WO2008072651A1 - 光塩基発生剤及び光硬化性樹脂組成物 - Google Patents
光塩基発生剤及び光硬化性樹脂組成物 Download PDFInfo
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- WO2008072651A1 WO2008072651A1 PCT/JP2007/073916 JP2007073916W WO2008072651A1 WO 2008072651 A1 WO2008072651 A1 WO 2008072651A1 JP 2007073916 W JP2007073916 W JP 2007073916W WO 2008072651 A1 WO2008072651 A1 WO 2008072651A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/111—Polymer of unsaturated acid or ester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/12—Nitrogen compound containing
Definitions
- the present invention relates to a photobase generator and a photocurable resin composition.
- Resin photocuring technology is superior to conventional thermosetting technology in that it is not only capable of curing at low temperatures and in a short time, but also enables microfabrication by optical patterning. Therefore, it is widely used especially in the field of electronic materials.
- the resin photo-curing technology is roughly divided into three types: radical type, cationic type including acid-cured type, and anion type including base-cured type. Conventionally, among these, radical type photocuring technology has been the mainstream.
- the force S the (meth) acrylic acid polymer used in this photocuring technology, has large room for shrinkage in curing and / or insufficient heat resistance and / or adhesiveness, so there is room for improvement in these respects.
- Patent Document 1 discloses an example in which basicity is increased by changing a 1,4-dihydropyridine skeleton to a pyridine skeleton by light irradiation.
- Patent Document 1 Japanese Patent Laid-Open No. 10-77264
- Patent Document 2 JP 2005-264156 A
- Patent Document 3 Japanese Patent Laid-Open No. 2003-212856
- Patent Document 4 Japanese Patent Laid-Open No. 2003-20339
- Non-Patent Document 1 1; ⁇ 8 Curing Technology 111 (1997, published by CMC), p. 78 Disclosure of the invention
- An object of the present invention is to provide a photobase generator suitable for curing a rayon curable resin by light irradiation.
- Japanese Examined Patent Publication No. 46-2574 discloses an example in which at least one selected from 5-phenyl trobolone, 5-cyantropolone, and 2-amino-5-phenyl tropone is used as an information recording material by ultraviolet irradiation. It is disclosed. This document states that it is also possible to use an epoxy resin as a dispersion medium for the above three compounds.
- the present inventors can express or increase the basicity while sufficiently suppressing the generation of unnecessary by-products using a photo-base generator having a predetermined characteristic or chemical structure including the above-mentioned compounds.
- the present invention has been completed.
- the present invention provides the following.
- 1 to ⁇ each independently represents an arbitrary atom or atomic group, and at least two of them may be bonded to each other to form a ring.
- X 8 to X 14 each independently represent any atom or atomic group, and at least two of them may be bonded to each other to form a ring.
- a photobase generator comprising at least one of the compounds represented by the following general formulas (3) and (4): [1] to [3].
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, or an aryl group
- R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, a forminole group, an asinole group, a nitro group, a nitroso group, an anolequinolole group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group, It represents a hydroxy group, a mercapto group, an alkylthioether group, an alkoxy group, a halogen atom, or an amino group.
- R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group represented by formula (3) or A monovalent group in which one hydrogen atom is eliminated from the compound represented by (4) may be substituted.
- Z represents an oxygen atom or a sulfur atom.
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group or an aryl group
- R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a cyan group, a formyl group, an acyl group, a nitro group, a nitroso group, an ananoleno group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryleno group, or a hydroxy group.
- RR 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independent of each other, at least two of them may be bonded to each other to form a saturated or unsaturated ring. May have a monovalent group in which one hydrogen atom is eliminated from the compound represented by formula (3) or (4) as a substituent.
- R 7 and R 8 forces The photobase generator according to [11] or [12], wherein each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group.
- R 1 and / or R 2 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group.
- Base generator represents an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group.
- R 1 represents a methyl group
- R 2 represents a hydrogen atom
- R 4 , R 5 , R 6 , R ? And R 8 each independently represents a hydrogen atom or an isopropyl group.
- a photocurable resin composition comprising V and one photobase generator.
- an anion curable resin is cured by light irradiation so that basicity can be expressed or increased while sufficiently suppressing generation of unnecessary by-products such as gas and water by light irradiation.
- a photobase generator suitable for the production can be provided.
- the photobase generator of this embodiment contains a compound having a nitrogen atom and a conjugated multiple bond.
- a photobase generator can exhibit basicity without generating unnecessary by-products such as gas and water only when these requirements are satisfied.
- this embodiment is a photobase generator particularly useful for curing resins for electronic materials that are strictly required to have insulation reliability, heat resistance, fine workability, and the like, and light containing the photobase generator.
- a curable resin composition can be provided.
- the “photobase generator” means a compound that expresses or increases basicity upon irradiation with light.
- basic means a property that cures a resin that is cured by a base. Whether or not the resin is cured can be confirmed by, for example, increasing the degree of polymerization, increasing the degree of crosslinking, or decreasing the solubility in a specific liquid (such as an aqueous alkali solution or an organic solvent).
- the basic expression and increase of the photobase generator due to light irradiation can be confirmed as follows. That is, prepare a photobase generator or its solution and measure ⁇ at room temperature. To do. Next, the photobase generator or a solution thereof is irradiated with light having a predetermined wavelength (for example, ultraviolet light having a wavelength of 365 nm) so as to have a predetermined light amount (for example, 6 to 9 j / cm 2 ), and then the photobase generator Or measure the pH of the solution at room temperature. As a result, it is recognized that basicity appears when the pH before light irradiation is 7.0 or less and the pH after light irradiation exceeds 7.0.
- a predetermined wavelength for example, ultraviolet light having a wavelength of 365 nm
- the photobase generator or its solution may be diluted with pure water or ion-exchanged water as necessary.
- the pH is measured using a commercially available pH meter (for example, Toa Denpa Kogyo Co., Ltd. ), Product name “HM-30G”)
- the photobase generator of the present embodiment is not particularly limited as long as it contains a compound containing a nitrogen atom and a conjugated multiple bond.
- the photobase generator contains a compound whose conjugate multiple bond is shortened or disappears by light irradiation.
- Examples of the compound in which the conjugated multiple bond is shortened or disappears by light irradiation include a compound in which a nitrogen atom is adjacent to the conjugated multiple bond, and a compound in which a nitrogen atom constitutes a conjugated multiple bond.
- the force S is not limited to the force S that includes a reaction represented by the following reaction formulas (5) to (; 12) in which the conjugated multiple bond is shortened or disappears by light irradiation.
- Y ⁇ Y 2 ⁇ may represent any atom or atomic group of the same or different type, and at least two of them may form a bond with each other to form a V atom.
- at least two of Y 11 and Y 12 , ⁇ 13 and ⁇ 14 , ⁇ 15 and ⁇ 16 , and ⁇ 17 to ⁇ 2 ° are each directly or via an organic group represented by a hydrocarbon group. To form a ring.
- ⁇ ⁇ ⁇ 2 may be a monovalent substituent derived from each component in the composition containing a photobase generator typified by the photocurable resin composition.
- the reaction represented by the above formulas (5) to (; 12) may be an intramolecular reaction or an intermolecular reaction. In the case of an intermolecular reaction, the reaction is not limited to the reaction between molecules of the same type, and may be a reaction of the same type of molecules.
- a multiple bond is a force that is a double bond.
- the photobase generator of the present embodiment has a five-membered ring structure or a seven-membered ring structure, which is preferable when the compound has a ring structure, from the viewpoint of further improving the curability of the cation polymerizable resin. It is more preferable.
- a more preferred example of a compound containing a nitrogen atom and a conjugated multiple bond contained in the photobase generator of the present embodiment is a compound represented by the above formula (1) or (2).
- X 1 and X 2 are each independently a substituent corresponding to R 1 and R 2 in the formula (3).
- X 4 and X 6 are each independently a substituent corresponding to R 3 to R 5 in the above formula (3).
- X 3 and X 7 are directly or hydrocarbons.
- a ring formed by bonding through an organic group typified by a group is preferred, and a ring having a substituent corresponding to Z in the above formula (3) is more preferred.
- the compound represented by the above formula (1) is in the second, the formula (1), preferably those which are substituents corresponding to R 9 tool in X 1 is described below formula (16)
- X 3 It is preferred that X 6 is independently a substituent corresponding to R 1Q to R 13 in formula (16).
- X 2 and X 7 are either directly or via an organic group typified by a hydrocarbon group. Are preferably bonded to form a ring.
- X 8 is a substituent corresponding to R 1 in the above formula (4) in the formula (2).
- X 1Q to X 13 are each independently X 9 and X 14 which are substituents corresponding to R 3 to R 6 in the above formula (4) are preferably bonded to each other directly or through an organic group typified by a hydrocarbon group. And forming a ring is preferable.
- Preferable examples of the compound in which the conjugated multiple bond is shortened or disappears by light irradiation include the compounds represented by the above formulas (3) and (4).
- the compound can be synthesized by a known method. For example, various methods can be applied by applying the method described in Dai Organic Chemistry, Volume 13, Non-enzymatic aromatic ring compounds (supervised by Fujio Kotake, published by Asakura Shoten Co., Ltd., 1957). It is possible to synthesize such compounds. Among them, the method of reacting with various amines after the tosylation of the hydroxy group of trobolone with p-toluenesulfurol chloride or methyl etheration with diazomethane or dimethylsulfuric acid is easy. is there.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group.
- R 3 to R 7 each independently represent a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, a formyl group, an asinole group, a nitro group, a nitroso group, an anorequinole group, an alkenyl group, a cycloalkyl group or an aralkyl group.
- the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a hydroxyethoxycarbonyl group.
- a methoxycarbonyl group is preferable from the viewpoint of ease of production.
- the acyl group is preferably an acetyl group from the viewpoint of ease of production.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Among them, isopropyl group is preferable from the viewpoint of availability of raw materials and performance.
- Examples of the alkenyl group include a propenyl group, a butyr group, and an isobutyr group.
- Examples of the cycloalkyl group include a cyclohexyl group.
- Examples of the aralkyl group include a benzyl group.
- the aryl group is preferably a phenyl group from the viewpoint of ease of production.
- alkoxy group examples include a methoxy group, an ethoxy group, and a propoxy group. Of these, a methoxy group is preferred from the viewpoint of ease of production.
- the halogen atom is preferably a chlorine atom or a bromine atom from the viewpoint of ease of production.
- the amino group may be substituted! /, Or may be substituted.
- Examples of the mono-substituted amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a cyclohexamino group, a benzylamino group, and a phenylamino group.
- a methylamino group is preferable from the viewpoint of easy availability of raw materials.
- Examples of the disubstituted amino group include a dimethylamino group, a jetylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a dicyclohexylamino group, a dibenzylamino group, and a diphenyl group.
- An amino group, a pyrrolidino group, a piperidino group, and a morpholino group are mentioned. Among them, a dimethylamino group is preferable from the viewpoint of easy availability of raw materials.
- I ⁇ to R 7 may be bonded to each other to form a saturated ring or an unsaturated ring.
- saturated ring and unsaturated ring include azole rings such as pyrazole ring, isoxazole ring, isothiazole ring, imidazole ring, oxazole ring, thiazole ring, triazole ring and tetrazole ring.
- I ⁇ to R 7 each independently has a monovalent group in which one hydrogen atom is eliminated from the compound represented by the above formula (3) or (4) as a substituent.
- Z represents an oxygen atom or a sulfur atom. From the viewpoint of improving the stability of the photobase generator during storage, Z is preferably an oxygen atom.
- R 1 represents a hydrogen atom, an arolequinol group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group.
- R 3 to R 8 each independently represent a hydrogen atom, a force lpoxyl group, an alkoxycarbonyl group, a cyano group, a honoreminole group, an asinole group, a nitro group, a nitroso group, an anorequinole group, an alkenyl group, a cycloalkyl group, an aralkyl group, A aryleno group, a hydroxy group, a mercapto group, an alkylthioether group, an alkoxy group, a halogen atom or an amino group;
- the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a hydroxyethoxycarbonyl group.
- a methoxycarbonyl group is preferred from the viewpoint of ease of production.
- the acyl group is preferably an acetyl group from the viewpoint of ease of production.
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group.
- an isopropylinole group is preferable from the viewpoint of availability of raw materials and performance.
- Examples of the alkenyl group include a propenyl group, a butyr group, and an isobutenyl group.
- Examples of the cycloalkyl group include a cyclohexyl group.
- Examples of the aralkyl group include a benzyl group.
- the aryl group is preferably a phenyl group from the viewpoint of ease of production.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Among them, from the viewpoint of ease of manufacturing, A toxi group is preferred.
- the halogen atom is preferably a chlorine atom or a bromine atom from the viewpoint of ease of production.
- the amino group may be unsubstituted or substituted.
- Examples of the mono-substituted amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a cyclohexylamino group, a benzylamino group, and a phenylamino group.
- a methylamino group is preferable from the viewpoint of easy availability of raw materials.
- di-substituted amino group examples include a dimethylamino group, a jetamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a dicyclohexylenoamino group, a dipentinoreamino group, a diphenenoreamino group, a pyrrolidino group, a piperidino group, A morpholino group is mentioned. Among them, a dimethylamino group is preferable from the viewpoint of easy availability of raw materials.
- At least two of ⁇ to may be bonded to each other to form a saturated ring or an unsaturated ring.
- saturated ring and unsaturated ring include azole rings such as pyrazole ring, isoxazole ring, isothiazole ring, imidazole ring, oxazole ring, thiazole ring, triazole ring and tetrazole ring.
- ⁇ ⁇ Each independently has a monovalent group in which one hydrogen atom is eliminated from the compound represented by the above formula (3) or (4) as a substituent! / ,.
- a compound is preferable as a photobase generator because of its excellent storage stability.
- R 1 and / or R 2 is more preferably alkyl group, alkenyl group, cycloalkyl group, aralkyl group or aryl group, R 1 represents a methyl group, and R 2 represents hydrogen. More preferably, it represents an atom, and R 3 to R 8 each independently represents a hydrogen atom or an isopropyl group.
- the compounds represented by the above formulas (3) and (4) express or increase basicity by utilizing a photomolecular cyclization reaction that is characteristic of a seven-membered ring.
- a photomolecular cyclization reaction that is characteristic of a seven-membered ring.
- the conjugated system of multiple bonds extending over the entire seven-membered ring is shortened by the intramolecular photomolecular cyclization reaction represented by the following reaction formulas (13) and (14), and the electron density on the nitrogen atom increases.
- R represents a hydrogen atom, an arolequinol group, an alkenyl group, a cycloalkyl group, an aralkyl group or an aryl group.
- R 1Q to R 13 are each independently a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, a honoreminole group, an asinole group, a nitro group, a nitroso group, an anorequinole group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group.
- alkyl group It represents an alkyl group, a hydroxy group, a mercapto group, an alkylthioether group, an alkoxy group, a halogen atom or an amino group.
- alkoxycarbonyl group include a methoxycarbon group, an ethoxycarbonyl group, and a hydroxyethoxycarbonyl group.
- a methoxycarbonyl group is preferred from the viewpoint of ease of production.
- the acyl group is preferably an acetyl group from the viewpoint of ease of production.
- Examples of the alkyl group include a methylol group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Among them, an isopyl pill group is preferable from the viewpoint of availability of raw materials and performance.
- Examples of the alkenyl group include a propenyl group, a butyr group, and an isobutyl group.
- Examples of the cycloalkyl group include a cyclohexyl group.
- Examples of the aralkyl group include a benzyl group.
- the aryl group is preferably a phenyl group from the viewpoint of ease of production.
- alkoxy group examples include a methoxy group, an ethoxy group, and a propoxy group. Of these, a methoxy group is preferred from the viewpoint of ease of production.
- the halogen atom is preferably a chlorine atom or a bromine atom from the viewpoint of ease of production.
- the amino group may be unsubstituted or substituted.
- Examples of the mono-substituted amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a cyclohexylamino group, a benzylamino group, and a phenylamino group.
- a methylamino group is preferable from the viewpoint of easy availability of raw materials.
- di-substituted amino group examples include a dimethylamino group, a jetylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a dicyclohexylenoamino group, a dipentinoreamino group, a diphenenoreamino group, a pyrrolidino group, a piperidino group, A morpholino group is mentioned. Among them, dimethylamino group is preferred from the viewpoint of easy availability of raw materials.
- R 9 to R 13 may be bonded to each other to form a saturated ring or an unsaturated ring.
- saturated ring and unsaturated ring include azole rings such as pyrazole ring, isoxazole ring, isothiazole ring, imidazole ring, oxazole ring, thiazole ring, triazole ring and tetrazole ring.
- R 9 to R 13 each independently have a monovalent group in which one hydrogen atom is detached from the molecule represented by the above formula (16) as a substituent! / ,.
- the compound represented by the above formula (16) expresses or increases basicity by utilizing a photomolecular cyclization reaction, which is a characteristic of pyrrole.
- a photomolecular cyclization reaction which is a characteristic of pyrrole.
- the conjugated system of multiple bonds that spanned the entire five-membered ring was shortened by the photointramolecular cyclization reaction represented by the following reaction formula (17).
- the basicity is expressed or increased by increasing the electron density on the nitrogen atom.
- the photobase generator of the present embodiment may contain one of the above-mentioned compounds alone or in combination of two or more! /.
- the composition contains a yuon polymerizable resin and the above-mentioned photobase generator.
- One photobase generator is used alone, or two or more photobase generators are used in combination.
- the ayu polymerizable resin according to this embodiment is not particularly limited as long as it is a resin curable by a base.
- a resin include an epoxy resin, a polyimide precursor, and a compound having a isocyanate group.
- epoxy resin is preferred from the viewpoint of overall performance and economy!
- Known epoxy resins can be used, such as glycidyl ethers of divalent phenols, polyglycidyl ethers of polyhydric phenols having 3 to 6 or more hydroxy groups, aliphatic 2 Diglycidyl ethers of monohydric alcohols, Daricidyl ether type epoxy resins such as polyglycidyl ethers of aliphatic polyhydric alcohols having a tri- to 6- or higher-valent hydroxy group, glycidyl ester type epoxy resins, aliphatic or alicyclic Glycidyl ester of a polycarboxylic acid of the formula, glycidylamine of an aromatic amine having an active hydrogen atom, glycidylamine of an alicyclic amine having an active hydrogen atom, glycidyla of a heterocyclic amine having an active hydrogen atom Mines, chain aliphatic epoxides, and alicyclic epoxides.
- glycidyl ethers of divalent phenols include, for example, bisphenol Nore F Diglycidyl Ether, Bisphenol A Diglycidyl Ether, Bisphenol S Diglycidyl Ether, Halogenated Bisphenol A Diglycidyl Ether, Tetrachrome Bisphenol A Diglycidyl Ether, Force Techin Diglycidyl Ether, Resorcino Monoresiglicid / Rate / Les, Hyde port Kinonjigurishiji / Reete / Les, 1, 5-dihydroxynaphthalene diglycidyl ether, dihydroxy-bi-phenylene Le diglycidyl ether, OTA Takuroro 4, 4 'over-dihydroxy-phenylene Le diglycidyl ether, tetramethyl Biff enyl diglycidyl ether, 9, 9, 1-bis (4-hydroxyphenyl) fluorenediglycidyl ether, diglycidyl ether obtained from the reaction of 2 mo
- polyglycidyl ethers of polyhydric phenols having a tri- to hexa- or higher-valent hydroxy group include, for example, pyrogallol triglycidyl ether, dihydroxynaphthinole cresol triglycidyl ether, and tris (hydroxyphenol) Methanetriglycidyl ether, dinaphthyltriglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p glycidylphenyldimethyltrilbisphenol A glycidyl ether, trismethyl-tert butyl-butylhydroxymethane triglycidyl ether, 4 , 4'oxybis (1,4 phenylethyl) tetracresol glycidyl ether, 4,4'oxybis (1,4 phenylethinole) phenyldarici
- Examples of the diglycidyl ether of the aliphatic dihydric alcohol include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene.
- Glyconoresidicyl glycidyl ether Polypropylene glyco monoresidicyl glycidyl ether, Polytetramethylene glycol diglycidyl ether, Neopentyl glycol Diglycidyl ether, diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A.
- polyglycidyl ethers of aliphatic polyhydric alcohols having a tri- to hexa- or higher-valent hydroxy group include, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexane.
- examples include glycidyl ether and polyglycerol polyglycidyl ether.
- Examples of the glycidyl ester type epoxy resin include glycidyl esters of aromatic polycarboxylic acids such as diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and triglycidyl ester of trimellitic acid. It is possible.
- Examples of glycidyl esters of aliphatic or cycloaliphatic polycarboxylic acids include aromatic nucleus hydrogenated products of diglycidyl esters of aromatic polycarboxylic acids, diglycidic acid / reseste / res, diglycidic / residual xalate, diglycidic acid.
- Examples of glycidylamines of aromatic amines having active hydrogen atoms include N, N-diglycidyl toluidine, N, N, ⁇ ', N'-tetraglycidyldiaminodiphenylmethane, ⁇ , ⁇ , ⁇ , -tetraglycidyldiaminodiphenylsulfone, ⁇ , ⁇ , ⁇ , ⁇ , tetraglycidyljetyldiphenylmethane, ⁇ , ⁇ , ⁇ -triglycidylaminophenol.
- Examples of glycidylamines of alicyclic amines having active hydrogen atoms include hydrogenated products of ⁇ , ⁇ , ⁇ ′, N′-tetraglycidylxylylenediamine.
- Examples of glycidylamines of heterocyclic amines having an active hydrogen atom include trisglycidylmelamine.
- Examples of chain aliphatic epoxides include epoxidized butadiene and epoxidized soybean oil.
- Examples of the alicyclic epoxides include burcyclohexenedioxide, limonene dioxide, dicyclopentagendi oxide, bis (2,3-epoxycycline pentinole) etherenole, and ethylene glycolenobis epoxy dicyclopentenoleateenole.
- the epoxy resin according to this embodiment is used singly or in combination of two or more. From the viewpoint of the performance and availability of the cured product, the epoxy resin is preferably a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin, and more preferably a glycidyl ether type epoxy resin.
- the photocurable resin composition preferably further contains a compound having two or more functional groups in the molecule having reactivity with the epoxy resin.
- the functional group having reactivity with the epoxy resin is not particularly limited as long as it is a functional group known to react with the epoxy resin.
- carboxyl group, thiol group, phenolic hydroxyl group, primary or 2 A class aromatic aromatic amino group is exemplified. Among them, thiol groups and / or phenolic hydroxyl groups are preferred from the viewpoint of high reactivity! /.
- the compound having two or more thiol groups is not particularly limited as long as it is a publicly known compound.
- alkylthiol compounds include 1,4 butanedithiol and 1,8-octanedithiol.
- compounds having other thiol groups include, for example, thiols obtained by the reaction of polyepoxide and hydrogen sulfide, mercaptocarboxylic acids having 2 to 20 carbon atoms and 2 to 3 or more functional groups (for example, mercaptoacetic acid, mercapto, etc.).
- an esterified product of propionic acid, mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid) and a polyol having 2 to 30 carbon atoms and 2 to 6 functional groups is preferred from the viewpoint of the performance of the cured product and availability.
- the compound having a phenolic hydroxyl group is not particularly limited as long as it is a known one, and examples thereof include phenol resins such as nopolac resin and resol resin.
- phenol resins such as nopolac resin and resol resin.
- nopolac resin is more preferable from the viewpoint of the performance of the cured product.
- nopolac resins include phenol nopolac resins and cresol nopolac resins. Among them, cresol nopolac resin is more preferable from the viewpoint of the performance of the cured product.
- the compound having two or more functional groups having reactivity with the epoxy resin in the molecule is based on the total amount of the above functional groups.
- ) / (Total amount of epoxy groups in the epoxy resin) (equivalent ratio) is preferably 0.5 ⁇ 1.5 to 1.5; 0.5 / 0.5. It is preferable that it is contained so as to have a ratio of 2 / 0.8.
- the photo-curable resin composition contains the above-mentioned compound in a forceful ratio, the curability tends to be further improved.
- polyamic acid which may be a single precursor or a mixture of two or more separately synthesized precursors, is preferably used.
- a polyamic acid can be obtained by mixing acid dianhydride and diamine in a solution. Therefore, the polyamic acid is preferable because it can be synthesized by a one-step reaction, can be easily synthesized, and can be obtained at low cost.
- the polyimide precursor has a portion derived from acid dianhydride having an aromatic structure
- the part derived from diamine is a wholly aromatic polyimide precursor containing an aromatic structure. Therefore, the structure of the portion derived from diamine is preferably a structure induced by aromatic diamine force.
- the wholly aromatic polyimide precursor refers to a polyimide precursor obtained by copolymerization of an aromatic acid component and an aromatic amine component, or polymerization of an aromatic acid / amino component, and a derivative thereof.
- the aromatic acid component means a compound in which all four acid groups forming the polyimide skeleton are substituted on the aromatic ring
- the aromatic amine component means two amino groups forming the polyimide skeleton. Both are compounds which are substituted on the aromatic ring.
- the aromatic acid / amino component is a compound in which both an acid group and an amino group forming a polyimide skeleton are substituted on the aromatic ring.
- a method for producing a polyimide precursor a conventionally known method can be applied. For example, it may be a method of synthesizing a precursor polyamic acid from acid dianhydride and diamine.
- a polyimide can be obtained by further reacting a diamino compound or a derivative thereof with a carboxylic acid such as an ester acid or an amido acid monomer obtained by reacting an acid dianhydride with a monohydric alcohol, an amino compound or an epoxy compound. It may be a method of synthesizing a precursor.
- the manufacturing method of a polyimide precursor is not limited to these.
- Acid dianhydrides applicable to the production of polyimide precursors include, for example, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic acid Dianhydride, pyromellitic dianhydride, 3, 3 ', 4, 4' benzophenone tetracarboxylic dianhydride, 2, 2 ', 3, 3'-benzophenone tetracarboxylic dianhydride, 3 , 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, 2, 2', 3, 3, monobiphenyltetracarboxylic dianhydride, 2, 2 ', 6, 6'-biphenyl lutetate Lacarboxylic acid dianhydride, 2, 2 bis (3,4 dicarboxyphenyl) propane dianhydride, 2, 2 bis (2, 3 di
- Particularly preferred tetracarboxylic dianhydrides include pyromellitic dianhydride, 3, 3, 4, 4, 4'-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, 2, 2 ', 6, 6, monobiphenyltetracarboxylic dianhydride, bis (3,4 dicarboxyphenyl) ether dianhydride, 2, 2 Bis (3,4 dicanoleboxoxyphenyl) 1, 1, 1, 3, 3, 3—hexafluoropropane dianhydride
- rigid acids such as pyromellitic anhydride, 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride
- dianhydride When dianhydride is used, the coefficient of linear thermal expansion of the final polyimide is reduced.
- Diamine which is an amine component, may be used alone or in combination of two or more.
- the diamine as the ammine component is not particularly limited, and examples thereof include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl.
- some or all of the hydrogen atoms on the aromatic ring of the diamine are selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group 1
- Diamines substituted with seeds or two or more substituents may be used.
- one or two selected from the group consisting of an ethur group, benzocyclobutene 4'-yl group, bur group, allyl group, cyano group, isocyanate group and isopropenyl group as a crosslinking point depending on the purpose. More than one species may be introduced as a substituent on some or all of the hydrogen atoms on the aromatic ring of the diamine.
- the diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient.
- the rigid diamine include diamines in which two amino groups are bonded to the same aromatic ring. Specifically, for example, p-phenylenediamine, m-phenylenediamine, 1, Examples include 4-diaminonaphthalene, 1,5 diaminonaphthalene, 2,6 diaminonaphthalene, 2,7 diaminonaphthalene, and 1,4-diaminoanthracene.
- two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded to a separate aromatic ring directly or as part of a substituent.
- An example of such a diamine is benzidine.
- the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance!
- the whole of the 60 mole 0/0 Jiamin preferably not exceeding 40 mole 0/0 range, other than the aromatic Jiamin, such as aliphatic Jiamin, siloxane Jiamin, the May be.
- the compound having an isocyanate group is not particularly limited as long as it has two or more isocyanate groups in the molecule, and a known one is adopted.
- examples of such compounds include p-phenylene diisocyanate, 2,4 toluene diisocyanate, 2,6 toluene diisocyanate, 1,5-naphthalenediisocyanate, hexamethylene diisocyanate.
- low molecular weight compounds represented by Other specific examples include, as such compounds, polymers having a weight average molecular weight of 3000 or more and having an isocyanate group at the side chain or terminal.
- the above-mentioned compound having an isocyanate group is used as the anion polymerizable resin, it is usually used in combination with a compound having two or more hydroxy groups in the molecule.
- the compound having a hydroxy group is not particularly limited, and known compounds are employed. Specific examples thereof include low molecular weight compounds typified by ethylene glycol, propylene glycol, glycerin, diglycerin, and pentaerythritol. Other specific examples include polymers having a weight average molecular weight of 3000 or more and having a hydroxy group at the side chain or terminal.
- a compound having two or more hydroxy groups in the molecule has a ratio (total amount of the hydroxy groups) / (total amount of the isocyanate groups) (equivalent ratio) to the compound having the isocyanate group of 0.5 / 1. It is preferable to use it in an amount that will give a ratio of 5/0. 5 In a quantity that will give a ratio of 2 / 0.8. More preferably it is used.
- the photocurable resin composition contains the above-mentioned compound in a strong proportion, the curability tends to be further improved.
- the content ratio of the photobase generator in the photocurable resin composition of the present embodiment is 100 parts by mass of the two-one polymerizable resin 0.001 to 100 parts by mass is preferable. 0.05 to 80 parts by mass is more preferable. When the content ratio of the photobase generator is within the above range, an effect that the performance of the cured product is more excellent can be obtained.
- the photocurable resin composition of the present embodiment may further contain an organic solvent as necessary.
- organic solvent include, but are not limited to, for example, jetyl ether, tetrahydrofuran, di-xane, ethylene glycol / resimethy / leete / le, ethylene glycol / legetinoleatenore, propyleneglyco-resinetinoreatenore, propyleneglycolone.
- Ethers typified by retinoic ethers: ethylene glycol monomethyl ether, ethylene glycol monomethenoate ethere, propylene glycol monomethinoate ethere, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, jetylene glycol Glyconore monoetherenoles (so-called cellosolves) represented by noremonocheinoreethenore; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclo Ketones typified by ntanone and cyclohexanone; ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above-mentioned glycol monoethers (for example, methylacetate) Sorbacetate,
- Organic polar solvents are mentioned. Furthermore, examples of the organic solvent include aromatic hydrocarbons represented by benzene, toluene and xylene, and other organic nonpolar solvents. These organic solvents can be used alone or in combination of two or more. Used.
- the photo-curable resin composition of the present embodiment further includes barium sulfate, if necessary, for the purpose of improving various properties such as adhesion between the cured product and the substrate and hardness of the cured product.
- barium sulfate if necessary, for the purpose of improving various properties such as adhesion between the cured product and the substrate and hardness of the cured product.
- Contains well-known inorganic fillers such as sodium titanate, calcium oxide powder, fine powdered silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc.
- the photo-curable resin composition of the present embodiment may be prepared by using phthalocyanine butylene, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black as necessary.
- Known colorants represented by: hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, known polymerization inhibitors represented by phenothiazine, known thickeners represented by asbestos, olben, benton, montmorillonite , Silicone-based, fluorine-based, high-molecular-weight antifoaming agents, and / or adhesion-imparting agents represented by leveling agents, imidazole-based, thiazole-based, triazole-based, and silane coupling agents.
- Known additives hindered phenol acids Inhibitor may contain etc. hindered amine light stabilizer (HALS).
- the photocurable resin composition of the present embodiment may contain one or more known photoradical initiators such as benzophenone, benzophenone derivatives, acetophenone, and acetophenone derivatives as necessary. ! /
- the photocurable resin composition of the present embodiment may be subjected to light irradiation only, light irradiation and heating at the same time, or heating after light irradiation.
- the light irradiation is preferably performed using irradiation light having a wavelength range of 150 to 750 nm. More specifically, low pressure mercury lamp, medium pressure mercury lamps, high pressure mercury lamp, ultra-high pressure mercury lamp, 0.0 using a key Senonranpu and / or a metal halide lamp; by performing light irradiation at an irradiation amount of ⁇ 100j / cm 2!
- the photocurable resin composition can be cured.
- the above-mentioned light irradiation is preferably performed with an irradiation dose of 0.05 to 20 j / cm 2 using irradiation light in a wavelength region of 200 to 400 nm.
- the heating temperature when heating is not particularly limited as long as it is a temperature below the decomposition point of the anion polymerizable resin, and a temperature of 30 to 400 ° C is preferable. More preferably, the temperature is 50 to 300 ° C.
- the heating time in the case of heating is preferably 1 second to 3 hours, and more preferably 30 seconds to 1 hour, in order to perform curing more sufficiently.
- the photocurable resin composition of the present embodiment can be patterned using the same.
- the pattern of the pattern is as follows. That is, the surface of a coating film or a molded body obtained by applying the resin composition to a base material is irradiated with light in a predetermined pattern through a photomask or the like. As a result, the coated film or the part of the molded body (light-irradiated part) irradiated with light is cured to form a latent image. Next, post-treatment such as heat treatment is applied to the coated film or molded body after light irradiation as necessary to selectively lower the solubility of the light irradiated site of the coated film or molded body. Thereafter, a pattern is formed by selectively removing a non-light-irradiated portion of the coating film or molded body using a developing solution such as an aqueous solution or an organic solvent.
- a developing solution such as an aqueous solution or an organic solvent.
- the method for applying the photocurable resin composition of the present embodiment to a substrate is not particularly limited.
- the developer used for selectively removing the non-light-irradiated portion of the coating film or molded product is not particularly limited, and examples thereof include basic aqueous solutions, organic solvents, acidic aqueous solutions, and neutral aqueous solutions. .
- the developer may be appropriately selected depending on the curable components such as the polymer precursor contained in the photocurable resin composition.
- the basic aqueous solution is not particularly limited.
- TMAH tetramethylammonium hydroxide
- potassium hydroxide aqueous solution sodium hydroxide aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, carbonate
- Examples include aqueous sodium hydrogen solution, aqueous solutions of primary, secondary, and tertiary amines, and aqueous solutions of hydroxide ions and ammonium ions.
- the alkali concentration of the basic aqueous solution is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass.
- the concentration is preferably 50% or more, more preferably 70% or more of the total mass.
- the basic aqueous solution may further contain a solvent other than water, such as an organic solvent, as long as it contains water.
- Basic aqueous solutions may be used alone or in combination of two or more.
- the organic solvent used as the developing solution is not particularly limited, and examples thereof include jetino reetenole, tetrahydrofuran, dixane, ethylene glyconoresin methinoreatenore, ethylene glycono lese chinenoreatenore, propylene glyconoresin methinoreatenore.
- Ethers typified by propylene glycol jetyl ether; ethylene glycol monomethylenoateolene, ethyleneglycolenomethinoleethenole, propyleneglycolonemonomethylether, propyleneglycolmonoethylether, diethyleneglycolmonomethylether , Glycol monoethers represented by diethylene glycol monoethyl ether (so-called cellosolves); methyl ethyl ketone, acetone, methyl isobutyl Ketones typified by ruketone, cyclopentanone, cyclohexanone; ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, , Methyl sucrose sorb acetate, To,
- these organic solvents may be used as a mixed solvent in combination with water, a basic aqueous solution and / or an acidic aqueous solution.
- the acidic aqueous solution is not particularly limited as long as it has a pH of less than 7.
- Examples of the acidic aqueous solution include aqueous solutions of organic acids represented by lactic acid, acetic acid, oxalic acid, and malic acid, and aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
- the photo-curable resin composition of the present embodiment includes an adhesive such as a paint and a conductive adhesive, an ink typified by a printing ink, a resist material such as a photoresist and a solder resist, a cover layer, and a coating material.
- composition of the photocurable resin composition of the present embodiment is adjusted according to various properties such as desired heat resistance, dimensional stability, and insulation in these applications.
- the photocurable resin composition of the present embodiment includes an anisotropic conductive adhesive, a silver paste, a silver film, as well as an adhesive that bonds wood, building materials, plastics, leather, and the like. It can be used as a semiconductor element adhesive material such as an anisotropic conductive material for flip chip that connects a circuit connecting material typified by an film, a semiconductor element typified by a flip chip, and a printed wiring board.
- the mixture was stirred and extracted twice with 30 mL of jetyl ether. After adding MgSO to the obtained jetyl ether extract, drying and filtering, the jetyl ether was extracted under reduced pressure.
- Bisphenol A type epoxy resin (trade name “AER250” manufactured by Asahi Kasei Chemicals Corporation) 70 parts by mass, tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 30 parts by mass and the above-mentioned 10 parts by mass of 2-methylaminotropone synthesized by the above method was mixed to obtain a photocurable resin composition.
- the obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of ⁇ .
- the coating film was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere, the curing reaction proceeded and a semi-solid film was obtained.
- the semi-solid film was heated at 120 ° C. for 10 minutes, it was completely cured, and a strong solid film (cured film) was obtained. Gas generation was not observed during light irradiation or heat curing, and a homogeneous solid film was obtained.
- the cyclohexane solution (1% by mass) of 2-methylaminotrobon obtained as described above was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere.
- ion-exchanged water was added to obtain a 0.01 mol / L aqueous solution.
- the pH of the obtained aqueous solution was measured with a pH meter (trade name “HM 30G” manufactured by Toa Denpa Kogyo Co., Ltd.).
- a pH meter trade name “HM 30G” manufactured by Toa Denpa Kogyo Co., Ltd.
- the cyclohexane solution (1% by mass) of 2-methylaminotrobon obtained as described above was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere.
- This ultraviolet The molecular weight before and after irradiation was measured with a mass spectrometer (manufactured by Shimadzu Corporation, trade name “MALDI-TOF / MAS, AXIMA CFR plus”).
- MALDI-TOF / MAS, AXIMA CFR plus mass spectrometer
- the cyclohexane solution (1% by mass) of methylaminoisopropyltrobon obtained as described above was irradiated with 6 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere.
- ion-exchanged water was added to obtain a 0. Olmol / L aqueous solution.
- the pH of the resulting aqueous solution was measured with a pH meter (trade name “HM-30G” manufactured by Toa Denpa Kogyo Co., Ltd.).
- a pH meter trade name “HM-30G” manufactured by Toa Denpa Kogyo Co., Ltd.
- the cyclohexane solution (1% by mass) of methylaminoisopropyltrobon obtained as described above was irradiated with 6 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere.
- the molecular weight before and after the ultraviolet irradiation was measured with a mass spectrometer (trade name “MALDI TOF / MAS, AXIMA CFR plus” manufactured by Shimadzu Corporation).
- MALDI TOF / MAS, AXIMA CFR plus manufactured by Shimadzu Corporation
- Bisphenol A type epoxy resin (trade name “AER 2 50” manufactured by Asahi Kasei Chemical Co., Ltd.) 70 parts by mass, tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 30 parts by mass and Examples
- a resin composition was obtained by mixing 10 parts by mass of 2-methylaminotropone synthesized by the same method as in 1. The obtained resin composition was applied on a glass plate to form a coating film having a thickness of 100 m. When the coating film was heated at 120 ° C for 30 minutes without irradiating it with ultraviolet rays, no hardening of the coating film was observed.
- Bisphenol A type epoxy resin (trade name “AER 2 50” manufactured by Asahi Kasei Chemical Co., Ltd.) 70 parts by mass, tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 30 parts by mass and Examples
- a resin composition was obtained by mixing 10 parts by mass of methylaminoisopropyltrobon synthesized in the same manner as in 2. The obtained resin composition was applied on a glass plate to form a coating film having a thickness of 100 ⁇ . When the coating film was heated at 120 ° C for 30 minutes without irradiating it with ultraviolet rays, no hardening of the coating film was observed.
- the coating film was irradiated with 6 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere and heated at 120 ° C. for 10 minutes. Although hardening of the coating film was observed, formation of bubbles was observed in the cured solid film, and a homogeneous solid film was not obtained.
- a photocurable resin composition was obtained by mixing 10 parts by mass of N-methyl-2-cyanobilol, which is a photobase generator. The obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100.
- the coating film was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 254 nm) in a nitrogen atmosphere, the curing reaction proceeded and a semi-solid film was obtained.
- the semi-solid film was heated at 120 ° C. for 10 minutes, it was completely cured and a strong solid film (cured film) was obtained. Gas generation was not observed during light irradiation or heat curing, and a homogeneous solid film was obtained.
- a methanol solution of N-methyl-2-cyanobilol obtained as described above (pH of 0.01 mol / U was measured to be 6.6.
- This solution was converted into a quartz cell (10 mm x 10 mm). X 45 mm, optical path length 10 mm)
- the cell was irradiated with UV light at a wavelength of 254 nm at 7.8 J / cm 2.
- the pH rose to 8.2 and became basic.
- the pH was measured using a pH meter (trade name “HM-30G” manufactured by Toa Denpa Kogyo Co., Ltd.) after the solution was diluted 8 times with ion-exchanged water.
- Epoxy resin manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name “SR—TMP” 50 parts by mass, tetrakis (mercaptoacetic acid) pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) 2 5 parts by mass, Talesol Nopolac resin (Asahi) 50% by mass ethanol from Organic Materials Industry Co., Ltd.
- the coating film was irradiated with 9j / cm 2 of ultraviolet rays (wavelength: 365nm) in a nitrogen atmosphere through a photomask on which predetermined characters were drawn. A latent image was formed.
- the coating film on which the latent image was formed was heated at 120 ° C for 3 minutes until the latent image portion was completely cured, then developed with 0.26N aqueous sodium hydroxide solution, washed with water and dried. Thus, a pattern in which characters drawn on the photomask were clearly engraved in a negative shape was formed. No gas was observed during light irradiation or heating, and a uniform and strong pattern was obtained.
- a pattern was formed in the same manner as in Example 4 except that N- (2-nitrobenzeneoxycarbonyl) pyrrolidine used in Comparative Example 1 was used instead of methylaminoisopropyl trobon.
- N- (2-nitrobenzeneoxycarbonyl) pyrrolidine used in Comparative Example 1 was used instead of methylaminoisopropyl trobon.
- a photocurable resin composition was obtained in the same manner as in Example 1 except that 2-aminotropone synthesized by a known method was used instead of 2-methylaminotrobon.
- the obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100 inches.
- the coating film was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere, the curing reaction proceeded and a semi-solid film was obtained.
- the semi-solid film was completely cured when heated at 120 ° C. for 20 minutes, and a solid solid film (cured film) was obtained. Gas generation was not observed during light irradiation or heat curing, and a homogeneous solid film was obtained.
- a photocurable resin composition was obtained in the same manner as in Example 1 except that 2-acetylaminotropone synthesized by a known method was used in place of 2-methylaminotropone.
- the obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100.
- the coating film was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere, the curing reaction proceeded and a semi-solid film was obtained.
- the semi-solid film was heated at 120 ° C. for 30 minutes, it was completely cured, and a strong solid film (cured film) was obtained.
- generation of gas was not observed during light irradiation or heat curing, and a homogeneous solid film was obtained.
- 2-Isopropylaminotropolone a photobase generator
- 2-Isopropylaminotropolone a photobase generator
- a photocurable resin composition was obtained in the same manner as in Example 1 except that 2-isopropylaminotrobolone was used in place of 2-methylaminotrobon.
- the obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100 ⁇ . 9j / cm 2 UV light under nitrogen atmosphere
- irradiated wavelength: 365 nm
- the curing reaction proceeded and a semi-solid film was obtained.
- the semi-solid film was heated at 120 ° C. for 20 minutes, it was completely cured, and a strong solid film (cured film) was obtained. Gas generation was not observed during light irradiation or heat curing, and a homogeneous solid film was obtained.
- a photocurable resin composition was obtained in the same manner as in Example 1 except that tetrakis (mercaptoacetic acid) pentaerythritol was not blended.
- the obtained photocurable resin composition was applied on a glass plate to form a coating film having a thickness of 100.
- the coating film was irradiated with 9 j / cm 2 of ultraviolet light (wavelength: 365 nm) in a nitrogen atmosphere, the curing reaction proceeded and a semi-solid film was obtained.
- the semi-solid film was heated at 120 ° C. for 30 minutes, it was completely cured and a solid solid film (cured film) was obtained. Gas generation was not observed during light irradiation or heat curing, and a homogeneous solid film was obtained.
- a photocurable resin composition was obtained in the same manner as in Example 4 except that no cresol nopolac resin was added.
- the obtained photocurable resin composition was apply
- the coating film was irradiated with 9j / cm 2 of ultraviolet light (wavelength: 365nm) in a nitrogen atmosphere through a photomask on which predetermined characters were drawn.
- a latent image was formed.
- the coating film on which the latent image was formed was heated at 120 ° C. for 15 minutes until the latent image portion was completely cured, then developed with 0.26N aqueous sodium hydroxide solution, washed with water and dried. In this way, a pattern in which the letters drawn on the photomask were clearly engraved in a negative shape was formed. Gas generation was not observed during light irradiation or heating, and a uniform and strong pattern was obtained.
- a pattern was formed in the same manner as in Example 5 except that N- (2-nitrobenzeneoxycarbonyl) pyrrolidine used in Comparative Example 1 was used instead of methylaminoisopropyl trobon.
- N- (2-nitrobenzeneoxycarbonyl) pyrrolidine used in Comparative Example 1 was used instead of methylaminoisopropyl trobon.
- the present invention can be used for a photobase generator suitable for photocuring of any curable resin such as epoxy resin and polyimide resin, and a photocurable resin composition containing the photobase generator. More specifically, the present invention strictly demands insulation reliability, heat resistance, fine workability, etc., while expressing or increasing basicity while sufficiently suppressing the generation of unnecessary by-products such as gas and water.
- the present invention can be used for a photobase generator particularly useful for curing a resin for electronic materials and a photocurable resin composition containing the photobase generator.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/518,313 US8137892B2 (en) | 2006-12-14 | 2007-12-12 | Photobase generator and photocurable resin composition |
KR1020097008290A KR101114694B1 (ko) | 2006-12-14 | 2007-12-12 | 광염기 발생제 및 광경화성 수지조성물 |
CN2007800456703A CN101553549B (zh) | 2006-12-14 | 2007-12-12 | 光产碱剂和光固化性树脂组合物 |
JP2008549327A JP5356828B2 (ja) | 2006-12-14 | 2007-12-12 | 光塩基発生剤及び光硬化性樹脂組成物 |
EP07850467A EP2093269A4 (en) | 2006-12-14 | 2007-12-12 | PHOTOBASE GENERATOR AND PHOTOCURABLE RESIN COMPOSITION |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2006-336901 | 2006-12-14 | ||
JP2006336901 | 2006-12-14 |
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WO2008072651A1 true WO2008072651A1 (ja) | 2008-06-19 |
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PCT/JP2007/073916 WO2008072651A1 (ja) | 2006-12-14 | 2007-12-12 | 光塩基発生剤及び光硬化性樹脂組成物 |
Country Status (7)
Country | Link |
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US (1) | US8137892B2 (ja) |
EP (1) | EP2093269A4 (ja) |
JP (1) | JP5356828B2 (ja) |
KR (1) | KR101114694B1 (ja) |
CN (1) | CN101553549B (ja) |
TW (1) | TW200848924A (ja) |
WO (1) | WO2008072651A1 (ja) |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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US8536242B2 (en) | 2007-08-09 | 2013-09-17 | Sekisui Chemical Co., Ltd. | Photocurable composition |
WO2009019979A1 (ja) * | 2007-08-09 | 2009-02-12 | Sekisui Chemical Co., Ltd. | 光硬化性組成物 |
JP2010095686A (ja) * | 2008-10-20 | 2010-04-30 | Asahi Kasei E-Materials Corp | 光塩基発生剤及び光硬化性樹脂組成物 |
JP2010105930A (ja) * | 2008-10-28 | 2010-05-13 | Asahi Kasei E-Materials Corp | 光塩基発生剤及び光硬化型樹脂組成物 |
JP2010111782A (ja) * | 2008-11-06 | 2010-05-20 | Asahi Kasei E-Materials Corp | 光硬化型樹脂組成物、その硬化物及び硬化物の製造方法 |
JP2010126662A (ja) * | 2008-11-28 | 2010-06-10 | Asahi Kasei E-Materials Corp | 光塩基発生剤、それを用いた光硬化性樹脂組成物及び硬化物 |
WO2010064632A1 (ja) * | 2008-12-02 | 2010-06-10 | 和光純薬工業株式会社 | 光塩基発生剤 |
JP2010174210A (ja) * | 2009-02-02 | 2010-08-12 | Asahi Kasei E-Materials Corp | 光硬化型樹脂組成物及びその硬化物 |
JP2011195616A (ja) * | 2010-03-17 | 2011-10-06 | Eiweiss Kk | 光硬化性樹脂組成物 |
JP2011236416A (ja) * | 2010-04-14 | 2011-11-24 | Tokyo Univ Of Science | 感光性樹脂組成物 |
JP2012001612A (ja) * | 2010-06-16 | 2012-01-05 | Asahi Kasei E-Materials Corp | 光硬化型樹脂組成物、パターン形成された基板の製造方法及び電子部品 |
JP2012159657A (ja) * | 2011-01-31 | 2012-08-23 | Asahi Kasei E-Materials Corp | 光硬化型樹脂組成物及びそれを用いたパターン形成された基材の製造方法、並びに該基材を備える電子部品 |
JP2017125101A (ja) * | 2016-01-12 | 2017-07-20 | 太陽インキ製造株式会社 | 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 |
Also Published As
Publication number | Publication date |
---|---|
CN101553549B (zh) | 2013-02-20 |
JP5356828B2 (ja) | 2013-12-04 |
TW200848924A (en) | 2008-12-16 |
EP2093269A4 (en) | 2011-03-30 |
US8137892B2 (en) | 2012-03-20 |
US20100151386A1 (en) | 2010-06-17 |
TWI367392B (ja) | 2012-07-01 |
KR101114694B1 (ko) | 2012-03-13 |
EP2093269A1 (en) | 2009-08-26 |
JPWO2008072651A1 (ja) | 2010-04-02 |
CN101553549A (zh) | 2009-10-07 |
KR20090057319A (ko) | 2009-06-04 |
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