WO2016208472A1 - 光硬化性樹脂組成物 - Google Patents
光硬化性樹脂組成物 Download PDFInfo
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- WO2016208472A1 WO2016208472A1 PCT/JP2016/067824 JP2016067824W WO2016208472A1 WO 2016208472 A1 WO2016208472 A1 WO 2016208472A1 JP 2016067824 W JP2016067824 W JP 2016067824W WO 2016208472 A1 WO2016208472 A1 WO 2016208472A1
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- photocurable resin
- resin composition
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- 0 C*CC(COC(C(CC=CC1)C1C(OCC(COC(C(CCCC1)C1C(O*(C)C)=O)=O)O)=O)=O)O Chemical compound C*CC(COC(C(CC=CC1)C1C(OCC(COC(C(CCCC1)C1C(O*(C)C)=O)=O)O)=O)=O)O 0.000 description 1
- NUEMXJGUIYNOCA-UHFFFAOYSA-N CC(C)CC(COC(CC1)CCC1C(C)(C)C(CC1)CCC1OCC(COC(C(CCCC1)C1C(OC)=O)=O)O)O Chemical compound CC(C)CC(COC(CC1)CCC1C(C)(C)C(CC1)CCC1OCC(COC(C(CCCC1)C1C(OC)=O)=O)O)O NUEMXJGUIYNOCA-UHFFFAOYSA-N 0.000 description 1
- SHKCAWMMMREMFC-UHFFFAOYSA-N CCC(CN(C(N(CC(COC(C(CCCC1)C1C(OC)=[U])=O)O)C(N1CC=C)=O)=O)C1=O)O Chemical compound CCC(CN(C(N(CC(COC(C(CCCC1)C1C(OC)=[U])=O)O)C(N1CC=C)=O)=O)C1=O)O SHKCAWMMMREMFC-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/065—Polyamides; Polyesteramides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
- C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a photocurable resin composition containing a polymer into which a site capable of radical crosslinking is introduced.
- Patent Document 1 discloses an isocyanuric ring-containing polymer used for an optical semiconductor adhesive and a composition containing the polymer.
- the isocyanuric ring-containing polymer is prepared by reacting N-monosubstituted isocyanuric acid with a dihalogen compound in the presence of an alkali metal compound, or hydrosilylating N, N ′, N ′′ -trisubstituted isocyanuric acid with a silane compound.
- the composition can be bonded as an adhesive for an optical semiconductor by heating in an oven at 50 ° C. to 250 ° C. for 30 minutes to 4 hours. Has been.
- a liquid crystal display uses a glass substrate as the base material of the display panel.
- PET resin, PEN resin, and PC resin which are known as resin materials used for known plastic substrates, have a heat resistance of only about 250 ° C., which has been conventionally required for thin film transistor (TFT) formation processes at 250 ° C. or higher.
- TFT thin film transistor
- Patent Document 2 discloses a composition capable of obtaining a cured film having high visible light transmittance and excellent heat resistance and solvent resistance. Further, the document discloses that the composition can be used as an adhesive.
- the cured product produced from the composition described in Patent Document 1 is evaluated to have a light transmittance of 90% or more at 470 nm, and is further evaluated for heat resistance.
- the transmittance at 470 nm after the cured product was left in an oven at 150 ° C. for 120 hours was measured, but the heat resistance at a temperature of 250 ° C. or higher is unknown. Therefore, when the composition described in Patent Document 1 is used in a process that requires a high temperature of 250 ° C. or higher, the cured product obtained from the composition may not have a high visible light transmittance. is there.
- the temperature is 200 ° C. or higher.
- the present inventors have devised the terminal structure of the polymer constituting the composition, thereby providing desired properties without requiring a heating step at the above temperature. It was found that a cured film can be formed from the composition.
- the first aspect of the present invention has a weight average molecular weight of 1,000 to 50,000 having a structural unit represented by the following formula (1) and having a structure represented by the following formula (2) at the terminal.
- a photocurable resin composition comprising a polymer of the above, a radical photopolymerization initiator, and a solvent.
- X represents an alkyl group having 1 to 6 carbon atoms, a vinyl group, an allyl group, or a glycidyl group
- m and n each independently represents 0 or 1
- Q represents 2 having 1 to 16 carbon atoms.
- Z represents a divalent linking group having 1 to 4 carbon atoms, the divalent linking group is bonded to the —O— group in the formula (1), and R 1 represents hydrogen. Represents an atom or a methyl group.
- the divalent hydrocarbon group represented by Q in the formula (1) is, for example, a linear or branched alkylene group, a group containing two carbon atoms connected by a double bond, or a substituent. Represents a group containing an alicyclic hydrocarbon group or an aromatic hydrocarbon group in the main chain.
- the divalent linking group represented by Z represents, for example, a linear or branched alkylene group which may have at least one hydroxy group as a substituent.
- the photocurable resin composition may further contain a bifunctional (meth) acrylate and / or a polyfunctional thiol.
- the photocurable resin composition can be used as an adhesive or a lens material.
- the second aspect of the present invention includes a step of applying the photocurable resin composition of the first aspect of the present invention onto a substrate, and a temperature of 50 ° C to 160 ° C of the photocurable resin composition applied onto the substrate. And a step of exposing the coating film formed on the substrate after the pre-baking, and a step of developing the coating film.
- the photocurable resin composition of the present invention does not require a heating step at a temperature of 200 ° C. or higher because it contains a polymer having a radical-crosslinkable site introduced at the terminal and a radical photopolymerization initiator.
- a cured film having high visible light transmittance and excellent heat resistance and solvent resistance can be formed. This cured film is useful as a lens material.
- the cured film formed from the photocurable resin composition of the present invention is also excellent in moisture permeability prevention. Furthermore, since the photocurable resin composition of the present invention has high adhesive force, it is useful as an adhesive for organic EL displays and image sensors.
- the photocurable resin composition of the present invention has a weight average molecular weight of 1,000 to 50, having a structural unit represented by the formula (1) and having a structure represented by the formula (2) at the terminal. 000 polymers.
- This weight average molecular weight is a standard polystyrene equivalent value, preferably 1,000 to 20,000, by gel permeation chromatography (hereinafter abbreviated as GPC in this specification) analysis described later.
- Examples of the alkyl group having 1 to 6 carbon atoms represented by X in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s -Butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl -N-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-buty
- the divalent hydrocarbon group having 1 to 16 carbon atoms represented by Q in the formula (1) is, for example, a linear or branched alkylene group or two carbon atoms connected by a double bond Or a group containing an alicyclic hydrocarbon group or aromatic hydrocarbon group which may have at least one substituent in the main chain.
- Examples of such groups include groups represented by the following formulas (a) to (m).
- the divalent linking group having 1 to 4 carbon atoms represented by Z may have, for example, at least one hydroxy group as a substituent, linear or branched Represents an alkylene group.
- Z represents such an alkylene group
- examples of the terminal structure represented by the formula (2) include structures represented by the following formulas (2-1) and (2-2).
- the polymer is synthesized, for example, through the following process. Diepoxy compound having a triazine trione structure is reacted with a compound having a carboxyl group or a hydroxy group at the terminal, and the structural unit represented by the formula (1) and a polymer intermediate having a carboxyl group or a hydroxy group at the terminal Get. Thereafter, the polymer intermediate having the terminal is reacted with (meth) acrylate having an epoxy group.
- the photocurable resin composition of the present invention contains a radical photopolymerization initiator.
- the photopolymerization initiator is not particularly limited as long as it is a compound having absorption in a light source used during photocuring.
- tert-butylperoxy-iso-butyrate 2,5-dimethyl-2,5-bis (benzoyl) Dioxy) hexane
- 1,4-bis [ ⁇ - (tert-butyldioxy) -iso-propoxy] benzene di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydro Peroxide, ⁇ - (iso-propylphenyl) -iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (Tert-Butyldioxy) valerate, cyclohexano Peroxide, 2,2 ′, 5,5′-tetra (tert-butylperoxycarbonyl) benzophenone,
- benzoin derivatives such as benzoin methyl, benzoin ethyl ether, ⁇ -methylbenzoin, ⁇ -phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl- Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy-2-methyl-propionyl) benzyl ⁇ -phenyl] -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethyl
- the radical photopolymerization initiator can be obtained as a commercial product, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW. 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, TPO, 4265, TPO (above, manufactured by BASF), KAYACURE [registered trademark] DETX, MBP , DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VISURE-10, 55 (manufactured by STAUFER Co.
- the content of the radical photopolymerization initiator in the photocurable resin composition of the present invention is, for example, 0.01 phr to 30 phr, preferably 0.1 phr to 15 phr with respect to the content of the polymer. When the content ratio is less than the lower limit, sufficient curability cannot be obtained.
- phr represents the mass of the radical photopolymerization initiator with respect to 100 g of the polymer.
- the photocurable resin composition of the present invention contains a solvent.
- the solvent is not particularly limited as long as it is an organic solvent that can be used in the semiconductor device manufacturing process.
- ketones such as cyclohexanone, methyl isoamyl ketone, 2-butanone, and 2-heptanone
- ethylene glycol ethylene glycol monoacetate, diethylene glycol , Diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate
- polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and the like, and Derivatives thereof
- cyclic ethers such as dioxane
- lactones such as ⁇ -butyrolactone
- methyl lactate ethyl lactate, methyl acetate Ethyl acetate, butyl a
- organic solvents may be used alone or in combination of two or more.
- the component excluding the solvent from the photocurable resin composition of the present invention is defined as a solid content
- the ratio of the solid content in the photocurable resin composition is, for example, 1% by mass to 80% by mass.
- the photocurable resin composition of this invention can contain a bifunctional (meth) acrylate as a crosslinkable compound as needed.
- the bifunctional (meth) acrylate is a compound having an acryloyl group or a methacryloyl group at both ends of the molecule.
- the compound include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, and tricyclodecane diethanol dimethacrylate.
- the bifunctional (meth) acrylate can be obtained as a commercial product, and examples thereof include A-DCP and DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more.
- the content of the bifunctional (meth) acrylate in the photocurable resin composition of the present invention is, for example, 5% by mass to 50% by mass, preferably 10% by mass to 30% by mass with respect to the content of the polymer. is there.
- the photocurable resin composition of the present invention can further contain a polyfunctional thiol as a crosslinkable compound, if necessary.
- the polyfunctional thiol is a compound having a plurality of (for example, two, three, or four) thiol groups at the end of the molecule.
- Examples of the compound include pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), and trimethylolethane tris (3-mercaptobutyrate).
- the polyfunctional thiol can be obtained as a commercially available product, and examples thereof include Karenz MT [registered trademark] PE1, BD1, and NR1 (manufactured by Showa Denko KK). These compounds may be used alone or in combination of two or more.
- the content of the polyfunctional thiol in the photocurable resin composition of the present invention is, for example, 0.1% by mass to 15% by mass, preferably 0.5% by mass to 10% by mass with respect to the content of the polymer. It is.
- the photocurable resin composition of this invention can further contain additives, such as an epoxy compound, a photo-acid generator, a thermal acid generator, an inorganic filler, and surfactant, as needed.
- additives such as an epoxy compound, a photo-acid generator, a thermal acid generator, an inorganic filler, and surfactant, as needed.
- the photocurable resin composition of the present invention contains an epoxy compound
- examples of the epoxy compound include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl.
- Ether diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4′-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p-aminopheno Tetraglycidyl meta-xylenediamine, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S-diglycidyl ether, pentaeryth
- the epoxy compound is available as a commercial product.
- Epolide registered trademark] GT-401, GT-403, GT-301, GT-302, PB3600, Celoxide [registered trademark] 2021P, 2000, 3000, EHPE3150, EHPE3150CE, Cyclomer [registered trademark] M100 (above, manufactured by Daicel Corporation), EPICLON [registered trademark] 840, 840-S, N-660, N-673-80M (Above, manufactured by DIC Corporation).
- the photoacid generator include IRGACURE [registered trademark] PAG103, PAG108, PAG121, PAG203, CGI725, GSID-26- 1 (above, manufactured by BASF), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (above, manufactured by Wako Pure Chemical Industries, Ltd.), TFE triazine, TME- And triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (manufactured by Sanwa Chemical Co., Ltd.).
- thermal acid generator examples include K-PURE [registered trademark] TAG-2690, TAG-2690, TAG-2700, and CXC. -1612, CXC-1614, CXC-1615, CXC-1821 (above, manufactured by King Industries).
- the photocurable resin composition of the present invention contains an inorganic filler
- examples of the inorganic filler include sols such as silica, aluminum nitride, boron nitride, zirconia, and alumina.
- the photocurable resin composition of the present invention contains a surfactant
- examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether.
- Polyoxyethylene alkyl aryl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl aryl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate Sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxye Nonionic interfaces such as polyoxyethylene sorbitan fatty acid esters such as lensorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate An activator is mentioned.
- the surfactant is available as a commercial product.
- EFTOP [registered trademark] EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), MegaFuck [registered trademark] F171 F173, R-30, R-30N, R-40, R-40, LM (above DIC Corporation), Florard FC430, FC431 (above, Sumitomo 3M Limited) Fluorosurfactants such as Asahi Guard [registered trademark] AG710, Surflon [registered trademark] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) And an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more.
- the following steps that is, the step of applying the photocurable resin composition of the present invention on a substrate, the photocurable resin composition applied on the substrate 50 A cured film can be formed through a step of pre-baking at a temperature of from 0 to 160 ° C., a step of exposing the coating film formed on the substrate after the pre-baking, and a step of developing the coating film.
- Examples of the method for applying the photocurable resin composition of the present invention to a substrate include, for example, spin coating, potting, dipping, flow coating, ink jet, spraying, bar coating, gravure coating, and slit coating. , Roll coating method, transfer printing method, brush coating, blade coating method, and air knife coating method.
- a substrate to which the photocurable resin composition of the present invention is applied for example, a silicon wafer coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, an alkali-free glass substrate, a low Alkali glass substrate, crystallized glass substrate, glass substrate on which indium tin oxide (ITO) film or indium zinc oxide (IZO) film is formed, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), polyethylene (PE), polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), polycycloolefin (PCO), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), polypropylene (PP) , Polycarbonate (PC), polystyrene ( S), polyacrylonitrile (PAN), ethylene vinyl acetate cop
- the prebaking is performed to remove the solvent from the photocurable resin composition applied on the substrate, and as a result, a coating film that loses fluidity is formed on the substrate. .
- post-exposure baking (abbreviated as Post Exposure Bake, PEB) is performed at a temperature of, for example, 50 ° C. to 160 ° C. May be.
- Examples of the light source used when exposing the coating film include g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser.
- Examples of the developer used for developing the coating film include a solvent contained in the photocurable resin composition.
- a known organic solvent can be used as a solvent for the photoresist solution used in the photolithography process.
- Examples of the organic solvent include propylene glycol 1-monomethyl ether 2-acetate, 1-methoxy-2-propanol, cyclohexanone, and 2-propanol. These organic solvents may be used alone or in combination of two or more.
- the obtained polymer is considered to be a polymer having a structure represented by the following formula (1a) and a structure represented by the following formula (2a) at the terminal.
- the obtained polymer is considered to be a polymer having a structural unit represented by the following formula (1b) and a structure represented by the following formula (2b) at the terminal.
- the obtained polymer is considered to be a polymer having a structure represented by the following formula (2c) at the terminal and a structural unit represented by the following formula (1c).
- the obtained polymer is considered to be a polymer having a structural unit represented by the following formula (1d) and a structure represented by the following formula (2d) at the terminal.
- the obtained polymer is considered to be a polymer having a structure represented by the following formula (2e) at the terminal and a structural unit represented by the following formula (3).
- the obtained polymer is considered to be a polymer having a structural unit represented by the following formula (4) and a structure represented by the following formula (2f) at the terminal.
- the obtained polymer is considered to be a polymer having a structural unit represented by the following formula (5) and a structure represented by the following formula (2g) at the terminal.
- the obtained polymer is considered to be a polymer having a structural unit represented by the following formula (8) and a structure represented by the following formula (2h) at the terminal.
- the obtained polymer is considered to be a polymer having a structural unit represented by the following formula (9) and a structure represented by the following formula (2i) at the terminal.
- Example 1 The solution containing the polymer obtained in Synthesis Example 1 was injected into a bottle filled with a cation exchange resin (15JWET, Organo Corp.) and an anion exchange resin (Monosphere 550A, Muromachi Technos Corp.). Stir for 4 hours.
- a cation exchange resin (15JWET, Organo Corp.)
- an anion exchange resin (Monosphere 550A, Muromachi Technos Corp.).
- IRGACURE [registered trademark] 184 (manufactured by BASF) 0.68 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.08 g, and pentaerythritol tetrakis (3-mercapto) Butyrate (0.34 g, Showa Denko KK) was dissolved in 8.90 g of propylene glycol 1-monomethyl ether 2-acetate to prepare a composition. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- Example 2 The solution containing the polymer obtained in Synthesis Example 2 was filled with a cation exchange resin (15 JWET, Organo Corporation) and an anion exchange resin (Monosphere [registered trademark] 550A, Muromachi Technos Co., Ltd.). Poured into and allowed to stir for 4 hours.
- IRGACURE184 manufactured by BASF 0.60 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.62 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa)
- a composition was prepared by dissolving 0.30 g of Denko Co., Ltd. in 3.62 g of propylene glycol 1-monomethyl ether 2-acetate. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- Example 3 The solution containing the polymer obtained in Synthesis Example 3 was injected into a bottle filled with a cation exchange resin (15JWET, Organo Corp.) and an anion exchange resin (Monosphere 550A, Muromachi Technos Corp.). Stir for 4 hours.
- a cation exchange resin (15JWET, Organo Corp.)
- an anion exchange resin (Monosphere 550A, Muromachi Technos Corp.).
- IRGACURE184 (manufactured by BASF) 0.72 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.30 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa)
- a composition was prepared by dissolving 0.36 g (manufactured by Denko Co., Ltd.) in 6.48 g of propylene glycol 1-monomethyl ether 2-acetate. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- Example 4 The solution containing the polymer obtained in Synthesis Example 4 was injected into a bottle filled with a cation exchange resin (15JWET, Organo Co., Ltd.) and an anion exchange resin (Monosphere 550A, Muromachi Technos Co., Ltd.). Stir for 4 hours.
- a cation exchange resin (15JWET, Organo Co., Ltd.)
- an anion exchange resin (Monosphere 550A, Muromachi Technos Co., Ltd.).
- IRGACURE184 (manufactured by BASF) 0.72 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.35 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa)
- a composition was prepared by dissolving 0.36 g of Denko Corporation in 7.78 g of propylene glycol 1-monomethyl ether 2-acetate. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- IRGACURE184 (manufactured by BASF) 0.65 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.91 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa) Electric composition (0.33 g) was dissolved in propylene glycol 1-monomethyl ether 2-acetate (6.67 g) to prepare a composition. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- IRGACURE184 (manufactured by BASF) 0.57 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.44 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa)
- a composition was prepared by dissolving 0.29 g (manufactured by Denko Co., Ltd.) in 4.99 g of propylene glycol 1-monomethyl ether 2-acetate. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- IRGACURE184 (manufactured by BASF) 0.67 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.03 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa) Electric composition (0.34 g) was dissolved in propylene glycol 1-monomethyl ether 2-acetate (6.58 g) to prepare a composition. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- IRGACURE184 (manufactured by BASF) 0.60 g, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.62 g, and pentaerythritol tetrakis (3-mercaptobutyrate) (Showa)
- a composition was prepared by dissolving 0.30 g of Denko Co., Ltd.) in 7.67 g of propylene glycol 1-monomethyl ether 2-acetate. Then, it filtered using the polyethylene micro filter with a hole diameter of 3 micrometers, and prepared the photocurable resin composition.
- Table 1 the transmittance of 95% or more is represented by ⁇ , and less than 95% is represented by ⁇ . Further, after the films formed from the photocurable resin compositions prepared in Examples 1 to 4 and Comparative Examples 2, 3, 7, and 8 were baked at 265 ° C. for 3 minutes, the transmittance at a wavelength of 400 nm was measured. did. The results are shown in Table 1, where the transmittance after baking is reduced by 1% or less with respect to the transmittance before baking at 265 ° C. for 3 minutes, and by ⁇ when the transmittance decreases by more than 1%. expressed.
- Table 1 show that the films formed from the photocurable resin compositions prepared in Examples 1 to 4 are more than the films formed from the photocurable resin compositions prepared in Comparative Examples 2 and 3. It indicates that the film has a high transmittance and has higher heat resistance at 265 ° C. than the film formed from the photocurable resin composition prepared in Comparative Examples 2, 3, 7, and 8.
- the initial total mass was measured and placed in a constant temperature / humidity bath at 40 ° C./90%, the total mass after 24 hours was measured, the mass increase in water was calculated, and the moisture permeability of the membrane was evaluated.
- the moisture permeability of the film obtained from the composition of Example 1 was 28 g / m 2 ⁇ day
- the moisture permeability of the film obtained from the composition of Example 3 was 35 g / m 2 ⁇ day
- the composition of Comparative Example 1 The water permeability of the film obtained from was 77 g / m 2 ⁇ day.
- the photocurable resin composition prepared in Examples 1 to 4 was applied on a 4-inch silicon wafer using a spin coater and baked at 80 ° C. for 3 minutes to form a film having a thickness of 10 ⁇ m. Then, using a bonding apparatus (Ayumi Kogyo Co., Ltd., VJ-300), the wafer was bonded to a 4-inch glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 80 ° C., and a bonding pressure of 175 kg. A 1 cm square was cut with a dicing apparatus (DAD321, manufactured by Disco Corporation), and an adhesive strength evaluation sample was prepared.
- DAD321 dicing apparatus manufactured by Disco Corporation
- Araldite [registered trademark] 2014 manufactured by Huntsman Advanced Materials was applied to both sides of the obtained adhesive strength evaluation sample, and both sides were bonded to a dedicated jig for measuring adhesive strength (shear), and then an autograph ((Co)
- the adhesive force was measured at a pulling speed of 5 mm / min.
- Table 2 the adhesive strength value of 2000 N or more means that the sample was broken at the application site of Araldite 2014 and was broken at the photocurable resin composition application portion prepared in Examples 1 to 4. Therefore, it shows that the adhesive force of this photocurable resin composition has the adhesive force more than the value in a table
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Abstract
Description
そのため、200℃又はそれ以上の温度での加熱工程が不要な、高い可視光の透過率、並びに優れた耐熱性及び耐溶剤性を備えた硬化膜を形成可能な組成物が求められている。
本発明の光硬化性樹脂組成物は、前記式(1)で表される構造単位を有し、末端に前記式(2)で表される構造を有する、重量平均分子量1,000乃至50,000の重合体を含む。この重量平均分子量は、後述するゲルパーミエーションクロマトグラフィ(以下、本明細書ではGPCと略称する。)分析による、標準ポリスチレン換算値であり、好ましくは1,000乃至20,000である。
前記式(1)においてQで表される炭素原子数1乃至16の二価の炭化水素基は、例えば、直鎖状もしくは分岐鎖状のアルキレン基、二重結合で結ばれた2つの炭素原子を含む基、又は置換基を少なくとも1つ有してもよい脂環式炭化水素基もしくは芳香族炭化水素基を主鎖に含む基である。そのような基として、下記式(a)乃至式(m)で表される基が例示される。
本発明の光硬化性樹脂組成物は、ラジカル型光重合開始剤を含む。その光重合開始剤として、光硬化時に使用する光源に吸収をもつ化合物であれば特に限定されないが、例えば、tert-ブチルペルオキシ-iso-ブチレート、2,5-ジメチル-2,5-ビス(ベンゾイルジオキシ)ヘキサン、1,4-ビス[α-(tert-ブチルジオキシ)-iso-プロポキシ]ベンゼン、ジ-tert-ブチルペルオキシド、2,5-ジメチル-2,5-ビス(tert-ブチルジオキシ)ヘキセンヒドロペルオキシド、α-(iso-プロピルフェニル)-iso-プロピルヒドロペルオキシド、tert-ブチルヒドロペルオキシド、1,1-ビス(tert-ブチルジオキシ)-3,3,5-トリメチルシクロヘキサン、ブチル-4,4-ビス(tert-ブチルジオキシ)バレレート、シクロヘキサノンペルオキシド、2,2’,5,5’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-アミルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ヘキシルペルオキシカルボニル)ベンゾフェノン、3,3’-ビス(tert-ブチルペルオキシカルボニル)-4,4’-ジカルボキシベンゾフェノン、tert-ブチルペルオキシベンゾエート、ジ-tert-ブチルジペルオキシイソフタレート等の有機過酸化物;9,10-アントラキノン、1-クロロアントラキノン、2-クロロアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン等のキノン類;ベンゾインメチル、ベンゾインエチルエーテル、α-メチルベンゾイン、α-フェニルベンゾイン等のベンゾイン誘導体;2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-[4-{4-(2-ヒドロキシ-2-メチル-プロピオニル)ベンジル}-フェニル]-2-メチル-プロパン-1-オン、フェニルグリオキシリックアシッドメチルエステル、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-1-ブタノン、2-ジメチルアミノ-2-(4-メチル-ベンジル)-1-(4-モリホリン-4-イル-フェニル)-ブタン-1-オン等のアルキルフェノン系化合物;ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド等のアシルホスフィンオキサイド系化合物;2-(O-ベンゾイルオキシム)-1-[4-(フェニルチオ)フェニル]-1,2-オクタンジオン、1-(O-アセチルオキシム)-1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]エタノン等のオキシムエステル系化合物が挙げられる。
本発明の光硬化性樹脂組成物は溶剤を含む。その溶剤として、半導体デバイス製造工程で使用できる有機溶剤であれば特に限定されないが、例えば、シクロヘキサノン、メチルイソアミルケトン、2-ブタノン、2-ヘプタノン等のケトン類;エチレングリコール、エチレングリコールモノアセテート、ジエチレングリコール、ジエチレングリコールモノアセテート、プロピレングリコール、プロピレングリコールモノアセテート、ジプロピレングリコール又はジプロピレングリコールモノアセテート、並びにこれらのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテル、モノフェニルエーテル等の多価アルコール類及びその誘導体;ジオキサン等の環式エーテル類;γ-ブチロラクトン等のラクトン類;及び乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル等のエステル類が挙げられる。これらの有機溶剤は単独で用いてもよく、二種以上を混合して用いてもよい。本発明の光硬化性樹脂組成物から溶剤を除いた成分を固形分とすると、該光硬化性樹脂組成物に占める固形分の割合は、例えば1質量%乃至80質量%である。
本発明の光硬化性樹脂組成物は、必要に応じて、二官能(メタ)アクリレートを架橋性化合物として含有することができる。ここで二官能(メタ)アクリレートとは、分子の両端にアクリロイル基又はメタクリロイル基を有する化合物である。その化合物として、例えば、トリシクロデカンジメタノールジアクリレート、トリシクロデカンジメタノールジメタクリレート、トリシクロデカンジエタノールジアクリレート、及びトリシクロデカンジエタノールジメタクリレートが挙げられる。
本発明の光硬化性樹脂組成物は、必要に応じて、エポキシ化合物、光酸発生剤、熱酸発生剤、無機フィラー、界面活性剤などの添加剤をさらに含有することができる。
本発明の光硬化性樹脂組成物を用い、以下の工程、すなわち、本発明の光硬化性樹脂組成物を基板上に塗布する工程、前記基板上に塗布された光硬化性樹脂組成物を50℃乃至160℃の温度でプリベークする工程、前記プリベーク後の前記基板上に形成された塗膜を露光する工程、及び前記塗膜を現像する工程、を経て硬化膜を形成することができる。
装置:一体型高速GPCシステム HLC-8220GPC 東ソー(株)製
カラム:KF-G,KF804L
カラム温度:40℃
溶媒:テトラヒドロフラン(THF)
流量:1.0mL/分
標準試料:ポリスチレン
ディテクター:RI
1,2-シクロヘキサンジカルボン酸80.45g、モノアリルジグリシジルイソシアヌル酸110.00g、及びベンジルトリエチルアンモニウムクロリド4.52gをプロピレングリコール1-モノメチルエーテル2-アセタート292.46gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル18.05g及びベンジルトリエチルアンモニウムクロリド0.72gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は2,700であった。得られたポリマーは、下記式(1a)で表される構造単位及び末端に下記式(2a)で表される構造を有するポリマーであると考えられる。
4-メチルシクロヘキサン-1,2-ジカルボン酸無水物14.29g、モノアリルジグリシジルイソシアヌル酸20.00g、及びベンジルトリエチルアンモニウムクロリド0.82gをシクロヘキサノン105.33gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル3.25g及びベンジルトリエチルアンモニウムクロリド0.13gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は10,900であった。得られたポリマーは、下記式(1b)で表される構造単位及び末端に下記式(2b)で表される構造を有するポリマーであると考えられる。
2-プロペン-1,2-ジカルボン酸18.24g、モノアリルジグリシジルイソシアヌル酸33.00g、及びエチルトリフェニルホスホニウムブロミド2.21gをシクロヘキサノン124.71gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル4.86g及びエチルトリフェニルホスホニウムブロミド0.30gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は3,900であった。得られたポリマーは、下記式(1c)で表される構造単位及び末端に下記式(2c)で表される構造を有するポリマーであると考えられる。
1,4-ブタンジカルボン酸20.48g、モノアリルジグリシジルイソシアヌル酸33.00g、及びエチルトリフェニルホスホニウムブロミド2.21gをシクロヘキサノン129.96gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル5.07g及びエチルトリフェニルホスホニウムブロミド0.30gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は4,700であった。得られたポリマーは、下記式(1d)で表される構造単位及び末端に下記式(2d)で表される構造を有するポリマーであると考えられる。
2,2-ビス(4-グリシジルオキシシクロヘキシル)プロパン25.00g、1,2-シクロヘキサンジカルボン酸11.35g、及びベンジルトリエチルアンモニウムクロリド0.64gをシクロヘキサノン86.31gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル13.78g及びベンジルトリエチルアンモニウムクロリド0.55gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は3,100であった。得られたポリマーは、下記式(3)で表される構造単位及び末端に下記式(2e)で表される構造を有するポリマーであると考えられる。
1,4-ナフタレンジカルボン酸22.11g、2,2-ビス(4-グリシジルオキシフェニル)プロパン32.00g、及びベンジルトリエチルアンモニウムクロリド0.99gをプロピレングリコール1-モノメチルエーテル2-アセタート82.65gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル6.41g及びベンジルトリエチルアンモニウムクロリド0.26gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は4,400であった。得られたポリマーは、下記式(4)で表される構造単位及び末端に下記式(2f)で表される構造を有するポリマーであると考えられる。
2,5-ピリジンジカルボン酸12.29g、2,2-ビス(4-グリシジルオキシフェニル)プロパン23.00g、及びベンジルトリエチルアンモニウムクロリド0.71gをシクロヘキサノン107.99gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル3.34g及びベンジルトリエチルアンモニウムクロリド0.13gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は6,200であった。得られたポリマーは、下記式(5)で表される構造単位及び末端に下記式(2g)で表される構造を有するポリマーであると考えられる。
イソフタル酸14.34g、2,2-ビス(4-グリシジルオキシフェニル)プロパン27.00g、及びベンジルトリエチルアンモニウムクロリド0.84gをプロピレングリコール1-モノメチルエーテル2-アセタート63.26gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は10,200であった。得られたポリマーは、下記式(6)で表される構造単位を有し、末端がアクリロイル基又はメタクリロイル基を有する構造で封止されていないポリマーであると考えられる。
2,2-ビス(4-グリシジルオキシシクロヘキシル)プロパン28.00g、モノアリルイソシアヌル酸12.49g、及びベンジルトリエチルアンモニウムクロリド0.71gをプロピレングリコール1-モノメチルエーテル2-アセタート61.81gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は4,100であった。得られたポリマーは、下記式(7)で表される構造単位有するポリマーであると考えられる。
1,2-シクロヘキサンジカルボン酸103.61g、モノアリルジグリシジルイソシアヌル酸150.00g、及びベンジルトリエチルアンモニウムクロリド3.08gをプロピレングリコール1-モノメチルエーテル2-アセタート256.69gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は3,300であった。得られたポリマーは、下記式(1a)で表される構造単位を有するポリマーであると考えられる。
2,2-ビス(4-グリシジルオキシシクロヘキシル)プロパン24.00g、1,4-ナフタレンジカルボン酸13.68g、及びベンジルトリエチルアンモニウムクロリド1.23gをプロピレングリコール1-モノメチルエーテル2-アセタート90.78gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル3.57g及びベンジルトリエチルアンモニウムクロリド0.14gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は6,400であった。得られたポリマーは、下記式(8)で表される構造単位及び末端に下記式(2h)で表される構造を有するポリマーであると考えられる。
ヘキサヒドロフタル酸ジグリシジルエステル15.00g、4-シクロヘキセン-1,2-ジカルボン酸9.86g、及びベンジルトリエチルアンモニウムクロリド1.12gをプロピレングリコール1-モノメチルエーテル2-アセタート103.93gに溶解させた後、140℃で4時間反応させポリマーを含む溶液を得た。室温に冷却後、メタクリル酸グリシジル2.36g及びベンジルトリエチルアンモニウムクロリド0.09gを本溶液に溶解させた後、140℃で3時間反応させポリマーを含む溶液を得た。得られたポリマーのGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は2,300であった。得られたポリマーは、下記式(9)で表される構造単位及び末端に下記式(2i)で表される構造を有するポリマーであると考えられる。
合成例1で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液20gにIRGACURE[登録商標]184(BASF社製)0.68g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)4.08g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.34gを、プロピレングリコール1-モノメチルエーテル2-アセタート8.90gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例2で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー[登録商標]550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液22gにIRGACURE184(BASF社製)0.60g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)3.62g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.30gを、プロピレングリコール1-モノメチルエーテル2-アセタート3.62gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例3で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液24gにIRGACURE184(BASF社製)0.72g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)4.30g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.36gを、プロピレングリコール1-モノメチルエーテル2-アセタート6.48gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例4で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液23gにIRGACURE184(BASF社製)0.72g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)4.35g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.36gを、プロピレングリコール1-モノメチルエーテル2-アセタート7.78gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例5で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液33gにIRGACURE184(BASF社製)0.93g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)2.78g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.46gを、シクロヘキサノン0.69gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例6で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液21gにIRGACURE184(BASF社製)0.65g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)3.91g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.33gを、プロピレングリコール1-モノメチルエーテル2-アセタート6.67gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例7で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液21gにIRGACURE184(BASF社製)0.57g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)3.44g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.29gを、プロピレングリコール1-モノメチルエーテル2-アセタート4.99gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例8で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液22gにIRGACURE184(BASF社製)0.71g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)4.26g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.35gを、プロピレングリコール1‐モノメチルエーテル2-アセタート8.16gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例9で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液22gにIRGACURE184(BASF社製)0.67g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)4.03g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.34gを、プロピレングリコール1-モノメチルエーテル2-アセタート6.58gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例10で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液22gにIRGACURE184(BASF社製)0.72g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)4.29g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.36gを、プロピレングリコール1-モノメチルエーテル2-アセタート8.42gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例11で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液20gにIRGACURE184(BASF社製)0.60g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)3.58g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.30gを、プロピレングリコール1-モノメチルエーテル2-アセタート5.36gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
合成例12で得られたポリマーを含む溶液を、陽イオン交換樹脂(15JWET、オルガノ(株))及び陰イオン交換樹脂(モノスフィアー550A、ムロマチテクノス(株))が充填されたボトル中に注入し、4時間撹拌させた。撹拌後の溶液18gにIRGACURE184(BASF社製)0.60g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製)3.62g、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製)0.30gを、プロピレングリコール1-モノメチルエーテル2-アセタート7.67gに溶解させ組成物を調製した。その後、孔径3μmのポリエチレン製マイクロフィルターを用いてろ過して、光硬化性樹脂組成物を調製した。
実施例1乃至実施例4、比較例2、3、7及び8で調製した光硬化性樹脂組成物を、石英基板上にスピンコーターを用いて塗布し、100℃でプリベーク、アライナー(PLA-501、キヤノン(株)製)を用い露光し(i線、露光量:3000mJ/cm2)、さらに100℃でベーク後、プロピレングリコール1-モノメチルエーテル2-アセタート及び1-メトキシ-2-プロパノール混合溶液にて現像し、膜厚10μmの膜を形成した。この膜を紫外線可視分光光度計UV-2550((株)島津製作所製)を用いて波長400nmの透過率を測定した。その結果を表1に示す。表1において、透過率が95%以上を○で表し、95%未満を×で表した。さらに、前記実施例1乃至実施例4、比較例2、3、7及び8で調製した光硬化性樹脂組成物から形成した膜を265℃で3分間ベークした後、波長400nmの透過率を測定した。その結果を表1において、前記265℃で3分間ベークする前の透過率に対する該ベークした後の透過率が1%以下低下するものを○で表し、1%を超えて低下するものを×で表した。下記表1の結果は、実施例1乃至実施例4で調製した光硬化性樹脂組成物から形成した膜は、比較例2及び比較例3で調製した光硬化性樹脂組成物から形成した膜よりも高い透過率を示し、且つ比較例2、3、7及び8で調製した光硬化性樹脂組成物から形成した膜よりも265℃での高い耐熱性を有することを示唆している。
実施例1乃至実施例4及び比較例4乃至比較例6で調製した光硬化性樹脂組成物を、シリコンウェハー上にスピンコーターを用いて塗布し、100℃でプリベークし、アライナー(PLA-501、キヤノン(株)製)を用い露光し(i線、露光量:3000mJ/cm2)、さらに100℃でベーク後、プロピレングリコール1-モノメチルエーテル2-アセタート及び1-メトキシ-2-プロパノール混合溶液にて現像し、膜厚10μmの膜を形成した。この膜をN-メチル2-ピロリドンに、23℃にて1分間浸漬した。末端にメタクリル基を有するポリマーを含む実施例1乃至実施例4で調製した光硬化性樹脂組成物から形成された膜は浸漬前後での膜厚変化が5%以下であることを確認したが、末端がアクリロイル基又はメタクリロイル基を有する構造で封止されていないポリマーを含む比較例4乃至比較例6で調製した光硬化性樹脂組成物から形成された膜はN-メチルピロリドン浸漬後、浸漬前の膜厚の20%以上が溶解してしまった。
JIS Z 0208(カップ法)
実施例1、3及び比較例1で調製した組成物をそれぞれカプトンフィルム(東レデュポン社製)上に成膜し、100℃でプリベークし、アライナー(PLA-501、キヤノン(株)製)を用い露光し(i線、露光量:3000mJ/cm2)、さらに100℃でベーク後、プロピレングリコール1-モノメチルエーテル2-アセタート及び1-メトキシ-2-プロパノール混合溶液にて現像し、目的の膜を得た。透湿度測定は、透湿度測定カップに塩化カルシウムを入れ、フィルム径が6cmとなるように得られた膜を設置した。初期の全体質量を測定し、40℃/90%の恒温恒湿槽に設置し、24時間後の全体質量を測定し水の質量増加量を算出して、膜の透湿度を評価した。実施例1の組成物から得られた膜の透湿度は28g/m2・day、実施例3の組成物から得られた膜の透湿度は35g/m2・day、比較例1の組成物から得られた膜の透湿度は77g/m2・dayであった。この結果は、実施例1の組成物から得られた膜及び実施例3の組成物から得られた膜の方が、比較例1の組成物から得られた膜よりも透湿防止性に優れることを示している。
実施例1乃至実施例4で調製した光硬化性樹脂組成物を、4インチシリコンウェハー上にスピンコーターを用いて塗布し、80℃で3分間ベークを行って、膜厚10μmの膜を形成した後、貼り合せ装置(アユミ工業(株)製、VJ-300)を使用して、真空度10Pa以下、温度80℃、貼り合せ圧力175kgの条件下で4インチガラスウェハーと接着させ、そのウェハーをダイシング装置(ディスコ(株)製、DAD321)で1cm角に切断し、接着力評価サンプルを作製した。得られた接着力評価サンプルの両面にアラルダイト[登録商標]2014(ハンツマン・アドバンスト・マテリアルズ社製)を塗布し、接着力(せん断)測定用専用冶具に両面を接着後、オートグラフ((株)島津製作所製、オートグラフAGS-100NX)で接着力(せん断)を評価した。接着力は5mm/分の引っ張り速度で測定した。その結果を下記表2に示す。表2中、接着力の値が2000N以上とは、サンプルの破断がアラルダイト2014塗布部で発生しており、実施例1乃至実施例4で調製した光硬化性樹脂組成物塗布部分で破断していないため、本光硬化性樹脂組成物の接着力は表中の値以上の接着力を有することを示す。実施例1乃至実施例4で調製した光硬化性樹脂組成物を用いて得られたサンプルは、十分な接着性を有することが確認された。
Claims (6)
- 前記式(1)においてQで表される二価の炭化水素基は、直鎖状もしくは分岐鎖状のアルキレン基、二重結合で結ばれた2つの炭素原子を含む基、又は置換基を少なくとも1つ有してもよい脂環式炭化水素基もしくは芳香族炭化水素基を主鎖に含む基を表す、請求項1に記載の光硬化性樹脂組成物。
- 前記式(2)においてZで表される二価の連結基は、置換基としてヒドロキシ基を少なくとも1つ有してもよい、直鎖状又は分岐鎖状のアルキレン基を表す、請求項1又は請求項2に記載の光硬化性樹脂組成物。
- さらに二官能(メタ)アクリレート及び/又は多官能チオールを含む請求項1乃至請求項3のいずれか一項に記載の光硬化性樹脂組成物。
- 接着剤用又はレンズ材用である請求項1乃至請求項4のいずれか一項に記載の光硬化性樹脂組成物。
- 請求項1乃至請求項5のいずれか一項に記載の光硬化性樹脂組成物を基板上に塗布する工程、前記基板上に塗布された光硬化性樹脂組成物を50℃乃至160℃の温度でプリベークする工程、前記プリベーク後の前記基板上に形成された塗膜を露光する工程、及び前記塗膜を現像する工程を有する、膜形成方法。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190049171A (ko) * | 2017-11-01 | 2019-05-09 | 삼성에스디아이 주식회사 | 레지스트 하층막용 조성물 및 이를 이용한 패턴형성방법 |
WO2023145703A1 (ja) * | 2022-01-25 | 2023-08-03 | 日産化学株式会社 | 末端封止ポリマーを含むレジスト下層膜形成組成物 |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007148627A1 (ja) * | 2006-06-19 | 2007-12-27 | Nissan Chemical Industries, Ltd. | 水酸基含有縮合系樹脂を含有するレジスト下層膜形成組成物 |
JP2008143954A (ja) * | 2006-12-06 | 2008-06-26 | Jsr Corp | イソシアヌル環含有重合体、その製造法およびそれを含有する組成物 |
JP2009093162A (ja) * | 2007-09-19 | 2009-04-30 | Nissan Chem Ind Ltd | 多環式脂肪族環を有するポリマーを含むリソグラフィー用レジスト下層膜形成組成物 |
JP4705311B2 (ja) * | 2000-09-14 | 2011-06-22 | 互応化学工業株式会社 | 紫外線硬化性樹脂組成物および同組成物を含むフォトソルダーレジストインク |
WO2013035787A1 (ja) * | 2011-09-08 | 2013-03-14 | 日産化学工業株式会社 | 重合体及びそれを含む組成物並びに接着剤用組成物 |
JP2013541524A (ja) * | 2010-09-15 | 2013-11-14 | スリーエム イノベイティブ プロパティズ カンパニー | 置換糖化合物及び歯科用組成物 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060173142A1 (en) * | 2005-02-01 | 2006-08-03 | Hildeberto Nava | Functionalized thermosetting resin systems |
JP5628489B2 (ja) * | 2009-06-10 | 2014-11-19 | 株式会社カネカ | 光硬化性組成物およびそれを用いた絶縁性薄膜および薄膜トランジスタ |
WO2013051615A1 (ja) * | 2011-10-07 | 2013-04-11 | 富士フイルム株式会社 | 半導体発光装置用封止剤、これを用いた半導体発光装置用封止材及び半導体発光装置 |
KR101566532B1 (ko) * | 2011-12-30 | 2015-11-05 | 제일모직주식회사 | 시아누릭산 유도체, 상기 시아누릭산 유도체를 포함하는 레지스트 하층막용 조성물 및 상기 레지스트 하층막용 조성물을 사용한 패턴 형성 방법 |
JP5882451B2 (ja) * | 2012-04-26 | 2016-03-09 | ミネベア株式会社 | 紫外線硬化性樹脂組成物及び摺動部材、並びに摺動部材の製造方法 |
US9434856B2 (en) * | 2012-05-11 | 2016-09-06 | Nissan Chemical Industries, Ltd. | Film-forming composition and embedding material |
EP2848967A4 (en) * | 2012-05-11 | 2015-11-25 | Nissan Chemical Ind Ltd | FILM-COMPOSITE COMPOSITION |
JP2014152214A (ja) * | 2013-02-06 | 2014-08-25 | Nippon Carbide Ind Co Inc | 樹脂硬化物の製造方法及び樹脂硬化物 |
US9745470B2 (en) * | 2013-03-08 | 2017-08-29 | Nissan Chemical Industries, Ltd. | Film-forming composition |
US20160160079A1 (en) * | 2013-07-31 | 2016-06-09 | Nissan Chemical Industries, Ltd. | Carbon material dispersed film formation composition |
-
2016
- 2016-06-15 SG SG11201710797QA patent/SG11201710797QA/en unknown
- 2016-06-15 WO PCT/JP2016/067824 patent/WO2016208472A1/ja active Application Filing
- 2016-06-15 KR KR1020177035548A patent/KR102281571B1/ko active IP Right Grant
- 2016-06-15 US US15/739,808 patent/US10866513B2/en active Active
- 2016-06-15 CN CN201680036679.7A patent/CN107709388B/zh active Active
- 2016-06-15 JP JP2017525265A patent/JP6569875B2/ja active Active
- 2016-06-23 TW TW105119752A patent/TWI704415B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4705311B2 (ja) * | 2000-09-14 | 2011-06-22 | 互応化学工業株式会社 | 紫外線硬化性樹脂組成物および同組成物を含むフォトソルダーレジストインク |
WO2007148627A1 (ja) * | 2006-06-19 | 2007-12-27 | Nissan Chemical Industries, Ltd. | 水酸基含有縮合系樹脂を含有するレジスト下層膜形成組成物 |
JP2008143954A (ja) * | 2006-12-06 | 2008-06-26 | Jsr Corp | イソシアヌル環含有重合体、その製造法およびそれを含有する組成物 |
JP2009093162A (ja) * | 2007-09-19 | 2009-04-30 | Nissan Chem Ind Ltd | 多環式脂肪族環を有するポリマーを含むリソグラフィー用レジスト下層膜形成組成物 |
JP2013541524A (ja) * | 2010-09-15 | 2013-11-14 | スリーエム イノベイティブ プロパティズ カンパニー | 置換糖化合物及び歯科用組成物 |
WO2013035787A1 (ja) * | 2011-09-08 | 2013-03-14 | 日産化学工業株式会社 | 重合体及びそれを含む組成物並びに接着剤用組成物 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190049171A (ko) * | 2017-11-01 | 2019-05-09 | 삼성에스디아이 주식회사 | 레지스트 하층막용 조성물 및 이를 이용한 패턴형성방법 |
KR102067081B1 (ko) | 2017-11-01 | 2020-01-16 | 삼성에스디아이 주식회사 | 레지스트 하층막용 조성물 및 이를 이용한 패턴형성방법 |
US11493848B2 (en) | 2017-11-01 | 2022-11-08 | Samsung Sdi Co., Ltd. | Resist underlayer composition, and method of forming patterns using the composition |
WO2023145703A1 (ja) * | 2022-01-25 | 2023-08-03 | 日産化学株式会社 | 末端封止ポリマーを含むレジスト下層膜形成組成物 |
WO2023181960A1 (ja) * | 2022-03-24 | 2023-09-28 | 日産化学株式会社 | 保護膜形成用組成物 |
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