WO2018159675A1 - Composition de résine thermodurcissable, film durci, substrat présentant un film durci, composant électronique, et composition d'encre pour jet d'encre - Google Patents

Composition de résine thermodurcissable, film durci, substrat présentant un film durci, composant électronique, et composition d'encre pour jet d'encre Download PDF

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Publication number
WO2018159675A1
WO2018159675A1 PCT/JP2018/007499 JP2018007499W WO2018159675A1 WO 2018159675 A1 WO2018159675 A1 WO 2018159675A1 JP 2018007499 W JP2018007499 W JP 2018007499W WO 2018159675 A1 WO2018159675 A1 WO 2018159675A1
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meth
acrylate
thermosetting resin
cured film
resin composition
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PCT/JP2018/007499
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English (en)
Japanese (ja)
Inventor
信太 諸越
智嗣 古田
敏行 高橋
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Jnc株式会社
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Priority to JP2019503061A priority Critical patent/JPWO2018159675A1/ja
Publication of WO2018159675A1 publication Critical patent/WO2018159675A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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

Definitions

  • the present invention relates to a thermosetting resin composition, a cured film obtained from the thermosetting resin composition, a substrate with a cured film having the cured film, an electronic component having the cured film or the substrate with the cured film, and an inkjet ink. Relates to the composition.
  • a protective layer called a cover lay or solder resist is coated on the circuit pattern in order to protect the circuit pattern formed on the substrate.
  • the specific role of the protective layer is to protect the electronic circuit from heat and moisture, to prevent oxidation and corrosion of copper forming the circuit, to insulate and protect the circuit in order to prevent short circuit, in the soldering process It is to protect the solder from being attached to unnecessary parts.
  • the protective layer is required to have characteristics such as heat resistance, moisture resistance, insulation, adhesion to a substrate and a circuit, flux resistance, solder resistance, and solvent resistance. .
  • a wafer level packaging (WLP) technique has attracted attention as a technique for realizing a high-density semiconductor package and a reduction in size and thickness, and its adoption is accelerating.
  • WLP wafer level packaging
  • solder balls are often used as interconnections from the die to the printed circuit board, and it is necessary to accurately arrange solder balls having a diameter of 100 to 300 ⁇ m at a pitch of 500 ⁇ m or less. Therefore, in addition to the above-described characteristics, a protective layer called a solder resist is also required to have a fine pattern shape, pattern position accuracy, heat resistance and insulation properties in a thin film, and the like.
  • Patent Document 1 describes a resist ink for screen printing mainly composed of a filler and a hydrophobic vehicle. Even if the ink is repeatedly printed by screen printing, the ink viscosity hardly fluctuates and maintains good printability. Yes. However, in screen printing, it is difficult to accurately arrange hole shapes having a diameter of 100 to 300 ⁇ m at a pitch of 500 ⁇ m or less.
  • an inspection device for confirming the covering of the protective layer is used.
  • an optical device is used for the inspection apparatus.
  • In order to inspect the coating of the protective layer it is necessary to color the protective layer.
  • In order to perform an accurate inspection with an optical inspection device it is necessary to darken the color of the protective layer so that the underlying circuit such as copper does not penetrate, and when the film thickness becomes as thin as 20 ⁇ m or less, etc.
  • black is required.
  • Patent Document 2 discloses a composition containing an active energy ray-curable resin having a specific structure, a photopolymerization initiator, an organic solvent and the like as a photocurable developable liquid solder resist ink composition.
  • a liquid solder resist ink composition that can be patterned by a photolithographic process can form a fine pattern and increase the positional accuracy of the pattern. Inspection is difficult.
  • Patent Document 3 as a photocurable developable black solder resist composition, a carboxyl group-containing resin, a photopolymerization initiator, a diluent, a polyfunctional epoxy compound having a specific structure, a black colorant, and other than black Compositions containing colorants and the like have been proposed.
  • a black color since it has a black color, light absorption at the time of exposure increases, and it is particularly difficult for light to reach the deep part of the solder resist coating film. Therefore, the photocuring in the deep part of the solder resist coating film is not sufficient, and the size of the solder resist coating film deep part becomes too small after development, and the cured coating film is peeled off from the printed wiring board. There was a problem.
  • the ink viscosity is required to be low to some extent in order to stably eject ink from the ink jet head.
  • a fine pattern shape such as a solder resist for WLP
  • an ink jet head having a small nozzle size is used. Therefore, the ink viscosity at the time of ejection needs to be 10 mPa ⁇ s or less.
  • An ink jet apparatus capable of printing by heating the ink jet head has been developed, but printing trouble such as nozzle clogging is likely to occur due to ink drying in the vicinity of the nozzle due to heating.
  • the discharge performance of an ink-jet head with a small nozzle size is improved, but the film thickness after drying and curing decreases as the solvent ratio increases. There is.
  • Patent Document 4 contains a monomer having a (meth) acryloyl group and a thermosetting functional group in the molecule, a photoreactive diluent having a weight average molecular weight of 700 or less, and a photopolymerization initiator, and having a viscosity of 25 m and 150 mPa.
  • -S or less curable composition for inkjet is disclosed. Although the viscosity can be lowered to 20 mPa ⁇ s or less by heating the ink jet head to 50 degrees or more, there is a problem that the storage stability in an environment of 50 degrees or more is poor.
  • Patent Document 5 discloses that a storage stability is good even in an environment inside an ink jet apparatus heated to 50 ° C. or more, which contains a photocurable compound, a thermosetting compound, a photopolymerization initiator, and a thermosetting agent.
  • Inkjet curable compositions have been proposed.
  • the viscosity at 25 degrees is 160 mPa ⁇ s or more and even when heated to 50 degrees or more, it becomes 10 mPa ⁇ s or more, so there is a problem that printing stability is deteriorated in an inkjet head with a small nozzle size. It was.
  • Patent Document 6 proposes a thermosetting black inkjet ink containing an epoxy resin, an oxetane compound, a copolymer having a specific structure, carbon black, a solvent, and the like.
  • the flux resistance and solder resistance when used as a solder resist have not been studied.
  • Solder resist used in high-density, small and thin semiconductor packages utilizing WLP technology, etc. has heat resistance, moisture resistance, insulation, adhesion to substrates and circuits, flux resistance, solder In addition to properties such as resistance and solvent resistance, heat resistance and insulation properties in thin films are required. In addition, it is necessary to form a fine pattern shape with high positional accuracy, and in order to inspect the pattern shape and the position of the pattern, there is a demand for dark black that can shield the underlying circuit even with a thin film of 20 ⁇ m or less. A resin composition that can achieve both the above characteristics and dark black has not yet been realized.
  • thermosetting resin composition Conventionally, the process of applying a thermosetting resin composition on a substrate to form a coating film and the process of thermosetting the coating film to form a cured film have been carried out as a series of processes. If the substrate with the pattern shape formed by the coating film of the thermosetting resin composition can be stacked and stored in the middle of the series of steps, workability at the time of manufacture is improved. In order to enable storage of the substrate, it is effective to temporarily cure the coating film of the thermosetting resin composition, but a thermosetting resin composition that can be temporarily cured has not been studied yet.
  • thermosetting resin composition that can form a cured product having excellent adhesion to a substrate, flux resistance, solder resistance, and solvent resistance and can be temporarily cured. Yes.
  • thermosetting resin composition By using (meth) acrylate (G) having three or more functional groups, the inventors can temporarily cure the thermosetting resin composition with light, as well as adhesion to the substrate, flux resistance, solder resistance, and solvent resistance. It discovered that the cured
  • the present invention relates to the following [1] to [14].
  • the trifunctional or higher (meth) acrylate (G) is trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, Epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta
  • thermosetting resin composition according to [1] or [2], wherein the colorant (E) contains titanium compound particles and / or carbon black particles.
  • the copolymer (C) having oxiranyl or oxetanyl is a copolymer (C1) of a radical polymerizable monomer (c1) having an oxiranyl group and another radical polymerizable monomer (c3), and / or
  • Composition Composition.
  • the radical polymerizable monomer (c1) having an oxiranyl group is selected from the group consisting of glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • the thermosetting resin composition according to any one of [1] to [4], which is one or more.
  • the radical polymerizable monomer (c2) having an oxetanyl group is 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) From the group consisting of 2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane
  • the thermosetting resin composition according to any one of [1] to [4], which is one or more selected.
  • thermosetting resin composition according to any one of [1] to [6], wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 30,000.
  • thermosetting according to any one of [1] to [7], wherein the polyester amic acid (A) is a compound having a structural unit represented by formulas (1) and (2). Resin composition. (Wherein R 1 is independently a tetravalent organic group having 1 to 30 carbon atoms, R 2 is independently a divalent organic group having 1 to 40 carbon atoms, and R 3 is independently 1 carbon atom) A divalent organic group of ⁇ 20.)
  • thermosetting resin composition according to any one of [1] to [8], further including an epoxy curing agent (F).
  • thermosetting resin composition obtained from the thermosetting resin composition according to any one of [1] to [10].
  • thermosetting resin composition comprising the thermosetting resin composition according to any one of [1] to [10].
  • thermosetting resin composition of the present invention can be temporarily cured using light such as ultraviolet rays by using (meth) acrylate (G) having three or more functional groups, and has good adhesion to the substrate.
  • a cured film having good flux resistance, solder resistance, and solvent resistance can be formed.
  • thermosetting composition according to an embodiment of the present invention (hereinafter also referred to as “composition” as appropriate) will be described in detail.
  • the composition according to one embodiment of the present invention has a polyester amic acid (A), an epoxy compound (B) having a weight average molecular weight of less than 10,000, a weight average molecular weight having oxiranyl or oxetanyl of 10,000 or more. It contains a copolymer (C), a solvent (D), a colorant (E), a (meth) acrylate (G) having three or more functional groups, and a photopolymerization initiator (H).
  • the composition which concerns on one Embodiment of this invention may contain an additive other than the said component.
  • polyester amide acid (A) used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond, and a carboxyl group, and specifically represented by the formulas (1) and (2). It is more preferable that the compound has a structural unit.
  • Polyester amide acid (A) may use only 1 type and may use 2 or more types.
  • R 1 is independently a tetravalent organic group having 1 to 30 carbon atoms
  • R 2 is independently a divalent organic group having 1 to 40 carbon atoms
  • R 3 is independently having 1 to 20 carbon atoms. It is a divalent organic group.
  • R 1 is preferably independently a tetravalent organic group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms.
  • the tetravalent organic group is more preferably a group represented by the formula (5).
  • R 4 represents —O—, —CO—, —SO 2 —, —C (CF 3 ) 2 —, —R 5 — or —COO—R 5 —OCO— (R 5 represents Independently, it is an alkylene having 1 to 4 carbon atoms.)
  • R 2 is a divalent compound having 2 to 35 carbon atoms in that a compound having good compatibility with other components in the composition is obtained and a cured film having good adhesion to glass or ITO is obtained.
  • the organic group is preferably a divalent organic group having 2 to 30 carbon atoms, and more preferably a group represented by the formula (6).
  • R 6 represents —O—, —CO—, —SO 2 —, —C (CF 3 ) 2 —, —R 7 — or —O—ph—R 8 —ph—O—).
  • a ph is a benzene ring
  • R 8 is, -O -, - CO -, - SO 2 -, - C (CF 3) 2 - or -R 7 -.
  • R 7 is Independently, it is an alkylene having 1 to 4 carbon atoms.
  • R 3 is preferably a divalent organic group having 2 to 15 carbon atoms, a group represented by the formula (7), —R 10 —NR 11 —R 12 — (R 10 and R 12 are independently , Alkylene having 1 to 8 carbon atoms, and R 11 is hydrogen or alkyl having 1 to 8 carbon atoms in which at least one hydrogen may be substituted with hydroxyl)), alkylene having 2 to 15 carbon atoms, Alternatively, at least one hydrogen of alkylene having 2 to 15 carbon atoms may be substituted with hydroxyl, and may be a group optionally having —O—, and is a divalent group having 2 to 6 carbon atoms. More preferably, it is alkylene.
  • R 9 is —O—, —CO—, —SO 2 —, —C (CF 3 ) 2 —, —R 7 — or —ph—R 8 —ph— (ph a benzene ring, R 8 is, -O is -, - CO -, - SO 2 -, - C (CF 3) 2 - or -R 7 -.. a is)
  • R 7 is independently carbon (Alkylene having a number of 1 to 4.)
  • the polyester amic acid (A) is a compound obtained by reacting a component containing a tetracarboxylic dianhydride (a1), a component containing a diamine (a2) and a component containing a polyvalent hydroxy compound (a3).
  • a component containing tetracarboxylic dianhydride (a1), a component containing diamine (a2), a component containing polyvalent hydroxy compound (a3) and a component containing monohydric alcohol (a4) It is also preferable that it is a compound obtained.
  • R 1 is independently a tetracarboxylic dianhydride residue
  • R 2 is a diamine residue
  • R 3 is a polyvalent hydroxy compound residue.
  • a reaction solvent (a5), an acid anhydride (a6) or the like may be used.
  • the component containing the tetracarboxylic dianhydride (a1) may contain other compounds having three or more acid anhydride groups other than this compound.
  • These (a1) to (a6) etc. may be used alone or in combination of two or more.
  • the polyester amide acid (A) When the polyester amide acid (A) has an acid anhydride group at the molecular end, it is preferably a compound obtained by reacting a monohydric alcohol (a4) if necessary.
  • the polyester amide acid (A) obtained using the monohydric alcohol (a4) becomes a compound having excellent compatibility with the epoxy compound (B) and the epoxy curing agent (C) having a weight average molecular weight of less than 10,000. There exists a tendency and it exists in the tendency for the composition which is excellent in applicability
  • Tetracarboxylic dianhydride (a1) The tetracarboxylic dianhydride (a1) is not particularly limited, but specific examples include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetra Carboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2 , 2 ′, 3,3′-diphenyl ether tetracarboxy
  • 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′ is used because a compound having good adhesion to a glass substrate can be obtained by using in combination with an epoxy compound.
  • 4,4'-Diphenyl ether tetracarboxylic dianhydride 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (Trade name: TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.) is preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetra Carboxylic dianhydride is particularly preferred.
  • the diamine (a2) is not particularly limited, and specific examples thereof include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-amino Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4 -Aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane is
  • 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are used in that a compound having good adhesion to a glass substrate can be obtained by using in combination with an epoxy compound.
  • 3,3′-diaminodiphenyl sulfone is particularly preferable.
  • Polyvalent hydroxy compound (a3) is not particularly limited as long as it is a compound having two or more hydroxy groups. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol having a molecular weight of 1,000 or less.
  • ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferable, and 1,4- Butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferable from the viewpoint of good solubility in the reaction solvent (a5).
  • the monohydric alcohol (a4) is not particularly limited as long as it is a compound having one hydroxy group. Specific examples include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol.
  • isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyl oxetane are preferable.
  • reaction solvent (a5) is not particularly limited, but specific examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether. Examples include acetate, dipropylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.
  • propylene glycol monomethyl ether acetate diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, methyl 3-methoxypropionate and N-methyl-2-pyrrolidone are preferable from the viewpoint of solubility.
  • reaction solvent (a5) examples include these solvents, but if these solvents are in a proportion of 30% by weight or less with respect to the total amount of the solvent used in the reaction, other than the solvent A mixed solvent obtained by mixing other solvents can also be used.
  • Acid anhydride (a6) The acid anhydride is not particularly limited, and specific examples thereof include carboxylic acid anhydrides such as 3- (triethoxysilyl) propyl succinic acid anhydride and maleic acid anhydride. Moreover, polyhydric anhydrides, such as a copolymer containing a carboxylic acid anhydride, can also be used. Examples of commercially available polyhydric anhydrides include SMA (trade name, manufactured by Kawa Crude Co., Ltd.), which is a styrene-maleic anhydride copolymer.
  • SMA trade name, manufactured by Kawa Crude Co., Ltd.
  • the method for synthesizing the polyester amic acid (A) is not particularly limited, but the tetracarboxylic dianhydride (a1), the diamine (a2), the polyvalent hydroxy compound (a3), and, if necessary, the monohydric alcohol (a4).
  • a method of reacting as an essential component is preferred, and this reaction is more preferably carried out in the reaction solvent (a5).
  • the order of adding each component during this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3) may be simultaneously added to the reaction solvent (a5) to cause the reaction, or the diamine (a2) and the polyvalent hydroxy compound may be reacted. After (a3) is dissolved in the reaction solvent (a5), the reaction may be carried out by adding tetracarboxylic dianhydride (a1), or tetracarboxylic dianhydride (a1) and diamine ( After reacting a2) in advance, the polyhydroxy compound (a3) may be added to the reaction product for reaction, and either method can be used. The monohydric alcohol (a4) may be added at any point in the reaction.
  • a synthetic reaction may be performed by adding a compound having 3 or more acid anhydride groups in order to increase the weight average molecular weight of the obtained polyesteramic acid (A).
  • Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.
  • the polyester amide acid synthesized in this way contains the structural units represented by the above formulas (1) and (2), and the terminal is derived from tetracarboxylic dianhydride, diamine or polyvalent hydroxy compound as raw materials. It is an acid anhydride group, an amino group or a hydroxy group, or a group derived from a component other than these compounds (for example, a monohydric alcohol residue).
  • the relationship of Formula (3) is preferably 0.7 ⁇ Z / Y ⁇ 7.0, and more preferably 1.3 ⁇ Z / Y ⁇ 7.0.
  • the relationship of the formula (4) is preferably 0.3 ⁇ (Y + Z) /X ⁇ 1.2, and more preferably 0.4 ⁇ (Y + Z) /X ⁇ 1.0.
  • the amount of the monohydric alcohol (a4) used in the reaction is Z ′ mol
  • the amount used is not particularly limited, but is preferably 0.1 ⁇ Z ′ / X ⁇ 5.0, more preferably Is 0.2 ⁇ Z ′ / X ⁇ 4.0.
  • reaction solvent (a5) When the reaction solvent (a5) is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3), the reaction proceeds smoothly. Therefore, it is preferable.
  • the reaction is preferably performed at 40 to 200 ° C. for 0.2 to 20 hours.
  • polyester amide acid (A) The weight average molecular weight of the polyester amic acid (A) measured by gel permeation chromatography (GPC) is the solubility in the solvent (E), especially the epoxy compound (B) having a weight average molecular weight of less than 10,000
  • GPC gel permeation chromatography
  • it is preferably 2,000 to 30,000. More preferably, it is from 3,000 to 30,000.
  • this weight average molecular weight can be measured by the method described in the Examples below.
  • the viscosity of the polyester amide acid (A) is preferably 5 to 200 mPa ⁇ s at 25 ° C., more preferably from the viewpoint of handling the polyester amide acid (A) to be obtained and adjusting the weight average molecular weight to the above-mentioned preferable range. Is 10 to 150 mPa ⁇ s, more preferably 15 to 100 mPa ⁇ s.
  • the content of the polyester amic acid (A) is excellent in the adhesion to the metal and the solid content of the composition according to an embodiment of the present invention (the composition is obtained) from the viewpoint of obtaining a cured film excellent in chemical resistance.
  • the residue obtained by removing the solvent from the product) is preferably 1 to 60 parts by weight, more preferably 5 to 55 parts by weight, still more preferably 5 to 50 parts by weight, and particularly preferably 10 to 40 parts by weight per 100 parts by weight. Parts, very preferably 12 to 30 parts by weight.
  • Epoxy compound (B) having a weight average molecular weight of less than 10,000 (hereinafter also referred to as “epoxy compound (B)” as appropriate).
  • the epoxy compound (B) used in the present invention is a compound containing two or more oxirane rings or oxetane rings in the molecule, and a compound having two or more oxirane rings is preferably used.
  • the epoxy compound (B) may be used alone or in combination of two or more.
  • the epoxy compound (B) may be obtained by synthesis or may be a commercially available product.
  • Examples of the epoxy compound (B) include bisphenol A type epoxy compounds, glycidyl ester type epoxy compounds, and alicyclic epoxy compounds.
  • a composition containing a trade name “Araldite CY184”, a trade name “Celoxide 2021P”, a trade name “TECHMORE VG3101L”, a trade name “157S70”, a trade name “EHPE3150” includes an aqueous sodium hydroxide solution and hydrochloric acid, and It is preferable in that a cured film having good resistance to chemicals such as sulfuric acid can be obtained, and among them, the trade name “157S70” and the trade name “EHPE3150” are more preferable.
  • the content of the epoxy compound (B) is excellent in resistance to flux (resistance to flux and heat resistance when reflow baking is performed by applying flux), resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid.
  • the amount is preferably 10 to 50 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the solid content of the composition according to an embodiment of the present invention (residue obtained by removing the solvent). Is 15 to 50 parts by weight, more preferably 20 to 50 parts by weight, particularly preferably 20 to 45 parts by weight, and most preferably 25 to 45 parts by weight.
  • the content of the epoxy compound (B) is preferably 10 to 600 parts by weight, more preferably 20 to 500 parts by weight, still more preferably 30 to 400 parts by weight based on 100 parts by weight of the polyester amide acid (A). Parts by weight.
  • the epoxy equivalent of the epoxy compound (B) is preferably 100 to 280 from the viewpoint of improving the flux resistance of the cured product formed from the composition and the resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid, and 120 270 is more preferable, and 140 to 240 is more preferable.
  • Copolymer (C) having oxiranyl or oxetanyl and a number average molecular weight of 10,000 or more (hereinafter also referred to as “copolymer (C)” as appropriate)
  • the copolymer (C) used in the present invention is a polymer obtained by copolymerizing a monomer containing at least one oxirane ring or oxetane ring in the molecule and another monomer, and forms the composition of the present invention. If compatibility with a component is favorable, it will not specifically limit.
  • the copolymer (C) is obtained, for example, by radical copolymerization of a monomer having oxiranyl or oxetanyl and another monomer.
  • the production method is not particularly limited, the copolymer (C) can be produced by heating the above-mentioned radical polymerizable compounds in the presence of a radical initiator.
  • a radical initiator organic peroxides, azo compounds and the like can be used.
  • the reaction temperature for radical copolymerization is not particularly limited, but is usually in the range of 50 to 150 ° C.
  • the reaction time is not particularly limited, but is usually in the range of 1 to 48 hours.
  • the reaction can be performed under any pressure of increased pressure, reduced pressure, or atmospheric pressure.
  • the monomer having oxiranyl examples include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • glycidyl methacrylate is preferable because it can give a cured film having good resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid.
  • the monomer having oxetanyl examples include 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane.
  • monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, methyl (Meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 2, 6] decanyl (meth) acrylate, glycerol model (Meth) acrylate, 5-
  • methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, 2 in that a copolymer (C) having excellent compatibility with the polyester amic acid (A) can be obtained.
  • -Hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and styrene are preferred.
  • N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide are more preferable because they can provide a cured film having flux resistance and solder heat resistance.
  • the solvent used in the above radical copolymerization reaction is preferably a solvent in which the produced polymer is dissolved.
  • the solvent include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, methyl 2-hydroxyisobutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4- Dioxane, propylene glycol dimethyl Ether, propylene glycol monomethyl ether,
  • the copolymer (C) used in the present invention may be a copolymer polymer solution in which handling properties and the like are taken into consideration while leaving the solvent used in the polymerization as it is. It may be a copolymer having a shape.
  • the proportion of the copolymer of oxiranyl-containing monomer and other monomer is preferably 30% by mole or more of the oxiranyl-containing monomer because it is excellent in resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid. It is more preferable that the monomer having oxiranyl is 50 mol% or more.
  • the proportion of the monomer used as a raw material for the copolymer (C) is 30 mol% or more and 80 mol% or less of the monomer having oxiranyl, and N— It is preferable that phenylmaleimide is 10 mol% or more and 30 mol% or less, and butyl methacrylate is 5 mol% or more and 20 mol% or less.
  • a copolymer (C) having excellent compatibility with the polyester amide acid (A) is obtained by copolymerization using a monomer at this ratio, and chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid are obtained. This is preferable in that a well-balanced cured film having both resistance to flux and flux resistance can be obtained.
  • the molecular weight of the copolymer (C) is compatible with the jetting property of the composition and the compatibility with the polyester amic acid (A) and the solvent (D).
  • the weight average molecular weight is preferably 10,000 or more and 100,000 or less, and more preferably 20,000 or more and 80,000 or less.
  • discharging ink by the ink jet method is also called jetting, and the characteristic is also called discharging property or jetting property.
  • the content of the copolymer (C) relieves stress due to curing shrinkage, and provides excellent adhesion with the substrate, and also provides a well-balanced cured film with excellent flux resistance.
  • the solvent (D) used in the present invention is preferably a solvent capable of dissolving the polyester amide acid (A), the epoxy compound (B) and the copolymer (C). Moreover, even if it is a solvent which does not dissolve polyester amide acid (A), epoxy compound (B) and copolymer (C) alone, it can be used as solvent (D) by mixing with other solvents. It may become. Only 1 type may be used for a solvent (D) and 2 or more types may be used for it.
  • solvent (D) examples include ethyl lactate, ethanol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol.
  • the composition of the present invention is composed of ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether in terms of solubility in the polyester amic acid (A), the epoxy compound (B) and the copolymer (C).
  • the content of the solvent (D) is not limited. However, when the composition is supplied onto the substrate by an ink jet method, the jetting property of the composition is improved, so that the content in 100 parts by weight of the composition
  • the content is preferably 45 to 90 parts by weight, and more preferably 50 to 80 parts by weight. Further, from the same viewpoint, it is preferable to adjust the solvent (D) so that the content of the solvent having a boiling point of 200 ° C. or more in 100 parts by weight of all the solvents contained in the composition is 50 parts by weight or more. It is more preferable to adjust the solvent (D) so as to be at least part by weight.
  • Colorant (E) The colorant (E) is blended in the composition according to the embodiment of the present invention.
  • the colorant (E) include inorganic and organic dyes and pigments.
  • inorganic and organic dyes and pigments For example, for insulating films that protect metal wiring, it is required to have a light shielding property so that the wiring pattern can be concealed and the inspection equipment can recognize it. Resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid, and solder heat resistance are also required. Therefore, it is preferable to use an inorganic pigment having excellent performance.
  • a commercially available product may be used as the colorant (E).
  • Examples of the inorganic pigment used as the colorant (E) include particles of titanium carbide such as silicon carbide, alumina, magnesia, silica, zinc oxide, titanium oxide and titanium nitride, graphite, and carbon black. Only 1 type may be used for an inorganic pigment, and 2 or more types may be mixed and used for it.
  • Examples of the organic pigment used as the colorant (E) include C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 128, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red
  • Examples of the dye include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes.
  • Examples of azo dyes are “VALIFASTBLACK 3810”, “VALIFASTBLACK 3820”, “VALIFASTRED 3304”, “VALIFASTRED 3320”, “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industries, Ltd.), Spiro blue GNH (trade name). Name; Hodogaya Chemical Co., Ltd.). Only one type of dye may be used, or two or more types may be mixed and used.
  • the colorant (E) contained in the composition according to an embodiment of the present invention can obtain a light shielding property so that, for example, an insulating film for protecting a metal wiring can recognize a wiring pattern and an inspection apparatus.
  • the dye and pigment content is preferably 2 parts by weight or more, and more preferably 3 parts by weight or more with respect to 100 parts by weight of the resin solid content excluding the solvent, dye and pigment of the composition.
  • the dye and pigment content is a resin solid content excluding the solvent, dye and pigment of the composition because the jetting property of the composition is improved.
  • the amount is preferably 15 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight.
  • the jetting property of the composition is improved when the composition is supplied onto the substrate by the inkjet method.
  • the average particle size is preferably 500 nm or less, and more preferably 400 nm or less.
  • the average particle size used in the present specification means the 50% volume particle size of the pigment dispersion, and is measured by a particle size distribution measuring apparatus (for example, Nikkiso Microtrac UPA150) using a dynamic light scattering method / laser Doppler method. It is the value of the measured MV (volume average diameter).
  • Trifunctional or higher (meth) acrylate (G) The trifunctional or higher polyfunctional (meth) acrylate (G) is not particularly limited as long as it has 3 or more (meth) acryl groups in one molecule, and only one type may be used. It may be used. Further, a trifunctional or higher polyfunctional (meth) acrylate (G) may be mixed with a bifunctional or lower (meth) acrylate.
  • Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and epichlorohydrin modified tri Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipen Erythritol penta (meth)
  • trifunctional or higher polyfunctional (meth) acrylates G
  • trimethylolpropane triacrylate pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate
  • isocyanuric acid ethylene oxide modified diacrylate It is preferable to use isocyanuric acid ethylene oxide-modified triacrylate or a mixture thereof from the viewpoint of solder heat resistance and resistance to chemicals such as sodium hydroxide aqueous solution, hydrochloric acid, and sulfuric acid.
  • Urethane (meth) acrylate is more preferable from the viewpoint of providing a cured film having an excellent balance of flux resistance in addition to solder heat resistance, resistance to chemicals such as sodium hydroxide aqueous solution, hydrochloric acid, and sulfuric acid.
  • Trimethylolpropane triacrylate pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, or a mixture thereof includes A commercially available product such as can be used.
  • a specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name, Toagosei Co., Ltd.).
  • the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are “Aronix M-306 (65 to 70% by weight)”, “M-305 (55 to 63% by weight)”, “M-303 (30 to 30%) 60% by weight) ”,“ M-452 (25 to 40% by weight) ”, and“ M-450 (less than 10% by weight) ”(name of product or developed product, manufactured by Toagosei Co., Ltd.)
  • the rate is the value listed in the catalog of the content of pentaerythritol triacrylate in the mixture.
  • dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate include “Aronix M-403 (50-60 wt%)”, “M-400 (40-50 wt%)”, “M-402 ( 30-40 wt%), “M-404 (30-40 wt%)”, “M-406 (25-35 wt%)”, and “M-405 (10-20 wt%)”
  • the developed product name, manufactured by Toagosei Co., Ltd., and the content in parentheses is the catalog value of the content of dipentaerythritol pentaacrylate in the mixture).
  • a specific example of the isocyanuric acid ethylene oxide-modified diacrylate is “Aronix M-215” (trade name, manufactured by Toagosei Co., Ltd.).
  • Specific examples of the mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate are Aronix M-313 (30-40 wt%) and M-315 (3-13 wt%, hereinafter abbreviated as “M-315”) (The product name, manufactured by Toagosei Co., Ltd., the content in parentheses is the catalog value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture).
  • urethane acrylate compound examples include “purple light UV-1400B”, “UV-1700B”, “UV-6300B”, “UV-7550B”, “UV-7600B”, “UV-7605B”, “UV-7610B”. , “UV-7620EA”, “UV-7630B”, “UV-7640B”, “UV-7650B”, “UV-6630B”, “UV-7000B”, “UV-7510B”, “UV-7550B”, “ “UV-7461TE”, “UV-3000B”, “UV-3200B”, “UV-3210EA”, “UV-3300B”, “UV-3310EA”, “UV-3310B”, “UV-3500BA”, "UV- 3520TL “,” UV-3700B “,” UV-6100B “,” UV-6640B “,” UV-2000B “ ”,“ UV-2010B ”,“ UV-2250EA ”,“ UV-2750B ”(trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.),“ UL-503LN ”(trade name, manufactured by Kyoeisha
  • the trifunctional or higher polyfunctional (meth) acrylate (G) is 50 (meth) acrylate monomer total amount.
  • the exposure amount required to make tack-free by photocuring hereinafter also referred to as “tack-free exposure amount” as appropriate is preferable.
  • the content of the trifunctional or higher polyfunctional (meth) acrylate (G) is such that the content of the composition according to an embodiment of the present invention is reduced from the viewpoint of reducing the tack-free exposure amount due to photocuring (from the composition to the solvent).
  • the remaining amount excluding) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more with respect to 100 parts by weight.
  • trifunctional or higher polyfunctional (meth) acrylate (G) The content of is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, based on 100 parts by weight of the solid content of the composition according to an embodiment of the present invention (residue obtained by removing the solvent from the composition). More preferably, it is 30 parts by weight or less.
  • Photopolymerization initiator (H) The composition of the present invention contains a photopolymerization initiator (H).
  • a photoinitiator (H) will not be specifically limited if it is a compound which generate
  • photopolymerization initiator (H) examples include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2- Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (eg IR ACURE 907; trade name: BASF Japan K
  • the photopolymerization initiator (H) may be used alone or in combination of two or more.
  • the photopolymerization initiators ⁇ -aminoalkylphenone-based, acylphosphine oxide-based, and oxime ester-based photopolymerization initiators are preferable from the viewpoint of reducing the tack-free exposure amount due to photocuring.
  • photopolymerization initiators 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime) is a photopolymerization initiator.
  • the photopolymerization initiator may be composed only of 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime).
  • the content of the photopolymerization initiator (H) is preferably 10 parts by weight or more, more preferably 100 parts by weight with respect to 100 parts by weight of the total (meth) acrylate in the composition, from the viewpoint of reducing the tack-free exposure amount due to photocuring. 15 parts by weight or more, more preferably 20 parts by weight or more. Further, from the viewpoint of good flux resistance of the cured film obtained by the photocuring reaction, the content of the photopolymerization initiator (H) is preferably 60 weights with respect to 100 weight parts of all (meth) acrylates in the composition. Parts or less, more preferably 55 parts by weight or less, still more preferably 50 parts by weight or less.
  • the composition of the present invention comprises a polyester amic acid (A), an epoxy compound (B), a copolymer (C), a solvent (D), a colorant (E), a trifunctional, depending on the intended properties.
  • You may contain additives other than (meth) acrylate (G) more than group, and a photoinitiator (H).
  • the additive include a polyimide resin, a polymerizable monomer (g), an epoxy curing agent (F), an epoxy curing accelerator, an antistatic agent, a coupling agent, an ultraviolet absorber, an antioxidant, and a surfactant ( i). Only 1 type may be used for an additive and 2 or more types may be used for it.
  • the polyimide resin is not particularly limited as long as it has an imide group. Only one type of polyimide resin may be used, or two or more types may be used.
  • the polyimide resin can be obtained, for example, by imidizing polyamic acid obtained by reacting acid dianhydride and diamine.
  • acid dianhydride the tetracarboxylic dianhydride (a1) which can be used for the synthesis
  • diamine examples include diamine (a2) that can be used for the synthesis of polyester amic acid (A).
  • the concentration of the polyimide resin in the composition of the present invention is not particularly limited, but a cured film having better heat resistance and chemical resistance can be obtained.
  • the content in 100 parts by weight of the composition is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight.
  • the polyimide resin does not contain a copolymer (C) obtained using an imide compound as a monomer.
  • the composition of the present invention may contain a polymerizable monomer other than the polyester amide acid (A), the epoxy compound (B), and the copolymer (C).
  • examples of the polymerizable monomer include a monofunctional polymerizable monomer and a bifunctional (meth) acrylate. Only 1 type may be used for a polymerizable monomer and it may use 2 or more types.
  • the concentration of the polymerizable monomer in the composition of the present invention is not particularly limited, but a cured film having a better chemical resistance and surface hardness can be obtained. From 1 to 40 parts by weight is preferably contained in 100 parts by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). Is more preferable.
  • Examples of the monofunctional polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 2, 6] decanyl (meth) acrylate, Gurisero Mono (meth) acrylate
  • bifunctional (meth) acrylate examples include bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanedi Ruji (meth) acrylate, trimethylolpropane di (meth
  • Epoxy curing agent (F) When the composition of the present invention includes an epoxy curing agent (F), the epoxy curing agent (F) is a compound different from the polyester amide acid (A), specifically, an acid anhydride curing agent, Examples include polyamine curing agents, polyphenol curing agents, and catalyst-type curing agents, but acid anhydride curing agents are preferred from the standpoints of storage stability and solder heat resistance. As the epoxy curing agent (F), only one type may be used, or two or more types may be used.
  • the acid anhydride-based curing agent examples include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; phthalic anhydride, trimellitic anhydride And aromatic polycarboxylic acid anhydrides such as styrene-maleic anhydride copolymer.
  • trimellitic anhydride is particularly preferable from the viewpoints of obtaining a compound having excellent solubility in the solvent (D) and obtaining a cured film having excellent heat resistance.
  • the content of the epoxy curing agent (F) is a solid of the composition according to an embodiment of the present invention in that a cured film having excellent balance in hardness, chemical resistance and adhesion to a metal such as copper can be obtained.
  • it is 35 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 25 parts by weight or less, and particularly preferably 20 parts by weight with respect to 100 parts by weight (the balance obtained by removing the solvent from the composition). It is as follows.
  • the content of the epoxy curing agent (F) is 100 parts by weight in total of the epoxy compound (B) and the copolymer (C) in the composition according to an embodiment of the present invention.
  • the amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight, and particularly preferably 3 to 20 parts by weight.
  • the ratio of the total of the epoxy compound (B) and copolymer (C) to be used and the epoxy curing agent (C) is the epoxy to be used from the viewpoint of obtaining a cured film having excellent solder heat resistance and chemical resistance.
  • the amount of oxiranyl and oxetanyl groups in compound (B) and copolymer (C) is 0.2. It is preferably ⁇ 2 times equivalent, and preferably 0.5 to 1.5 times equivalent. Thereby, since the chemical resistance of the cured film obtained improves further, it is further more preferable.
  • the epoxy compound (B) and the copolymer (C) 1 equivalent of a compound having one oxiranyl group is used as the epoxy compound (B) and the copolymer (C), and a compound having one acid anhydride group is used as the epoxy curing agent (F).
  • the amount of the epoxy curing agent (F) is 2 times equivalent to the total amount of the epoxy compound (B) and the copolymer (C).
  • Epoxy curing accelerator for example, a tertiary amine, a tertiary amine salt, an imidazole, or the like from the viewpoint that the curing temperature of the composition of the present invention can be lowered or the curing time can be shortened.
  • Epoxy curing accelerators such as phosphine, phosphonium salts and thiols can be used.
  • Each of the epoxy curing accelerators may be used alone or in combination of two or more.
  • epoxy curing accelerators are “DBU”, “DBN”, “U-CAT”, “U-CAT SA1”, “U-CAT SA102”, “U-CAT SA506”, “U-CAT SA603”, “U-CAT SA810”, “U-CAT 5002”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT SA841”, “U-CAT851”, “U-CAT SA881”, “U -CAT 891 "(trade name, manufactured by San Apro),” CP-001 ",” NV-203-R4 "(trade name, manufactured by Osaka Gas Chemical Co., Ltd.),” Karenzu MT PE1 ",” Karenzu MT BD1 " ”,“ Karenz MT NR1 ”,“ TPMB ”,“ TEMB ”(trade names, manufactured by Showa Denko KK) and the like.
  • the content of the epoxy curing accelerator is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight with respect to 100 parts by weight of the epoxy curing agent (F).
  • the amount is preferably 30 to 150 parts by weight.
  • the content of the epoxy curing accelerator is preferably 1 to 20 parts by weight, more preferably 100 parts by weight based on the total amount of the epoxy compound (B) and the copolymer (C). Is 1 to 15 parts by weight, more preferably 1 to 10 parts by weight.
  • Antistatic agents antistatic agents may be used to prevent the charging of the compositions of the present invention, when the composition of the invention includes an antistatic agent, in 100 parts by weight of the composition of the present invention, 0 It is preferably used in an amount of 0.01 to 1 part by weight.
  • a known antistatic agent can be used as the antistatic agent.
  • Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; quaternary ammonium salts, and the like. Only one type of antistatic agent may be used, or two or more types may be used.
  • the coupling agent is not particularly limited, and a known coupling agent such as a silane coupling agent can be used for the purpose of improving the adhesion of a substrate such as metal or glass.
  • a coupling agent such as a silane coupling agent
  • the amount of the coupling agent is 10 parts by weight or less with respect to 100 parts by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). It is preferable to add and use as described above. Only one type of coupling agent may be used, or two or more types may be used.
  • silane coupling agent examples include trialkoxysilane compounds and dialkoxysilane compounds.
  • ⁇ -vinylpropyltrimethoxysilane, ⁇ -acryloylpropyltrimethoxysilane, ⁇ -methacryloylpropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -isocyanatopropyltriethoxysilane are particularly preferable.
  • what is used as a silane coupling agent among the silane compounds which have an epoxy group shall not be contained in (B) an epoxy compound.
  • the composition of the present invention contains an ultraviolet absorber, it is possible to prevent deterioration when a cured film obtained from the composition is exposed to light.
  • the antioxidant is 0.1% with respect to 100 parts by weight of the solid content of the composition excluding the ultraviolet absorber (residue obtained by removing the solvent from the composition). It is preferable to add up to 20 parts by weight. Only one type of ultraviolet absorber may be used, or two or more types may be used.
  • UV absorber examples include benzotriazole and hydroxyphenyl triazine.
  • TINUVIN PS, TINUVIN99-2, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (above, manufactured by BASF), LA-29, LA-31, LA-31, LA-31 31G, LA-31RG, LA-32, LA-36, LA-36RG, LA-46, LA-1413, LA-F70 (trade names, manufactured by ADEKA Corporation) and the like.
  • the composition of the present invention contains an antioxidant, it is possible to prevent deterioration when a cured film obtained from the composition is exposed to high temperature or light.
  • the antioxidant is 0.1 parts by weight based on 100 parts by weight of the solid content of the composition excluding the antioxidant (residue obtained by removing the solvent from the composition). It is preferable to add up to 10 parts by weight. Only one type of antioxidant may be used, or two or more types may be used.
  • antioxidant examples include hindered amine compounds and hindered phenol compounds.
  • composition of the present invention contains a surfactant
  • the surfactant is preferably used in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the composition of the present invention. Only one type of surfactant may be used, or two or more types may be used.
  • the surfactant for example, from the viewpoint of improving the coating property of the composition of the present invention, for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (all trade names: Kyoeisha Chemical Co., Ltd.), Disperbeek 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-335, BYK-341, BYK-342, BYK-344, BYK-346, BYK-354, BYK-358, BYK-361, BYK-361N, BYK-370, BYK-UV3500, BYK-UV3570 (all trade names: Big Chemie Japan Co., Ltd.), KP-112, KP-326, KP
  • thermosetting resin composition comprises a polyester amide acid (A), an epoxy compound (B), a copolymer (C), a solvent (D), a colorant (E), a trifunctional group. It can be prepared by mixing the above (meth) acrylate (G), photopolymerization initiator (H), and other additives used as necessary.
  • composition of the present invention as it is, the epoxy compound (B), the solvent (D), the reaction liquid and the mixed liquid obtained at the time of synthesizing the polyester amic acid (A) and the copolymer (C), It can also be prepared by mixing the colorant (E), the (meth) acrylate (G) having three or more functional groups, the photopolymerization initiator (H), and other additives used as necessary.
  • composition of the present invention is preferably stored in the range of ⁇ 30 ° C. to 25 ° C., since the stability of the composition over time is good.
  • a storage temperature of ⁇ 25 ° C. to 10 ° C. is more preferable because there is no precipitate.
  • Manufacturing method of cured film The method of manufacturing a cured film using the composition which concerns on one Embodiment of this invention is not limited.
  • the manufacturing method of the cured film which concerns on one Embodiment of this invention is equipped with the arrangement
  • an uncured film made of the composition according to one embodiment of the present invention is arranged on a substrate in a predetermined shape.
  • the uncured film may be disposed so as to cover the entire surface of the substrate, or may be disposed so as to form a pattern on the surface of the substrate.
  • the method for supplying the composition according to one embodiment of the present invention onto the substrate is not limited. Spray coating method, spin coating method, roll coating method, dipping method, slit coating method, bar coating method, gravure printing method, flexographic printing method, offset printing method, dispenser method, screen printing method and ink jet printing method are conventionally known. It can be done by a method.
  • the ink-jet method can significantly reduce the amount of ink used compared to other methods, and it is not necessary to use a photomask or the like. For this reason, according to the ink jet method, a large variety of cured films can be produced in large quantities, and the number of steps required for producing these cured films is small. Therefore, the inkjet method may be particularly preferred when the uncured film has a pattern.
  • the composition according to the embodiment of the present invention is suitable as an inkjet ink composition.
  • coating methods such as spin coating, slit coating, gravure printing, flexographic printing, offset printing, dispenser, screen printing, etc. May be preferred.
  • a step of surface-treating the substrate may be provided.
  • the shape stability of the uncured film on the substrate can be improved, or the adhesion of the cured film on the substrate to the substrate can be improved There is.
  • the surface treatment performed in the surface treatment step include silane coupling agent treatment, UV ozone ashing treatment, plasma treatment, alkali etching treatment, acid etching treatment, and primer treatment.
  • the substrate on which the uncured film is disposed is not particularly limited, and a member made of a known material can be used.
  • the shape of the substrate is not limited, and for example, it may be a plate, that is, a substrate.
  • Specific examples of substrates include glass epoxy substrates, glass composite substrates, paper phenol substrates, paper epoxy substrates, green epoxy substrates, BT, which comply with various standards such as FR-1, FR-3, FR-4 or CEM-3.
  • (Bismaleimide triazine) resin substrate a substrate made of metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or stainless steel (a substrate having a layer made of these metals on the surface)
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • PCT polycyclohexylene dimethylene terephthalate
  • PPS polyphenylene sulfide
  • polycarbonate Substrates made of resin such as polyacetal, polyphenylene ether, polyimide, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer or liquid crystal polymer (It may be a substrate having a resin-containing layer on its surface); Semiconductor substrate such as silicon, germanium or gallium arsenide; Glass substrate; Electrode material such as tin oxide, zinc oxide, ITO or ATO (antimony tin oxide) A substrate on which (wiring) is formed; a gel sheet such as ⁇ GEL (alpha gel), ⁇ GEL (be
  • the cured film in the member with a cured film according to an embodiment of the present invention can be appropriately attached to the substrate. For this reason, even when an external force is applied to the cured film, it is difficult to peel off from the base material (that is, excellent adhesion), and even if the member with the cured film is immersed in boiling water, the cured film peels off. Difficult (that is, excellent in water resistance). Therefore, the member with a cured film according to an embodiment of the present invention can maintain an excellent appearance even when placed under various environments.
  • the uncured film formed on the substrate by the above-described arrangement process is cured to obtain a cured film on the substrate.
  • the method for curing the uncured film is not limited. It is set as appropriate according to the composition of the composition. Specific examples include heating and irradiation with ionizing radiation such as ultraviolet rays, ion beams, electron beams, and gamma rays. As a process, for example, a final cured film can be obtained by proceeding with a curing reaction by final heating after drying by heating or temporary curing by ultraviolet irradiation.
  • ionizing radiation such as ultraviolet rays, ion beams, electron beams, and gamma rays.
  • the heating method is not limited.
  • the uncured film may be heated together with the substrate by a hot plate or an oven, or may be heated by irradiating the uncured film with infrared rays. By heating in this way, the solvent in the uncured film is volatilized (drying treatment), the ring opening reaction of the oxiranyl and oxetanyl of the epoxy compound (B), the copolymer (C), and the trifunctional or higher functional group.
  • the radical polymerization reaction of (meth) acrylate (G) proceeds (curing treatment), and a cured film is formed from the uncured film.
  • the method is not limited in the case where the uncured film is temporarily cured by ultraviolet irradiation to form a temporarily cured film.
  • an uncured film is irradiated with ultraviolet rays together with a substrate using an ultraviolet irradiation device.
  • the amount of ultraviolet irradiation is suitably 5 to 10,000 mJ / cm 2 for i-line.
  • the solvent in the uncured film is volatilized (drying treatment) and the polymerizable double bond of (meth) acrylate (G) having three or more functional groups is polymerized to form a three-dimensional crosslinked product. Therefore, a part of the uncured film is cured.
  • this state is referred to as pre-curing, and the pre-cured film in the pre-cured state is a tack-free state having no stickiness on the surface. Saving is possible.
  • the drying conditions vary depending on the type and mixing ratio of each component contained in the composition to be used. Usually, the heating temperature is 70 to 120 ° C., and the heating time is 5 to 15 for an oven. 1 minute for a hot plate for 1 to 10 minutes.
  • a coating film capable of maintaining the shape can be formed on the substrate from the uncured film.
  • a curing treatment is usually performed at 80 to 300 ° C., preferably 100 to 250.
  • a cured film can be obtained by heat treatment usually for 10 to 120 minutes when using an oven, and usually 5 to 60 minutes when using a hot plate.
  • the above drying treatment may be performed by heating, and the coating film may be irradiated with ionizing radiation to perform the curing treatment.
  • a process group including an arrangement process and a curing process may be performed a plurality of times.
  • a cured film having a laminated structure can be formed on the substrate.
  • a cured film having a laminated structure by repeating a process group consisting of an arranging process and a drying process in a curing process, laminating a coating film, and performing a curing process in the curing process on the laminate of the obtained coating film You may get
  • the cured film produced in this way may be used after being peeled off from the base material, depending on the desired application and the base material used, or may be used as it is without being peeled off from the base material.
  • Cured film-coated substrate according to one embodiment of the cured film-coated substrate present invention (member) comprises a substrate and the above cured film provided on the substrate.
  • the substrate with a cured film according to an embodiment of the present invention is an insulating film for a wiring board. Further, since the insulating film serves as a light shielding member, the wiring concealability is good, and the substrate with a cured film is also excellent in design.
  • the thickness of the cured film in the member with a cured film according to an embodiment of the present invention is not limited. If it is excessively thin, it may be difficult to obtain a desired color tone, and if it is excessively thick, production efficiency may decrease (specifically, an increase in manufacturing time and an increase in manufacturing cost may be exemplified). In consideration of the occurrence of the above, the thickness of the cured film is appropriately set. From the viewpoint of obtaining a cured film exhibiting a dark color tone more stably, the thickness of the cured film in the member with a cured film according to an embodiment of the present invention may be 3 ⁇ m or more because excellent flux resistance can be obtained.
  • the thickness is preferably 4 ⁇ m or more, and more preferably 5 ⁇ m or more.
  • the thickness of the cured film in the member with the cured film according to one embodiment of the present invention may be preferably 20 ⁇ m or less, and may be 15 ⁇ m or less. It may be more preferable.
  • An electronic / electrical component according to an embodiment of the present invention includes a member with a cured film according to an embodiment of the present invention.
  • Examples of the electronic / electrical component according to one embodiment of the present invention include a semiconductor package and a printed wiring board used in electronic devices such as smartphones and tablet terminals.
  • the names and abbreviations of the monomer (c1), the polymerization initiator (c2) and the reaction solvent (c3) used in the synthesis of (a5), the polyhydric acid anhydride (a6), and the copolymer (C) are shown. This abbreviation is used in the following description.
  • ⁇ Polyester amide acid > ⁇ Tetracarboxylic dianhydride (a1)> ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride ⁇ Diamine (a2)> DDS: 3,3′-diaminodiphenylsulfone ⁇ Polyvalent hydroxy compound (a3)> BDOH: 1,4-butanediol ⁇ monohydric alcohol (a4)> BzOH: benzyl alcohol ⁇ Reaction solvent (a5)> MPM: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate EDM: diethylene glycol methyl ethyl ether ⁇ acid anhydride (a6)> SM: SMA1000 (trade name, manufactured by Kawa Crude Co., Ltd.)
  • EHPE3150 EHPE3150 (trade name, manufactured by Daicel Corporation), 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (epoxy equivalent 177, weight) Average molecular weight 2,400) 157S70: 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), special novolac type epoxy resin (epoxy equivalent 200 to 220, weight average molecular weight 3,000 or less)
  • C620 NANOPOX C620 (trade name, manufactured by EVONIK), epoxy resin containing 40% nanosilica (epoxy equivalent 220) VG3101L: TECHMORE VG3101L (trade name, manufactured by Printec Co., Ltd.)
  • High heat resistant trifunctional epoxy resin epoxy equivalent 210, molecular weight 592-1,129, mixture of monomer and dimer
  • EG200 OGSOL EG200 (trade name, manufactured by Osaka Gas
  • UV-1700B Purple light UV-1700B (trade name), manufactured by Nippon Synthetic Chemical Co., Ltd., UV curable urethane acrylate resin (10 functional groups)
  • M305 Aronix M305 (trade name), manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (3 to 4 functional groups)
  • GMA Glycidyl methacrylate (1 functional group) CH: Light ester CH (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), cyclohexyl methacrylate (1 functional group) THFMA: Light ester THF (1000) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate (1 functional group) FA513M: FANCLIL FA513M (trade name, manufactured by Hitachi Chemical Co., Ltd.), cyclopentanyl methacrylate (bifunctional group) M208: Aronix M208 (trade name, manufactured by Toagosei Co., Ltd.), Bisphenol F EO-modified (n ⁇ 2) diacrylate (2 functional groups) M211B: Aronix M211B (trade name, manufactured by Toagosei Co., Ltd., bisphenol A EO-modified (n ⁇ 2) diacrylate (2 functional groups) FA321
  • OXE-02 IRGACURE OXE-02 (trade name, manufactured by BASF Japan Ltd.) Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 (0-acetyloxime) (oxime ester photopolymerization initiator)
  • IW-15 Nikkaure IW-15 (trade name, manufactured by Nippon Chemical Industry Co., Ltd.) (oxime ester photopolymerization initiator)
  • IRGACURE 907 IRGACURE 907 (trade name, manufactured by BASF Japan Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ( ⁇ -aminoalkylphenone-based photopolymerization started) Agent)
  • RS-72K Megafax RS-72-K (trade name, manufactured by DIC Corporation), fluorine-containing group / hydrophilic group / lipophilic group / UV-reactive group-containing oligomer BYK342: BYK342 (trade name, Big Chemie Co., Ltd.) )), Polyether-modified polydimethylsiloxane solution
  • polyester amic acid was synthesized as shown below (Synthesis Examples 1 and 2).
  • the rotational viscosity of this solution was 29 mPa ⁇ s.
  • the rotational viscosity is a value measured at 25 ° C. using an E-type viscometer (trade name: VISCONIC END, manufactured by Tokyo Keiki Co., Ltd.) (hereinafter the same).
  • the weight average molecular weight of the obtained polyester amide acid was 4,300.
  • the weight average molecular weight of the polyester amide acid was measured as follows.
  • the obtained polyester amic acid was diluted with N, N-dimethylformamide (DMF) so that the polyamic acid concentration was about 1% by weight, and GPC apparatus: manufactured by JASCO Corporation, Chrom Nav (differential refractive index).
  • GPC apparatus manufactured by JASCO Corporation, Chrom Nav (differential refractive index).
  • the diluted solution was measured by a GPC method using a developing agent, and was calculated by polystyrene conversion.
  • Three columns GF-1G7B, GF-510HQ and GF-310HQ manufactured by Showa Denko Co., Ltd. were connected in this order, and the column was measured under conditions of a column temperature of 40 ° C. and a flow rate of 0.5 ml / min. .
  • the copolymer (C) was obtained by cooling to 30 degrees C or less.
  • the rotational viscosity of this solution was 320 mPa ⁇ s, and the weight average molecular weight of the obtained copolymer (C) was 43,000.
  • the proportions of the monomers constituting the copolymer (C) were 20 mol% for N-phenylmaleimide, 70 mol% for glycidyl methacrylate, and 10 mol% for n-butyl methacrylate.
  • Example 1 A 300 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 2.80 g of the polyester amic acid (A) solution obtained in Synthesis Example 1 (the amount of the polyester amic acid (A) in the solution was 0.00). 84 g), 1.34 g of EHPE3150 (epoxy compound (B)), 0.84 g of the copolymer (C) solution obtained in Synthesis Example 3 (the amount of copolymer (C) is 0.252 g), GBL 6.41 g of (solvent (D), high-temperature solvent) was charged. Then, it stirred at 25 degreeC (room temperature) for 2 hours, and dissolved each component uniformly.
  • thermosetting resin-containing composition 0.56 g of Marco 2011 as the colorant (E) (0.168 g of the pigment (solid content) contained therein), 0.17 g of TMA as the epoxy curing agent (F), having a trifunctional group or more ( 0.84 g of UV-1700B as a (meth) acrylate, 0.33 g of OXE-02 as a photopolymerization initiator, 0.03 g of RS-72K as a surfactant, and agitation for 1 hour at 25 ° C. : Nylon, pore diameter: 5 ⁇ m) to obtain a thermosetting resin-containing composition as a filtrate.
  • thermosetting resin compositions were prepared in the same manner as in Example 1 except that the types and amounts of each component were changed as shown in Tables 3 and 4.
  • thermosetting resin compositions were prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 5.
  • Substrate Copper substrate (4cm square)
  • Application method inkjet printing Printer: DMP-2831 (manufactured by FUJIFILM Dimatix)
  • Head DMC-11610 (manufactured by FUJIFILM Dimatix)
  • UV curing tack-free exposure amount UV curing tack-free exposure amount: mJ / cm
  • UV curing tack-free exposure amount mJ / cm
  • the exposure amount is a value measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC.
  • thermosetting resin composition obtained by a sample substrate having a cured film formed on the substrate.
  • substrate flux tolerance, solder heat resistance, chemical resistance, and OD value were evaluated by the method mentioned later.
  • Curing conditions Main baking process Clean oven DT-610 manufactured by Yamato Scientific Co., Ltd. Temperature setting: 170 ° C, 60 minutes
  • UV exposure required for temporary curing (UV tack-free exposure)
  • the substrate before provisional curing with the coating film formed on the surface is irradiated with ultraviolet light having a wavelength of 365 nm, and the surface of the substrate before provisional curing is touched by hand for every 1000 mJ / cm 2 of ultraviolet irradiation amount. It was confirmed whether temporary hardening was completed.
  • the UV irradiation amount required to temporarily cure the coating film to such an extent that the ink does not adhere to the hand and the pre-curing substrate can be stacked and stored can be found in the UV curing tack-free exposure column in Tables 6 to 8. Indicated.
  • solder heat resistance In order to evaluate the solder heat resistance of the cured film, a flux is applied to the surface of the sample substrate of the example and the comparative example, dipped in a solder bath at 260 ° C. for 10 minutes, washed with water, air dried, Whether or not swelling occurred was examined by microscopic observation and evaluated using the following criteria. The results are shown in Tables 6-8. ⁇ : No peeling occurred. X: Peeling occurred.
  • OD value (Optical Density)
  • the cured film with a film thickness of 4 micrometers was formed on a glass substrate, and the Y value was measured using the JASCO Corporation ultraviolet visible spectrophotometer V-670. did.
  • any of the cured films (sample substrates) obtained from the inks (curable resin compositions) according to Examples 1 to 16 and Comparative Examples 1 to 8 were subjected to the flux resistance test. Before performing (the 0th time), the remaining number of grids after tape peeling was 100, and it was confirmed that the cured film has excellent adhesion to the copper substrate. However, after the flux resistance test (first time), all of Examples 1 to 16 had 100 remaining grids, whereas Comparative Examples 1 to 8 all had 100 grid remaining. Instead, peeling occurred in a part of the cured film.
  • solder heat resistance None of the cured films (sample substrates) obtained from the inks (curable resin compositions) according to Examples 1 to 16 were peeled after the solder heat resistance test. On the other hand, the cured films (sample substrates) obtained from the inks according to Comparative Examples 1 to 8 all peeled after the solder heat resistance test. From this result, it can be seen that the solder heat resistance of the cured film is improved by using the copolymer (C) and a (meth) acrylate having three or more functional groups.
  • the cured film formed of the inks of Examples 1 to 16 has an OD value of 2.3 or more and has a sufficiently dark color to perform an accurate inspection using an optical inspection apparatus. Met.
  • the coating films formed with the inks of Examples 1 to 16 could be temporarily cured with a smaller amount of ultraviolet light exposure than the coating films formed with the inks of Comparative Examples 1 to 7. From these results, in addition to being able to form a cured film excellent in flux resistance, solder heat resistance and chemical resistance, the inks of Examples 1 to 16 have a short time required for temporary curing and are easy to handle. It was good.
  • thermosetting resin composition of the present invention has excellent heat resistance, moisture resistance, insulation, adhesion to substrates and circuits, flux resistance, solder resistance, solvent resistance, heat resistance and insulation in thin films.
  • a thin film having a thickness of 20 ⁇ m or less has a dark black color enough to shield the underlying circuit, and can be stably printed with an ink jet head having a small nozzle size, so that it can be used as an ink composition for ink jet.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne la formation d'un produit durci présentant une adhésion à un substrat, une résistance au flux de soudage, une résistance au soudage, et une résistance au solvant supérieures, et afin de permettre le durcissement dans le temps, cette composition de résine thermodurcissable contient un poly(acide d'ester amide) (A), un composé époxy (B) présentant un poids moléculaire moyen en poids inférieur à 10 000, un copolymère (C) ayant un groupe oxiranyle ou oxétanyle, un solvant (D), un agent colorant (E), un (méth)acrylate (G) ayant trois groupes fonctionnels ou plus, et un initiateur de polymérisation (H).
PCT/JP2018/007499 2017-03-02 2018-02-28 Composition de résine thermodurcissable, film durci, substrat présentant un film durci, composant électronique, et composition d'encre pour jet d'encre WO2018159675A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112625479A (zh) * 2019-10-09 2021-04-09 捷恩智株式会社 热硬化性组合物、硬化膜及彩色滤光片
US11026298B2 (en) * 2016-04-01 2021-06-01 Lg Chem, Ltd. Ink composition, cured patterns produced thereby, heating element including same, and manufacturing method therefor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372691B (zh) * 2021-06-23 2022-06-28 宁波长阳科技股份有限公司 树脂组合物、强化液、强化层和光学保护膜

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996011239A1 (fr) * 1994-10-05 1996-04-18 Goo Chemical Co., Ltd. Encre resist de photosoudure, carte a circuit imprime et procede de fabrication
JP2014169353A (ja) * 2013-03-01 2014-09-18 Jnc Corp 熱硬化性組成物
JP2015081336A (ja) * 2013-10-24 2015-04-27 Jnc株式会社 熱硬化性樹脂組成物
WO2015068703A1 (fr) * 2013-11-05 2015-05-14 太陽インキ製造株式会社 Composition durcissable, film de revêtement durci utilisant celle-ci, et carte de circuit imprimé
JP2016103010A (ja) * 2014-11-18 2016-06-02 Jnc株式会社 感光性組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996011239A1 (fr) * 1994-10-05 1996-04-18 Goo Chemical Co., Ltd. Encre resist de photosoudure, carte a circuit imprime et procede de fabrication
JP2014169353A (ja) * 2013-03-01 2014-09-18 Jnc Corp 熱硬化性組成物
JP2015081336A (ja) * 2013-10-24 2015-04-27 Jnc株式会社 熱硬化性樹脂組成物
WO2015068703A1 (fr) * 2013-11-05 2015-05-14 太陽インキ製造株式会社 Composition durcissable, film de revêtement durci utilisant celle-ci, et carte de circuit imprimé
JP2016103010A (ja) * 2014-11-18 2016-06-02 Jnc株式会社 感光性組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11026298B2 (en) * 2016-04-01 2021-06-01 Lg Chem, Ltd. Ink composition, cured patterns produced thereby, heating element including same, and manufacturing method therefor
CN112625479A (zh) * 2019-10-09 2021-04-09 捷恩智株式会社 热硬化性组合物、硬化膜及彩色滤光片

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