monomer. Polymer, and the like.
  • the monomer having a xylan examples include glycidyl (meth) acrylate, 3,4 epoxy hexyl (meth) acrylate, and methyldaricidyl (meth) acrylate.
  • monomers that copolymerize with oxysilane-containing monomers include (meth) acrylic acid, methinole (meth) acrylate, ethinole (meth) acrylate, isopropyl (meth) acrylate, ⁇ — Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butynole (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2—hydrochuchchinole (meth) acrylate —Hydroxypropyl (meth) acrylate, styrene, methyl styrene, chloro methyl styrene, (3-ethyl-3-hexetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide it can.
  • Specific examples include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butynole methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate monoglycidyl methacrylate copolymer
  • examples thereof include a polymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene monoglycidyl methacrylate copolymer.
  • Product name "Epicoint 1004", "Epicoto 12 56” (manufactured by Japan Epoxy Resin Co., Ltd.), product name “Araldite CY177", product name “Araldite CY184J (manufactured by Ciba Geigy Japan)”
  • Product name "Celoxide Id 2021 P", “Celoxide 3000", “EHPE-3150” manufactured by Daicel Chemical Industries
  • product name Techmore VG3101 L” (manufactured by Mitsui Chemicals)
  • the product name “Araldite CY184”, the product name “Celoxide 2021 ⁇ ”, the product name “Techmore VG3101 L”, and the product name “Epicoat 828” are preferred because the flatness of the resulting polyimide film is particularly good. Masle.
  • Only one kind of epoxy resin may be used, or two or more kinds may be mixed and used.
  • the inkjet ink of the present invention may further contain an acrylic resin.
  • the acrylic resin contained in the ink jet ink is not particularly limited as long as it has an acryl group or a methacryl group.
  • the concentration of the acrylic resin in the inkjet ink is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight. Within this concentration range, the heat resistance, chemical resistance and flatness of the coating film formed from the ink jet ink are good.
  • Acrylic resins include, for example, monofunctional polymerization having hydroxyl ⁇ ⁇ biomonomer, monofunctional polymerizable monomer having no hydroxyl, bifunctional (meth) acrylate, and trifunctional or higher polyfunctional (meth) acrylate. Etc.
  • the monofunctional polymerizable monomer having hydroxyl examples include 2-hydroxyethinore (meth) acrylate, 2-hydroxypropinole (meth) acrylate, 4-hydroxy butyl (meth) acrylate, or 1, 4-cyclohexane dimethanol mono (meth) acrylate, etc. can be mentioned.
  • 4-hydroxypropylene ⁇ ⁇ attalylate and 1,4-cyclohexanedimethanolol monoacrylate are used because the film formed is flexible. Particularly preferred.
  • raw monomers include glycidyl (meth) acrylate, 3,4 epoxy hexyl (meth) acrylate, methinoreglicidino acrylate (meth) acrylate, 3-methyl mono 3— (meth) atari-mouthed xymethinoleoxetane, 3 —ethylyl 3 _ (meth) atari-mouthed oxymethyloxetane, 3-methyl-3— (meth) acrylic head (Meth) Atari-mouthed Kichetino Leoxetane, p-bi-Nolefueninore 3—Ethenoreoxeter 3-—Inole Methyl etherenole, 2-—Fuenore 3 1 (Meth) Ataloxy Methyl / Leoxetane, 2-Trifluoromethinore 3 — (Meta) Atari Mouth Methyl
  • bifunctional (meth) acrylate examples include bisphenol F ethylene oxide modified diacrylate, bisphenol ⁇ ethylene oxide modified diacrylate, isocyanurate ethylene oxide modified diacrylate, polyethylene glycol diacrylate, poly Propylene glycol diatalylate, pentaerythritol diatalylate.
  • trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, ethylene oxide modified 1 "raw trimethylolole propane tri (meth) acrylate, propylene oxide modified tri Methylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylone propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichloronohydrin modified Glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol Tonoretri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol 1, monopenta (meth) attaly Alkylate, alkyl-modified dipentaerythritol penta (
  • acrylic resins may be used alone or in combination of two or more.
  • surfactant added to the ink jet ink of the present invention include the product names “Byk—300”, “Byk—306”, “Byk—335”, “Byk—310”, “Byk— Silicone surfactants such as “341”, “Byk— 344”, “Byk— 370” (by Bic 'Chemie); trade names “Byk— 354”, “ByK— 358”, “B yk— 361” "Acrylic surfactants (such as Bic 'Chemie Co., Ltd.) Fluorine-based surfactants such as trade names “DFX-18”, “Furgent 2 50”, “Furgent 2 51” (manufactured by Nes Co., Ltd.) can be mentioned.
  • surfactants may be used alone or in combination of two or more.
  • the surfactant is used to improve the wettability, leveling property, or coating lifetime of the substrate S3 ⁇ 4, and is 0.1 to 1 part by weight relative to 100 parts by weight of the ink jet ink. It is preferable to use it in addition.
  • the antistatic agent added to the ink jet ink of the present invention is not particularly limited, and a known antistatic agent can be used. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide, and quaternary ammonium salts.
  • antistatic agents may be used alone or in combination of two or more.
  • the antistatic agent is used to prevent electrification, and is preferably used by adding 0.01 to 1 part by weight to 100 parts by weight of the ink jet ink.
  • the coupling agent added to the inkjet ink of the present invention is not particularly limited, and a known force coupling agent can be used.
  • the force coupling agent added is preferably a silane coupling agent, and specific examples include trialkoxysilane compounds and dialkoxysilane compounds.
  • y-Buylpropyltrimethyoxysilane ⁇ -Bulpropynoletriethoxysilane, ⁇ -Atarylloylpropylmethyldimethoxysilane, ⁇ -Atarylloylpropyl trimethoxysilane, ⁇ -Ataloylpropylmethylmethoxysilane , 1-acryloylpropynoletriethoxysilane, -methacryloylpropinoremethinoresimethoxysilane, y-methacryloylpropyl trimethoxysilane, ⁇ -methacryloylpropylmethyljetoxysilane, ⁇ -metatalyl oral propyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropinoretrimethoxysilane, ⁇ -glycidoxypropylmethylenoger
  • y-Buluprovir trimethoxysilane ⁇ -Atarylloyl mouth building trimethoxysilane, ⁇ -methacryloylpropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane and the like can be mentioned.
  • These coupling agents may be used alone or in combination of two or more.
  • the coupling agent is preferably used by adding 0.01 to 3 parts by weight to 100 parts by weight of ink for ink jet. (6) Epoxy curing agent
  • the epoxy curing agent added to the ink jet ink of the present invention is not particularly limited, and a known epoxy curing agent can be used. Specific examples include organic acid dihydrazide compounds, imidazole and its derivatives, dicyandiamide, aromatic amines, polyvalent carboxylic acids, carboxylic acid anhydrides, and the like.
  • dicyandiamides such as dicyandiamide, adipic acid dihydrazide, organic acid dihydrazides such as 1,3-bis (hydrazinocanolepo- terone) 5-isopropinorehydantoin, 2,4-diamino-6- [2 , Ethyl imidazolyl mono (1,;)] — imidazolyl derivatives such as ethitririadine, 2-phenylimidazole, 2-phenyl-4-methylenoreimidazole, 2-phenyl-1-methylenoleyl 5-hydroxymethylimidazole, etc.
  • Phthalic anhydride, trimellitic anhydride, and acid anhydrides such as 1,2,4-cyclohexanetricarboxylic acid 1,2-anhydride.
  • trimellitic anhydride having good transparency and 1,2,4, -hexanetricarboxylic acid-1,2-anhydride are preferable.
  • epoxy curing agents may be used alone or in combination of two or more.
  • the epoxy curing agent is preferably used in an amount of 0.2 to 5 parts by weight added to 100 parts by weight of ink jet ink.
  • aminosilicon compound can be added to the ink jet ink of the present invention.
  • the aminosilicon compound include paraaminophenyltrimethoxysilane, paraaminophenol trimethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropinotrimethoxysilane, aminopropyltriethoxysilane, and the like.
  • aminoamino compounds may be used alone or in a mixture of two or more.
  • the aminosilicon compound is used to improve adhesion to the sickle, and is preferably used by adding 0.05 to 2 parts by weight to 100 parts by weight of ink for ink jetting. . 6 Viscosity of ink jet ink
  • the viscosity of the ink jet ink is not particularly limited. However, when jetting is performed at room temperature, it is preferably 1 to 50 m Pa in that the jetting accuracy by the ink jet coating method is improved. ⁇ S (25 ° C), more preferably 5 to 3 O m Pa ⁇ s (25 ° C), more preferably 8 to 2 O m Pa * s (25 ° C) .
  • the temperature is 1 to 50 m at a heating temperature (a temperature at which the alkenyl-substituted naphthimide compound is not cured, preferably 40 to 120 ° C.).
  • P a • s preferably 5 to 30 mPa ⁇ s, more preferably 8 to 20 mPa ⁇ s. 7
  • Polyimide film The ink jet ink of the present invention can be applied to the substrate surface by an ink jet and heat-treated with a hot plate or oven to form a polyimide film having a whole surface or a predetermined pattern (line shape or the like).
  • a pattern-like polyimide film is formed using photolithographic technology.
  • a large amount of chemicals such as photoresist, developer, etching solution, stripping street night are required, and more complicated processes are required. Met.
  • the patterned polyimide film formed using the ink jet ink of the present invention draws on only the necessary portion by ink jet printing, so the amount of material used is overwhelmingly small and does not use a photomask. Therefore, it is possible to produce many kinds of products in large quantities and has the characteristics that the number of processes required for manufacturing is small.
  • ink jet application methods There are various types of ink jet application methods depending on the ink discharge method. Examples include a piezoelectric element type, a bubble jet (registered trademark) type, a continuous injection type, and a static induction type.
  • the ink according to the present invention can be jetted by various methods by appropriately selecting each component contained in the ink, and the ink jet ink can be applied in a predetermined pattern.
  • a more preferable ejection method in which coating is performed using the ink according to the present invention is a piezoelectric element type.
  • This piezoelectric element type head is composed of a nozzle having a plurality of nozzles, a pressure generating element composed of a piezoelectric material and a conductive material disposed opposite to the nozzles, and a ink filling the periphery of the pressure generating element.
  • An on-demand ink jet coating head, and the pressure generating element is displaced by application [3] to discharge small ink droplets from the nozzle.
  • the ink jet coating device is not limited to the one in which the coating head and the ink container are separated, but may be one in which they are inseparably integrated.
  • the ink storage unit is integrated with the coating head so as to be separable or non-separable and is mounted on the carriage, but is provided at a fixed portion of the apparatus, and is provided via an ink supply member such as a tube. It may be in the form of supplying ink to the coating head.
  • the ink tank is provided with a configuration for applying a preferable negative pressure to the coating head
  • an absorber is disposed in the ink storage portion of the ink tank, or the operation ink is accommodated.
  • the coating apparatus may take the form of a line printer in which coating elements are aligned over a range corresponding to the entire width of the coating medium.
  • the ink jet ink of the present invention is applied onto the substrate by the ink jet, and then the solvent (C) is heated by heating in a hot plate or oven. By removing, that is, drying, a film of the alkenyl-substituted nadiimide compound (A) can be formed.
  • the inkjet ink further contains a high molecular compound (B): ⁇ can form a composite film of an alkenyl-substituted nadiimide compound (A) and a polymer compound (B).
  • the heating conditions vary depending on the type and mixing ratio of each component, but the temperature at which the alkenino-converted nadiimide compound (A) does not harden is preferable, usually at 70 to 120 ° C using an oven. A film is formed in 5 to 15 minutes in the case of 1 to 5 minutes in the case of using a hot plate.
  • a polyimide film can be obtained by heat treatment at 0 to 3500 ° C, more preferably 2300 to 300 ° C (using an oven for 30 to 90 minutes, hot plate ⁇ Is between 5 and 30 minutes).
  • the polymer compound (B) is polyamide or polyamic acid esteno! ⁇ : Tj ⁇ undergoes imidization reaction by calo-heat treatment at the same time.
  • the film is formed in a pattern, a patterned polyimide film is formed.
  • the polyimide film includes a patterned polyimide film.
  • the polyimide film thus obtained is an insulating film excellent in heat resistance and electrical insulation.
  • the ink-jet ink as a raw material containing an epoxy resin is preferable because it is a relatively tough insulating film excellent in chemical resistance, flatness, adhesion, and sputtering resistance. 8 Film substrate
  • the film substrate of the present invention may be formed on the entire surface or a predetermined pattern (line shape, etc.) of the ink jet ink of the present invention by a inkjet coating method on a polyimide film or the like on which a winding line is formed by a method such as ink jet. After that, the substrate is dried and further heated to form a polyimide film.
  • the ink jet ink of the present invention is applied to a film substrate such as a polyimide film on which wiring has been formed in advance by an ink jet coating method, and then the finolem substrate is dried and further heated, thereby providing an insulating property.
  • a film substrate such as a polyimide film on which wiring has been formed in advance by an ink jet coating method
  • the finolem substrate is dried and further heated, thereby providing an insulating property.
  • AN IM N—Methyl-arylbicyclo [2. 2. 1] Hepto-5-en-2,3-didecanolimide bisalkenyl-substituted nadiimide (a 2)
  • BAN IM Bis ⁇ 4 -1 (Aralbicyclo [2. 2. 1] Hepto-5-ene-2,3-dicarboximide) Phenyl ⁇ Methane Trisalkenyl-substituted nadimide ( a 3)
  • TrisANITAEA Tris ⁇ 4 -1 (Alinolebicyclo [2. 2. 1] Hept. 1-5-Chenololepoxyimide) Trietyl ⁇ Amine
  • TrisANITrisAM Tris ⁇ 4 -1 (Aralbicyclo [2.2.1] heptoe-5-en-2,3-dicarboximid) Triphenyl ⁇ Methane
  • TrisANIPARARO Tris ⁇ 4 I (Arilbicyclo [2. 2. 1] heptoe-5-ene-2,3-dicarboximide) phenyl ⁇ hydroxymethane tetrakisalkenyl-substituted nadiimide (a 4)
  • TetrakisANITAM Tetrakis ⁇ 4 I (Aralbicyclo [2. 2. 1] Heptoe 5_en-2,3-dicarboximide) Tetraphenyl ⁇ Methane Compound with two or more anhydride groups (b 1)
  • HFBAP P 4, 4, 1 [[2, 2, 2-trifluoro-1-ethyl (trifluoromethyl) ethylidene] bis-1,1-phenyleneoxy] bisbenzeneamine
  • HMD A Hexamethylenediamine
  • BAPEE Bis [2- (3-aminopropoxy) ethyl ether]
  • FM3311 In the above formula (XV), R 3 and R 4 are both methyl, and R 5 is methyl. A compound with an average molecular weight of 1,000 (trade name “FM3311” (manufactured by Chisso Corporation)) Monoamine (b 3)
  • TAEA Triaminoethinoreamine
  • Tris AM Triaminophenol methane
  • TAM Tetraaminophenol methane solvent (C)
  • EDM Diethyleneglycolenomethinereethinoreetenore
  • GBL ⁇ —petit mouth rata ton
  • a 200 m 1 three-necked flask equipped with a stirrer and a raw material charging inlet is charged with raw materials as shown below, stirred until the solids are completely dissolved, and 40 weight of yellow transparent BAN IM 0/0 to obtain a solution.
  • the viscosity of this night was 15.2 mPa ⁇ s (25 ° C) and the surface tension (25 ° C) was 33 mNZm.
  • This solution was used as it was as an inkjet ink (1).
  • the viscosity of the solution was measured with an E-type viscometer (VI SCON IC ELD manufactured by TOKYO KE IKI).
  • the surface tension was measured with an automatic dynamic surface tension meter (Kyowa Interfacial Chemical Society B P-D4).
  • Example 1 To use V, was three-necked flask in Example 1 was charged with raw materials shown below, stirring until the solids completely dissolved, to obtain a 50 weight 0/0 ' ⁇ of B AN IM.
  • the viscosity at this time was 42.7 mPa ⁇ s (25 ° C), 15.4 mPa ⁇ s (50 ° C), and the surface tension (25 ° C) was 34 mN / m.
  • Example 1 the three-necked flask was charged with the raw materials as shown below, and stirred until the solid content was completely dissolved to obtain 60% by weight of AN IM / B AN IM. .
  • the viscosity at night was 108 mPa ⁇ s (25 ° C), 18.4 mPa ⁇ s (60 ° C), and the surface tension (25 ° C) was 33 mNZm.
  • a 500 ml four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet was charged with the raw materials as shown below and stirred for 5 hours at 40 ° C in a dry nitrogen stream. to obtain a 30 weight 0/0? Gakuyoru transparent polyamic acid (B).
  • the viscosity of this intense night was 15.5 mPa ⁇ s.
  • the weight average molecular weight measured by GPC was 2,100.
  • the weight average molecular weight of the polyamic acid is obtained by diluting the obtained polyamic acid with tetrahydrofuran (THF) so that the polyamic acid concentration is about 1% by weight.
  • THF tetrahydrofuran
  • GPC apparatus JASCO GULLIVER 1500 (Intelligent) Using a differential refractometer RI-1530), the above dilution was used as a developing agent, measured by the GPC method, and obtained by polystyrene analysis.
  • the column is Tosoh Co., Ltd. Nekara Column G4000HXL, G3000HXL, G250 OH Four XL and G200 OHXL were used in this order, and the measurement was performed under the conditions of column 40 ° C and flow rate 1.0 m 1 / min.
  • Example 1 Using the ink jet ink (1) prepared in Example 1 as the ink jet ink, both sides of a 1.5 mm thick glass epoxy resin with a FUJ IFI LM D ima tix nematic ink jet applicator DMP -2831 A line of 5 cm in length was applied on the same plate with a dot width of 20 dots and a dot pitch of 20 microns.
  • the ink jet head heater setting was 30 ° C
  • the piezoelectric was 16 V
  • the drive frequency was 5 kHz. 80.
  • the obtained polyimide film was observed for the line width and the uniformity of the line width with an optical microscope, and was measured.
  • the film thickness was KL A—Ten cor J apan Co., Ltd .: fc metallurgy step 200 was used, and the average value of three measured values was B ff.
  • the results are shown in Table 1.
  • the line had a sufficient thickness.
  • a polyimide insulating film was obtained under the same conditions as in Example 5 except that the ink jet ink (2) prepared in Example 2 was used as an inkjet ink and the head heater was set at 50 ° C.
  • the word Wffi was performed under the same conditions as in Example 5. The results are shown in Table 1. The line had a sufficient thickness.
  • a polyimide insulating film was obtained under the same conditions as in Example 5 except that the ink-jet ink (3) prepared in Example 3 was used as an ink-jet ink and the head heater was set at 60 ° C.
  • the obtained polyimide film was surfaced under the same conditions as in Example 5. The results are shown in Table 1. The line had a sufficient thickness.
  • An polyimide insulating film was obtained under the same conditions as in Example 5 except that the ink jet ink (4) prepared in Example 4 was used as the ink jet ink and the head heater was set at 60 ° C.
  • the obtained polyimide film was surfaced under the same conditions as in Example 5. The results are shown in Table 1.
  • the line had a sufficient thickness.
  • the term overnight is used: ⁇ refers to a time of about 12-18 hours, and when "room temperature” is used, it refers to a temperature of about 20-25 ° C.
  • a 20 Oml eggplant-shaped flask with a stirring bar and glass stopper is prepared on a stirrer.
  • the raw materials are charged as shown below.
  • the solvent is used at room temperature (vacuum gauge pressure 0.1 Pa).
  • the amic acid was transferred to a petri dish, placed in an oven heated to 180 ° C. for 30 minutes, and cyclized to obtain 4.1 g of solid imidized product BANIHFBAPP. Identification of imidized substance was confirmed by infrared absorption scan Bae spectrum (stretching vibration of an imide ring Cal Boniru group 1710 cm- 1778 cm- 1) using FT-IR.
  • a 30 Oml eggplant-shaped flask with a stir bar was prepared on a stirrer, and the heating temperature of the oven was 160.
  • a viscous liquid imidized product BA NIH 5.97 g was obtained through the same method as in Synthesis Example 1 except that it was C.
  • the identity of the imidized product was confirmed by using FT-IR with an infrared absorption spectrum (stretching vibration of the imido ring carbocycle group 1690 cm-1766 cm-).
  • a 30 Om 1 eggplant-shaped flask containing a stir bar was prepared on a stirrer, and a viscous liquid imidized product BANIBAPB 28.0 g was obtained through the same method as in Synthesis Example 1. Identification of imidized compounds was confirmed by using FT-IR with an infrared absorption spectrum (stretching vibration of imido ring carbonyl group 1690 cm ' ⁇ 1766 cm 1 ).
  • a 30 Oml eggplant-shaped flask containing a stir bar was prepared on a stirrer, and a viscous liquid imidized product BANIBAPEE 28.1 g was obtained through the same method as in Synthesis Example 1.
  • the identity of the imidized product was confirmed by FT-IR using an infrared absorption spectrum (stretching vibration of imido ring carbonyl group, 1692 cm 1 , 1766 cm “ 1 ).
  • a 30 Oml eggplant-shaped flask containing a stirring bar was prepared on a stirrer, and a solid imidated product BANIDDET 8.26 g was obtained through the same method as in Synthesis Example 1.
  • the identity of the imidized product was confirmed by FT-IR using an infrared absorption spectrum (stretching vibration of imido ring carbocycle group: 1702 cm-1 770 cm 1 ).
  • a bottle was prepared in the same manner as in Example 9, and the raw materials were charged as shown below, and the mixture was stirred until the BAN I M solid content was completely dissolved. Thus, 40% by weight of BAN IM was obtained. this? The viscosity at night was 15.2 mPa ⁇ s (25 ° C).
  • Example 9 Similarly prepared bottle as in Example 9 was charged with raw materials shown below, stirring until BANIM solids completely dissolved, to obtain a 60 weight 0/0? Night yellow transparent BAN IM. The viscosity of this night was 189.6 mPa-s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9, and the raw materials were charged as shown below.
  • the BANIDDET solid content was stirred, but dropped to room temperature and did not dissolve.
  • a bottle was prepared in the same manner as in Example 9, and the raw materials were charged as shown below, followed by stirring until the BANIDDP solid content was completely dissolved, and a brown transparent BANIDDP 30% by weight solution was obtained.
  • the viscosity of this night was 7.2 mPa-s (25 ° C).
  • a lab ran pack screw one-tube bottle A bottle was prepared in the same manner as in Example 9 except that 13.5 cc was used. Charged raw materials shown below, stirring until BANIHFBAPP solids completely dissolved, to obtain a 30 weight 0/0 ⁇ yellow transparent BANIHFBAPP. The viscosity at night was ⁇ .5 mPa ⁇ s (25 ° C).
  • a lab ran pack screw one-tube bottle A bottle was prepared in the same manner as in Example 9 except that 13.5 cc was used. Charged raw materials as shown below, and ⁇ to BANIIPD solids completely dissolved, to obtain a 40 weight 0/0 solution of yellow transparent BANIIPD. The viscosity of this solution was 14.6 mPa ⁇ s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9, except that a Labo Lampak Star Tube 20 cc was used. The raw materials were charged as shown below and stirred until the BANIAPDS solids were completely mixed to obtain a 55 wt% solution of brown transparent BANIAPDS. The viscosity of this solution was 14.6 mPa ⁇ s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9. Charged raw materials shown below, stirring until BANIAPDS solids are mixed thoroughly to obtain a 70 weight 0/0 Takigiyoru brown transparent BANIAPDS. this? The sickle viscosity was 16.5 mPa ⁇ s (70 ° C).
  • a bottle was prepared in the same manner as in Example 9 except that 20 cc of Labo Lampak Scry tube was used. Charged raw materials shown below, stirring until BANIFM3311 solids are mixed thoroughly to obtain a 60 weight 0/0 night brown transparent BANIFM3311. This night viscosity was 14.7 m Pa ⁇ s (25 ° C).
  • Example 9 Use the same bottle as in Example 9, except that 20 cc Lablab Pack screw one bottle was used. I intended. Charged raw materials shown below, stirring until BANIH solids are mixed thoroughly to obtain a 50 weight 0/0 solution of a brown clear BANIH. This midnight viscosity was 14.3 mPa-s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9 except that 20 cc of Laborampak Stallyu tube was used. Charged raw materials shown below, stirring until BANI12DA solids are mixed thoroughly to obtain a 50 weight 0/0 Takigiyoru brown transparent BANI12DA. The viscosity of this solution was 15.8 mPa ⁇ s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9. Charged raw materials shown below, stirring until BANIBAEE solids are mixed thoroughly to obtain a 50 weight 0/0 night brown transparent BANIBAEE. The viscosity of this midnight was 17.3 mPa ⁇ s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9. Charged raw materials shown below, stirring until BANIBAPB solids are mixed thoroughly to obtain a 50 weight 0/0? Takigiyoru brown transparent BANIBAPB. The viscosity of this sickle was 18.4 mP a-s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9. The raw materials were charged as shown below, and stirred until ⁇ solids were completely mixed to obtain a brown transparent BA IBAPEE 50 wt% solution. The viscosity of this gel was 17.7 mPa ⁇ s (25 ° C).
  • a bottle was prepared in the same manner as in Example 9. The raw materials were charged as shown below, and stirred until the solid content of TrisANITAEA was completely mixed to obtain a brown transparent 50% by weight solution of TrisANITAEA. The viscosity of this solution was 16. ImPa ⁇ s (25 ° C).
  • TrisANITAEA 4. 40 g
  • a bottle was prepared in the same manner as in Example 9 except that a laboratory tube pack screw tube 20 cc was used. The raw materials were charged as shown below and stirred until the solid content of TrisANITrisAM was completely dissolved to obtain a 30% by weight solution of TrisANITrisAM that was transparent in reddish brown. The viscosity of this solution was 8.9 mPa ⁇ s (25 ° C).
  • TrisANITrisAM 60 g
  • a bottle was prepared in the same manner as in Example 9 except that 20 cc of Laborampak Stallyu tube was used. Prepare the raw materials as shown below until the TrisANIPARARO solids are completely dissolved. And Misao ⁇ to obtain a 30 weight 0/0 solution of red purple transparent TrisANIPARARO. This viscosity was 13.8 mPa ⁇ s (25 ° C).
  • TrisANIPARARO 60 g
  • a bottle was prepared in the same manner as in the implementation of J9, except that 20 cc of the Lab Lampac Skull tube was used. Charged raw materials shown below, stirring until TetrakisANITAM solids completely dissolved, to obtain a 30 weight 0/0 Nada brown transparent TetrakisANIT eyebrows. This severe viscosity was 13.8 mPa ⁇ s (25 ° C).
  • TetrakisANITAM 3. 60 g
  • Example 2 The raw materials were charged into the three-necked flask used in Example 1 as shown below, stirred for 10 hours at 40 ° C under a dry air flow, then heated to 70 ° C and stirred for 8 hours. As a result, 8 weight 0 / night of yellow transparent polyamic acid was obtained. The night viscosity was 9. ImP a -s (25 ° C.) and the surface tension (25 ° C.) was 43 mN / m. In this synthesis example, NMP was used because the reaction product precipitated when EDM was used as the solvent. The weight average molecular weight measured by GPC was 25,000. This solution was directly used as inkjet ink (5).
  • a polyimide film was obtained under the same conditions as in Example 5 except that the inkjet ink (5) prepared in Comparative Example 1 was used as the inkjet ink.
  • the obtained polyimide film was whisked under the same conditions as in Example 5. The results are shown in Table 1. Shown in The line width was significantly larger than the width when applied, the line edge was not sufficiently linear, and the line was not thick enough. Table 1
  • Example 10 Of the ink jet inks obtained in Examples 9 to 27, Examples 10 0, 11 1, 12 and 17 were removed, and the heat-resistant I 1 life test of the ink was performed.
  • Ink jet ink 1 ml was dropped onto a glass substrate, and spin coating was performed. The substrate was dried on a hot plate at 80 ° C. for 5 minutes and then heated at 230 ° C. for 30 minutes to obtain a polyimide insulating film. Further 2 5 0. Heated in an oven heated to C for 30 minutes. 8 0. After drying C, heating at 230 ° C., heating at 250 ° C., and then measuring the film thickness, the reduction rate was calculated. At the same time, the presence or absence of film flow (reblowing) during heating was also examined. The results are shown in Table 2. Table 2
  • Example 9 The storage stability test of the ink jet inks obtained in Example 9 and Example 10 was performed.
  • the ink was placed in a sample bottle, and the viscosity on the day of preparation and the viscosity after storage at room temperature for 140 days were measured. The results are shown in Table 3.
  • Example 10 The ink jet ink (7) prepared in Example 10 was used as an inkjet ink.
  • the heater setting of the inkjet head was set to 30 ° C.
  • the piezoelectric value was 30 V
  • the driving frequency was 5 kHz.
  • the substrate was dried for 5 minutes on a hot plate at 80 ° C and then heated in an oven at 230 ° C for 30 minutes to obtain a polyimide insulating film formed in a line.
  • the resulting polyimide film was observed for line width and line width uniformity with an optical microscope, and Biff was measured.
  • the film thickness was measured by using a tl ⁇ Iff meter ⁇ -step 200 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of the measured values at three locations was taken as the film thickness. The results are shown in Table 4.
  • the line had a sufficient thickness.
  • Ink-jet ink prepared in Example 16 (13) was used as the ink-jet ink, except that the piezoelectric voltage was 16 V and the head heater setting was 70. Got.
  • the obtained polyimide film was stated under the same conditions as in Example 30. The results are shown in Table 4. The line had a sufficient thickness.
  • a polyimide insulating film was obtained under the same conditions as in Example 30 except that the ink for ink jet (16) prepared in Example 19 was used as the ink jet ink, and the piezoelectric layer was set to 18 V.
  • the obtained polyimide film was coated under the same conditions as in Example 30. The results are shown in Table 4. The line had a sufficient thickness. Table 4
  • Examples of the utilization method of the present invention include an insulating film for a flexible film spring substrate and an electronic component using the same.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une encre pour impression jet d'encre capable de former un film relativement épais par un seul jet. L'encre pour impression jet d'encre selon l'invention contient au moins un composé nadimide à substitution alcényle. L'invention concerne également une telle encre pour impression jet d'encre contenant un composé polymère et une telle encre pour impression jet d'encre contenant également un solvant.
PCT/JP2007/072488 2006-11-16 2007-11-14 Encre pour impression jet d'encre WO2008059986A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123190A1 (fr) * 2007-03-29 2008-10-16 Chisso Corporation Encre pour jet d'encre
JP2009029777A (ja) * 2007-06-27 2009-02-12 Chisso Corp アリル置換ナジイミド化合物、液晶配向剤、液晶配向膜および液晶表示素子
JP2009203440A (ja) * 2008-02-29 2009-09-10 Chisso Corp インクジェット用インク
JP2010053323A (ja) * 2008-08-29 2010-03-11 Chisso Corp 熱硬化性組成物、該組成物の製造方法および該組成物の用途
JP2010106212A (ja) * 2008-10-31 2010-05-13 Chisso Corp アルケニル置換ナジイミド、溶媒および硬化剤を含む組成物および該組成部の用途
JP2010189631A (ja) * 2009-01-20 2010-09-02 Chisso Corp インクジェット用インク
EP2568019A1 (fr) 2011-09-07 2013-03-13 JNC Corporation Encre pour jet d'encre
EP2657307A2 (fr) 2012-04-25 2013-10-30 JNC Corporation Encre à jet dýencre
CN114057608A (zh) * 2021-11-16 2022-02-18 北京理工大学 一种纯化三异氰酸酯的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006075654A1 (fr) * 2005-01-12 2006-07-20 Taiyo Ink Mfg. Co., Ltd. Composition de resine durcissable conçue pour l'impression au jet d'encre, objet obtenu par durcissement de cette composition, et carte de circuits imprimes produite au moyen de ladite composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006075654A1 (fr) * 2005-01-12 2006-07-20 Taiyo Ink Mfg. Co., Ltd. Composition de resine durcissable conçue pour l'impression au jet d'encre, objet obtenu par durcissement de cette composition, et carte de circuits imprimes produite au moyen de ladite composition

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123190A1 (fr) * 2007-03-29 2008-10-16 Chisso Corporation Encre pour jet d'encre
JP5604869B2 (ja) * 2007-03-29 2014-10-15 Ｊｎｃ株式会社 インクジェット用インク
JP2009029777A (ja) * 2007-06-27 2009-02-12 Chisso Corp アリル置換ナジイミド化合物、液晶配向剤、液晶配向膜および液晶表示素子
JP2009203440A (ja) * 2008-02-29 2009-09-10 Chisso Corp インクジェット用インク
JP2010053323A (ja) * 2008-08-29 2010-03-11 Chisso Corp 熱硬化性組成物、該組成物の製造方法および該組成物の用途
JP2010106212A (ja) * 2008-10-31 2010-05-13 Chisso Corp アルケニル置換ナジイミド、溶媒および硬化剤を含む組成物および該組成部の用途
JP2010189631A (ja) * 2009-01-20 2010-09-02 Chisso Corp インクジェット用インク
EP2568019A1 (fr) 2011-09-07 2013-03-13 JNC Corporation Encre pour jet d'encre
EP2657307A2 (fr) 2012-04-25 2013-10-30 JNC Corporation Encre à jet dýencre
CN114057608A (zh) * 2021-11-16 2022-02-18 北京理工大学 一种纯化三异氰酸酯的方法

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