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TWI326300B - - Google Patents

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Publication number
TWI326300B
TWI326300B TW95118307A TW95118307A TWI326300B TW I326300 B TWI326300 B TW I326300B TW 95118307 A TW95118307 A TW 95118307A TW 95118307 A TW95118307 A TW 95118307A TW I326300 B TWI326300 B TW I326300B
Authority
TW
Taiwan
Prior art keywords
adhesive
carboxyl group
group
pattern
laminated structure
Prior art date
Application number
TW95118307A
Other languages
English (en)
Other versions
TW200710570A (en
Inventor
Shigeru Ushiki
Shohei Makita
Masatoshi Kusama
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of TW200710570A publication Critical patent/TW200710570A/zh
Application granted granted Critical
Publication of TWI326300B publication Critical patent/TWI326300B/zh

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G02B6/138—Integrated optical circuits characterised by the manufacturing method by using polymerisation
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B32B37/1292—Application of adhesive selectively, e.g. in stripes, in patterns
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1496—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation making use of masks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4835—Heat curing adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4845—Radiation curing adhesives, e.g. UV light curing adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • B29C65/487—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their shape, e.g. being fibres or being spherical
    • B29C65/4875—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their shape, e.g. being fibres or being spherical being spherical, e.g. particles or powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • B29C65/4885—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their composition being non-plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • B29C65/4885—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their composition being non-plastics
    • B29C65/489—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their composition being non-plastics being metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2463/00—Presence of epoxy resin
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0502—Patterning and lithography
    • H05K2203/0514—Photodevelopable thick film, e.g. conductive or insulating paste
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0502—Patterning and lithography
    • H05K2203/0525—Patterning by phototackifying or by photopatterning adhesive
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/303—Surface mounted components, e.g. affixing before soldering, aligning means, spacing means
    • H05K3/305—Affixing by adhesive
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24174—Structurally defined web or sheet [e.g., overall dimension, etc.] including sheet or component perpendicular to plane of web or sheet
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(1) 1326300 . 九、發明說明 - 【發明所屬之技術領域】 本發明係關於一種黏著劑圖型形成組成物、使用其所 得到之層合構造物及其製造方法，更詳而言之，係關於一 種由亦具有作爲黏著功能以及間隙物等之結構構件的功能 之光硬化型/熱硬化型黏著劑所構成的黏著劑圖型形成組 成物、藉由使用其所形成之黏著劑圖型的硬化物而接合構 Φ 件間之層合構造物及其製造方法。本發明之光硬化型/熱 硬化型黏著劑係適用於作爲精細圖型之結構支撐部（被稱 爲間隙物、肋或隔壁）的黏著劑圖型必須之各種顯示裝置 ’ 中的層合構造物之形成，又，要求精細之圖型時，亦適用 • 於一對於各種基板上所形成之微細佈線圖型而使其他之佈 線圖型或各種電子零件的電極進行導電連接之層合構造、 背光裝置（背面照明裝置）的光反射部等之形成。 # 【先前技術】 以往，此種層合構造物的形成所使用的黏著劑圖型， 一般係可使用熱硬化型之黏著劑。例如，於以往背光裝置 ' 中的光反射部的形成，一般係於作爲黏結劑之透明樹脂凡 立水中混入氧化鈦等的反射材料，藉有機溶劑稀釋成適於 印刷之黏度的油墨，於導光板之背面以點狀等特定之圖型 藉網版印刷等進行塗佈，或，如記載於特開平6- 1 94527 號公報，於白色之塑膠片（反射材薄片）之單面使用一含 反射材料之油墨而印刷反射圖型，利用該反射圖型本身的 -5- (2) 1326300 • 接著性而黏著於透明壓克力板（導光板）。 • 但’熱硬化型之黏著劑的情形，必須藉印刷而形成特 定之圖型狀’故很難形成精細的黏著劑圖型。 爲解決如此之問題，近年開發出一種藉光微影法形成 黏著劑圖型之方法，可使用於各種層合構造的黏著劑圖型 之形成（例如參照特開平3- 1 85086號公報）。但，光硬 化型之黏著劑圖型所使用的感光性樹脂組成物時，因一般 # 由（甲基）丙烯酸酯系化合物-光聚合起始劑的組成所構 成，故對基板或所層合之薄片構件的黏著性不充分之問題 仍存在。又，於所形成之黏著劑圖型的硬化物之硬度或耐 * 熱性、耐藥品性等的特性面仍殘留亦應改善之餘地。 【發明內容】 (發明之揭示） (發明欲解決之問題） # 本發明係有鑑於前述之習知技術的問題點者。其目的 在於提供一種組成物，其係藉光微影法解決一形成精細的 黏著劑圖型時之前述問題，對於各種構件例如各種基板或 ' 其表面所層合之各種薄片構件的接著性優，同時可形成硬 • 度或耐熱性、耐藥品性等之特性優的黏著劑圖型之硬化物 :藉由使用其所形成之黏著劑圖型的硬化物而接合構件間 之層合構造物及其製造方法。 (用以解決問題之手段） -6- (3) 1326300 ' 爲達成前述目的，若依本發明，可提供一種層合結構 • 物之黏著劑圖型形成用組成物，其係爲一使用於構件之間 藉由以驗顯像型微影法所形成之黏著劑圖型的硬化物而黏 合之組成物’其特徵在於：該組成物爲由含有（A)於1 分子中一併具有羧基與乙烯性不飽和鍵，且具有酸價 30~160mgKOH/g之含羧基的感光性預聚物、（B)環氧樹 脂及（C)光聚合起始劑作爲必須成份之光硬化型/熱硬化 • 型接著劑所構成。 進一步，若依本發明，可提供一種層合結構物之製造 方法’其特徵在於：使上述黏著劑圖型形成用組成物塗佈 ' 於被黏著構件表面，以活性能量束選擇性圖型曝光後，藉 • 顯像除去未曝光部而形成黏著劑圖型，然後，使爲接合之 黏著構件壓接於上述黏著劑圖型而使上述黏著劑圖型熱硬 化。 進一步又，若依本發明，可提供一種層合結構物，其 • 特徵在於：構件之間藉由一由上述黏著劑圖型形成用組 成物所形成之黏著劑圖型的硬化物而接合。 又，在本說明書中，所謂「層合構造物」意指於被黏 ' 著構件上藉由一由本發明之光硬化型/熱硬化型黏著劑所 - 形成的黏著劑圖型之硬化物，而接合黏著構件之結構體。 前述被黏著構件及黏著構件係可使用各種絕緣性構件、各 種導電性構件、各種透明或半透明構件或著色構件等依用 途之任意性質的構件。又，被黏著構件及黏著構件係可使 用玻璃、陶瓷、金屬、塑膠、紙等之各種材料所製作之成 (4) 1326300 形品、板狀成型品、薄片等，依所希望的用途而可使用各 種之構件。 (發明之效果） . 於本發明之層合構造物的黏著劑圖型形成使用之前述 光硬化型/熱硬化型黏著劑’係含有（A)含羧基的感光性 預聚物、（B )環氧樹脂及（C )光聚合起始劑作爲必須成 • 份’藉活性能量線之選擇性圖型曝光、顯像，可形成高精 細的黏著劑圖型，且亦具有作爲黏著功能以及間隙物等之 結構構件的功能’故可得到構件之間藉由上述黏著劑圖型 ' 的硬化物而被牢固地接合之層合構造物。又，使構件之間 • 接合之黏著劑圖型的硬化物，係硬度或耐熱性、耐藥品性 等之特性亦優’故可用於各種用途之層合結構物的製造。 (用以實施發明之最佳形態） • 本發明人等爲解決前述課題，經專心硏究之結果，將 —含有（A)含羧基的感光性預聚物、（B)環氧樹脂及（ C)光聚合起始劑作爲必須成份之光硬化型/熱硬化型黏著 ' 劑用於層合結構物的黏著劑圖型形成時，可於被黏著構件 • 表面藉鹼顯像型光微影法形成精細的黏著劑圖型，同時並 驚訝地發現，若使曝光、顯像後爲接合之黏著構件壓接於 上述黏著劑圖型而熱硬化，構件之間藉由黏著劑圖型之硬 化物而極牢固地接合，終完成本發明。以下，參照添附圖 面同時並進行說明。 -8 - (5) 1326300 ' 使用本發明之光硬化型/熱硬化型黏著劑而 法形成黏著劑圖型之方法的一例表示於圖1中》 圖1 ( A )所示般，於被黏著構件例如基板1之 光硬化型/熱硬化型黏著劑之塗膜2。 塗膜之形 - 硬化型/熱硬化型黏著劑依需要而添加稀釋劑（ 性稀釋劑之後述的光聚合性單體或有機溶劑）而 後’藉網版印刷法、簾塗法' 輥塗法、浸漬塗佈 # 塗法等之適當塗佈方法塗佈於所希望之基板上， 60 °C ~ 120 °C之溫度暫時乾燥以除去組成物中所含 溶劑，形成塗膜。 * 然後，如以上般做法所形成的光硬化型/熱 • 著劑的塗膜進行圖型曝光。圖型曝光係例如圖 示般，於該塗膜2之上重疊一已形成特定曝光圖 3 (亦可爲接觸或非接觸之任一方式，但一般係 觸方式）、選擇性照射活性能量束而進行曝光。 # 型般藉雷射光線等直接描繪而進行曝光。 上述活性能量束之照射光源適宜爲低壓水銀 水銀燈、高壓水銀燈、超高壓水銀燈、氙燈、金 ' 或各種雷射光線等。其他，亦可利用電子束、α - 、7線、X線中子束等。 其後，除去光罩3後，（或，藉雷射光線等 而進行曝光之情形係以原來的狀態），藉由使未 如以稀鹼水溶液進行顯像，如圖1(C)槪略地 可得到特定之黏著劑圖型4。又，亦可反覆塗佈 藉光微影 首先，如 表面形成 成係於光 作爲反應 調整黏度 法、及旋 例如以約 有之有機 硬化型黏 1 ( Β )所 形的光罩 可採用接 或，如圖 燈、中壓 屬鹵素燈 線、冷線 直接描繪 曝光部例 表不般^ '曝光、 -9- (6) 1326300 * 顯像之各步驟而形成所希望之高度的黏著劑圖型。黏著劑 • 圖型係依所希望的用途而構成點、線、面等之圖樣的要素 隔開任意的距離而配置之圖樣例如條狀 '斑點狀、網目狀 等之各種圖樣。 . 用於上述顯像之鹼水溶液係可使用氫氧化鈉、氫氧化 鉀、碳酸鈉、碳酸鉀、矽酸鈉、氨、有機胺、四甲基銨氫 氧化物等之水溶液。顯像液中之鹼的濃度只要約爲 • 〇」~5wt%即可。顯像方式係可使用浸漬顯像、槳式顯像、 噴塗顯像等之公知的方法。 然後，如圖1(D)所示般，使爲接合之黏著構件例 • 如薄片構件 5壓接於黏著劑圖型 4，加熱至例如約 - l4〇~200°C之溫度，宜爲約150t：而進行熱硬化。藉此，加 於光硬化型/熱硬化型黏著劑中之熱硬化性成份的硬化反 應，而經由與光硬化性樹脂成份之聚合促進以及熱硬化性 成份之共聚合，可提昇所得到之黏著劑圖型的硬化物之耐 • 熱性、耐溶劑性、耐酸性'密著性'電氣特性、硬度等之 各特性。 又，壓接之壓力係只要爲所形成之黏著劑圖型不崩潰 ' 程度之壓力即可，可依曝光、顯像後之黏著劑圖型的硬度 - 而任意地設定。 前述被黏著構件及黏著構件係可使用玻璃、陶瓷、金 屬、塑膠、紙等之各種材料所製作之成形品、板狀成形品 、薄片等，可依所希望的用途而使用各種構件。 尤其被黏著構件係適合使用於玻璃板 '玻璃-環氧基 •10- (7) 1326300 • 板、陶瓷基板 '金屬板、塑膠板、此等之複合板或其他之 材料的複合板等的各基板’可依所希望的用途而使用各種 材料》又’即使就爲接合之黏著構件而言，可適宜使用合 成樹脂膜、金屬膜、玻璃片、紙、紙-合成樹脂複合膜、 紙-金屬箔-合成樹脂複合膜等之薄片構件，可依所希望的 用途而使用各種材料。此等被黏著構件及/或黏著構件係 亦可實施開孔加工等之機械加工者。 # 又’此等被黏著構件及/或黏著構件必須可承受熱硬 化處理之溫度者。 然後’進一步詳細說明有關本發明之黏著劑圖型之形 ' 成所使用的光硬化型/熱硬化型黏著劑。 - 首先於本發明使用之含有羧基的感光性預聚物（A) 係於1分子中至少具有2個環氧基之多官能環氧基化合物 (a)的環氧基與不飽和單羧酸（b)之羧基進行酯化反應 (全酯化或部分酯化、較佳係全酯化），對所生成之2級 ^ 羥基進一步使飽和或不飽和的多價酸酐（c)加成反應所 得到之含有羧基的感光性預聚物（A-1 )。 如此之含有羧基的感光性預聚物（A-1)係於骨架/聚 合物之側鏈賦予多數游離之羧基者，故含有此含感光性預 ' 聚物之光硬化型/熱硬化型黏著劑係可以稀鹼水溶液進行 顯像，塗佈於基板，選擇性曝光後，可藉鹼水溶液顯像而 形成特定的圖型。
前述多官能環氧化合物（a )係可使用所有之環氧樹 脂，但，代表性之例係可舉例雙酚A型、添加氫雙酚A -11 - (8) 1326300 ' 型、雙酚F型、雙酚S型、酚酚醛清漆型、甲酚酚醛清漆 型、雙酚A之酚醛清漆型 '聯酚型、聯二甲苯酚型、N-縮 水甘油基型等之公知慣用的多官能環氧基化合物。此等之 多官能環氧基化合物（a )，係可單獨或組合2種以上而 , 使用。 另外’不飽和單羧酸（b)之具體例係可舉例：丙烯 酸、甲基丙烯酸、巴豆酸、馬來酸、富馬酸、衣康酸、桂 • 皮酸、α-氰基桂皮酸、沒-苯乙烯基丙烯酸、/5-糠基丙烯 酸等。此等不飽和單羧酸（b)係可單獨或組合2種以上 而使用。 • 飽和或不飽合之多價酸酐（c)之具體例可舉例：琥 • 珀酸酐、馬來酸酐、衣康酸酐 '己二酸酐' 酞酸酐、四氫 酿酸酌1 '六氫酞酸酐、甲基六氫酞酸酐 '衣康酸酐、甲基 末端亞甲基四氫酞酸酐、偏苯三酸酐、均苯四甲酸酐等》 進一步’可舉例如：均苯四甲酸酐與2-羥乙基（甲基）丙 ® 嫌酸酯、2-羥丙基（甲基）丙烯酸酯等之羥烷基（甲基） 丙烯酸酯類等之羥基之不飽和化合物的部分反應生成物等 。此等多價酸酐（c )係可單獨或組合2種以上而使用。 ' 進一步，其他之含羧基之感光性預聚物（A)係可舉 • 例如： (1)於側鏈具有環氧基之寡聚物或聚合物、例如具 有烷基（甲基）丙烯酸酯等之不飽和雙鍵之化合物、與於 縮水甘油基（（甲基）丙烯酸酯等之1分子中具有不飽和 雙鍵與環氧基之不飽和化合物所構成的共聚合物中，使（ -12- 1326300 Ο) • 甲基）丙烯酸等之不飽和單羧酸反應後，對所生成之2級 . 羥基進一步使飽和或不飽和之多價酸酐部分加成反應所得 到之含羧基之感光性預聚物； (2) 於具有羥基與環氧基之寡聚物或聚合物，例如 羥烷基（甲基）丙烯酸酯與烷基（甲基）丙烯酸酯與縮水 甘油基（甲基）丙烯酸酯之共聚合物，使（甲基）丙烯酸 等之不飽和單羧酸反應後，進一步使飽和或不飽和之多價 φ 酸酐部分加成反應所得到之含羧基之感光性預聚物； (3) 具有羧基之寡聚物或聚合物例如烷基（甲基） 丙烯酸酯與（甲基）丙烯酸之共聚合物，i分子中具有不 ' 飽和雙鍵與環氧基之不飽和化合物例如使縮水甘油基（甲 . 基）丙烯酸酯部分反應所得到之含羧基之感光性預聚物； (4) 對含羥基之聚合物使飽和或不飽和多價酸酐加 成反應，於所得到之反應生成物的羧基之一部分，使於1 分子中具有不飽和雙鍵與環氧基之不飽和化合物進一步反 # 應所得到之含羧基之感光性預聚物； (5) 對馬來酸酐等之不飽和多價酸酐、與苯乙烯、 異丁烯等具有乙烯基之芳香族烴或脂肪族烴之共聚合物， 使羥烷基（甲基）丙烯酸酯等之含羥基之（甲基）丙烯酸 - 酯反應所得到之含羧基之感光性預聚物；等之含羧基之感 光性預聚物（A-2)。此等含羧基之感光性預聚物（A-2) 係亦可單獨使用。但就所形成之黏著劑圖型的被黏著構件 及黏著構件的接著性而言，宜與前述之含羧基之感光性預 聚物（A-1)倂用。此等含羧基之感光性預聚物（A-2)之 -13- (10) 1326300 - 量的比率，宜爲含羧基之感光性預聚物全體量之50質量％ . 以下。 如此之含羧基之感光性預聚物（A)的酸價係依其種 類而適宜的範圍相異’但必須在於30~160mg K〇H/g的範 圍，較佳之範圍爲 45~120mg KOH/g。酸價小於 30mg KOH/g時，係對鹼水溶液之溶解性變差，反之，若大於 160mg KOH/g，親水性太高，故顯象時易產生皮膜之密著 φ 性的劣化或光硬化部（曝光部）之溶解，故不佳。 前述環氧樹脂（B)係可使用以往公知之全部的多官 能環氧樹脂，可舉例如 JAPAN EPOXY RESIN (股）製之 Epikote 828、Epikote 834、Epikote 1001、Epikote 1004、 . 大日本油墨化學工業（股）製之 Epichlon 840、
Epichlon850、Epichlon 1050 ' Epichlon2055 ' 東都化成( 股）製之 Epotote YD-011' YD-013、YD· 1 27、YD-128、 住友化學工業（股）製之Sumi-Epoxy ESA-011、ESA-014 # 、ELA-1 15、ELA-128 (任一者均爲商品名）等之雙酚 A 型環氧樹脂；JAPAN EPOXY RESIN (股）製之 Epikote YL903 '大日本油墨化學工業（股）製之 Epich】onl52、 Epichlonl65、東都化成（股）製之 Epotote YDB-400、 - YDB-500、住友化學工業（股）製之 Sumi-Epoxy ESB-400 、ESB-700 (任一者均爲商品名）等之溴化環氧樹脂； JAPAN EPOXY RESIN (股）製之 Epikote 152、Epikote 154、大日本油墨化學工業（股）製之Epichlon N-730' EpichlonN-770、EpichlonN-8 65、東都化成（股）製之 -14- (11) 1326300 • Epotote YDCN-701、YDCN-704、日本化藥（股）製之 EPPN-201 ' EOCN- 1 025、EOCN- 1020、EOCN-104S、RE-306、住友化學工業（股）製之Sumi-Epoxy ESCN-195X、 ESCN-22 0 (任一者均爲商品名）等之酚醛清漆型環氧樹脂
. ;大日本油墨化學工業（股）製之Epichlon 830、JAPAN EPOXY RESIN (股）製之 Epikote 807、東都化成（股） 製之 Epotote YDF-170、YDF-175、YDF-2 004 (任一者均
# 爲商品名）等之雙酚F型環氧樹脂；東都化成（股）製之 Epotote ST-2004、ST-2007、ST-3 000 (任一者均爲商品名 )等之添加氫雙酚A型環氧樹脂；JAPAN EPOXY RESIN ' (股）製之Epikote 604、東都化成（股）製之Epotote - YH-434、住友化學工業（股）製之 Sumi-Epoxy ELM-120 (任一者均爲商品名）等之縮水甘油基胺型環氧樹脂； Dai cel化學工業（股）製之Cer oxide 202 1 (商品名）等 之脂環式環氧樹脂；JAPAN EPOXY RESIN (股）製之YL- # 933、日本化藥（股）製之 ΕΡΡΝ·501、EPPN-502 (任一 者均爲商品名）等之三羥基苯基甲烷環氧樹脂；JAPAN EPOXY RESIN (股）製之 YL-6056、YX-4000、YL-6121 ' (任一者均爲商品名）等之聯二甲苯酚型或雙酚型環氧樹
# 脂或其等之混合物；日本化藥（股）製之EBPS-200、旭 電化工業（股）製之EPX-30、大日本油墨化學工業（股 )製之EXA-15 14 (任一者商品名）等之雙酚S型環氧樹 月旨；JAPAN EPOXY RESIN (股）製之 Epikote 157S (商品 名）等之雙酚A酚醛清漆型環氧樹脂；JAPAN EPOXY -15- (12) 1326300 ' RESIN (股）製之 Epikote YL-93 1 (商 - 乙烷型環氧樹脂；日產化學（股）製之 (商品名）等之雜環式環氧樹脂；曰 Blemmer DGT (商品名）等之二縮水甘 . 東都化成（股）製之ΖΧ·ΐ〇63(商品名 基二甲苯酚乙烷樹脂；新日鐵化學（股 ESN-360、大日本油墨化學工業（股 • EXA-4750、EXA-4700 (任一者均爲商 的環氧樹脂；大日本油墨化學工業（股 HP-7200H (任一者均爲商品名）等之具
·之環氧樹脂；日本油脂（股）製之CP - 一者均爲商品名）等的縮水甘油基（甲 合系環氧樹脂；進一步於環己基馬來醯 (甲基）丙烯酸酯共聚合系環氧樹脂等 個以上的環氧基之化合物等。此等係可 • 上而使用。 作爲上述熱硬化性成份之環氧樹月I 係相對於前述含羧基之感光性預聚物（ ，宜爲環氧基爲0.6~2.0當量，更宜爲 • 率。環氧基之調配量不定〇.6當量時， 性或電絕緣性會降低，故不佳。另外’ 過2.0當量時，過剩之環氧樹脂作用爲 降低，故不佳。 又，此等環氧樹脂（B)與前述含 品名）等之四苯基 TEPIC ' TEPIC-H 本油脂（股）製之 油基酞酸酯樹脂： )等之四縮水甘油 )製之 ESN-190 ' )製之 HP-4032 、 品名）等之含萘基 )製之 HP-7200 、 有二環戊二烯骨架 -50S ' CP-50M (任 基）丙烯酸酯共聚 亞胺與縮水甘油基 的一分子中具有2 單獨或組合2種以 i ( B)的調配量， A)之羧基1當量 0.8~1.6當量的比 羧基會殘存，耐鹼 環氧基之調配量超 可塑劑，塗膜強度 羧基之感光性預聚 -16- (13) 1326300 * 物（A)之反應促進劑，可倂用胺類、二氰二醯胺、尿素 . 衍生物、三聚氰胺' S -三氮雜苯化合物、鳥糞胺化合物、 2-乙基-4·甲基咪唑等之咪唑化合物及其衍生物等之公知的 環氧硬化促進劑。藉倂用此等且熱硬化，可提昇硬化塗膜 . 之耐熱性、耐藥品性、黏著性 '鉛筆硬度等之各特性。 前述光聚合起始劑（C )之具體例，可舉例如苯偶因 、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚等之苯 • 偶因與苯偶因烷基醚類；乙醯苯、2,2-二甲氧基-2-苯基乙 醯苯、2,2-二乙氧基-2-苯基乙醯苯、1,1-二氯乙醢苯等之 乙醯苯類；2 -甲基- 】·〔4-(甲基硫）苯基〕-2 -嗎啉基丙 ' 烷-卜酮、2-苯甲基-2-二甲基胺基-1-( 4-嗎啉基苯基）-丁 • 酮-1等之胺基乙醯苯類；2-甲基蒽醌、2-乙基蒽醌、2-第 三丁基蒽醌、1-氯蒽醌等之蒽醌類；2,4 -二甲基硫雜蒽酮 、2，4-二乙基硫雜蒽酮、2-氯硫雜蒽酮、2,4-二異丙基硫 雜蒽酮等之硫雜蒽酮類；乙醯苯二甲基縮酮、苯甲基二甲 Φ 基縮酮等之縮酮類；二苯甲酮等之二苯甲酮類；或氧雜蒽 酮類；（2,6-二甲氧基苯甲醯基）-2,4,4-戊基磷氧化物、 雙（2,4,6-三甲基苯甲醯基）-苯基磷氧化物、2,4,6-三甲 ' 基苯甲醯基二苯基磷氧化物、乙基- 2,4,6-三甲基苯甲醯基 • 苯基膦酸酯等之磷氧化物類；各種過氧化物類等，可使此 等公知慣用之光聚合起始劑單獨或2種類以上組合而使用 。此等之光聚合起始劑之調配比率以一般之量比率即充分 ，前述感光性預聚合物（A)每100重量份宜爲1〜20重量 份。 -17- (14) 1326300 - 又，如上述之光聚合起始劑係可與N，N -二甲基胺基安 ; 息香酸乙酯、N，N-二甲基胺基安息香酸異戊酯、戊基·4-二甲基胺基苯甲酸酯、三乙胺、三乙醇等之三級胺類、白 色染料等之光增感劑的1種或2種以上組合而使用。 . 進一步’要求更深之光硬化深度時，依需要，而組合 一·在可見區域起始自由基聚合之Ciba Specialty Chemical 公司製CG 1784等之二茂鈦系光聚合起始劑等作爲硬化助 _ 劑而使用。 又，用於本發明之光硬化型/熱硬化型黏著劑中，以 光硬化性之提高等作爲目的，而依需要可調配光聚合性單 . 體。 . 光聚合性單體之代表例，可舉例如2-羥乙基（甲基） 丙烯酸酯' 2·羥丙基（甲基）丙烯酸酯等之羥基烷基（甲 基）丙烯酸酯類；乙二醇、甲氧基四乙二醇、聚乙二醇等 之甘醇的單體或二（甲基）丙烯酸酯類；Ν,Ν-二甲基（甲 Φ 基）丙烯醯胺、Ν-羥甲基（甲基）丙烯醯胺等之（甲基） 丙烯醯胺類；Ν，Ν-二甲基胺基乙基（甲基）丙烯酸酯等之 胺基烷基（甲基）丙烯酸酯類；己二醇、三羥甲基丙烷、 ' 季戊四醇、雙三羥甲基丙烷 '二季戊四醇、三羥基乙基三 * 聚異氰酸酯等之多元醇或此等環氧乙烷或環氧丙烷加成物 之多價（甲基）丙烯酸酯類；苯氧基乙基（甲基）丙烯酸 酯、雙酚Α之聚乙氧基二（甲基）丙烯酸酯等之酚類的環 氧乙烷或環氧丙烷加成物之（甲基）丙烯酸酯類；甘油二 縮水甘油基醚 '三羥甲基丙烷三縮水甘油基醚、三縮水甘 •18- (15) 1326300 • 油基三聚異氰酸酯等之縮水甘油基醚的（甲基）丙烯酸酯 類；及三聚氰胺（甲基）丙烯酸酯類等。進一步，可舉例 如含有羥基之（甲基）丙烯酸酯與多價羧酸化合物的酸酐 之反應物。此等之光聚合性單體係與如前述之感光性預聚 . 物混合而使用時’不僅作用爲稀釋劑，亦有助於組成物之 光硬化性的促進及顯像性提昇。 又’光聚合性單體之調配量係相對於前述含羧基之感 # 光性預聚物（A) 100質量份，宜以60質量份以下之比率 使用’較此多時，指觸乾燥性變差，故不佳。 用於本發明之光硬化型/熱硬化型黏著劑中係可依需 ' 要而添加各種顏料或導電性粒子。顔料係可依所希望之用 - 途而酞菁綠等之綠色顏料、酞菁藍等之藍色顏料、單偶氮 顏料、二偶氮顏料等之黃色顔料 '鉬紅、氧化鐵紅等之紅 色顏料、碳黑、燈黑 '骨黑 '石墨、鐵黑 '銅鉻系黑 '銅 鐵鐘系黑、姑鐵鉻系黑、四三氧化銘等之氧化銘、氧化金了 ® 等之黑色顏料、喹吖酮紫、二氧化紫等之紫色顏料、氧化 鈦（二氧化鈦顏料或鈦白）'氧化鋅等之白色顏料等、以 往公知的任意顔料單獨或組合2種以上而使用。導電性粒 ' 子可舉例如銅 '銀、鎳、鋁、錫、鉑、鎢 '金、鈀、焊錫 _ 等之金屬粒子、或於樹脂粒子被覆上述金屬之層者等。 如上述之顏料或導電性粒子之平均粒徑，就解析度而 言’爲20/zm以下，更宜爲5//m以下。又，此等之調配 比率只要無損本發明之效果，可依所希望的用途而爲任意 的比率。 -19- (16) 1326300 ' 用於本發明之光硬化型/熱硬化型黏著劑，係進—步 • 提昇塗膜之密著性、硬度等之特性的目的，或依所希望的 用途’而可含有玻璃片、或氧化鋁' 堇青石、锆石等之陶 瓷微粒子' 硫酸頻 '滑石、氧化砂、氧化欽' 氧化銘 '碳 - 酸鈣等之墳充劑成份。又，以顏料或導電性粒子、塡充劑 成份之防止2次凝集、分散性之提昇爲目的，可使用一以 作用爲安定化劑之有機酸' 無機酸或碟酸化合物（無機磷 • 酸、有機磷酸）、或矽烷偶合劑、鈦酸酯系偶合劑、鋁系 偶合劑等經預先表面處理者，或在調配組成物之時序，可 添加少量上述處理劑。 ' 用於本發明之光硬化型/熱硬化型黏著劑中進一步依 - 需要而爲調整黏度，亦可添加稀釋劑。稀釋劑係可使用如 前述之液狀單官能的光聚合性單體等之反應性稀釋劑之外 、尙可使用有機溶劑。有機溶劑係可使用甲乙酮、環己酮 等之酮類；甲苯、二甲苯、四甲基苯等之芳香族烴類；溶 • 纖劑、甲基溶纖劑、丁基溶纖劑'卡必醇溶纖劑、甲基溶 纖劑、丁基溶纖劑 '丙二醇單甲基醚、二丙二醇單甲基醚 、二丙二醇二乙基醚、三丙二醇單甲基醚等之甘醇醚類； • 醋酸乙酯、醋酸丁酯、乳酸丁酯 '溶纖劑乙酸酯、丁基溶 - 纖劑乙酸酯' 卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇 單甲基醚乙酸酯、二丙二醇單甲基醚乙酸酯、碳酸丙烯酯 等之酯類；辛烷、癸烷等之脂肪族烴類；石油醚、石腦油 '溶劑石腦油等之石油系溶劑等之公知慣用的有機溶劑。 此等之有機溶劑係可單獨或2種類以上組合而使用。 -20- (17) 1326300 * 進一步用於本發明之光硬化型/熱硬化型黏著劑依需 . 要而爲形成安定之糊劑，可添加一適於顏料或導電性粒子 、塡充劑成份之分散劑，或以無損本發明之效果的量比率 添加公知慣用之熱聚合抑制劑' 增黏劑、可塑劑、流動性 . 賦予劑、安定劑、消泡劑、流平劑、防止壓黏劑等。分散 劑係可使用羧基、羥基、酸酯等之顔料或與塡充劑成份具 有親和性之極性基的化合物或高分子化合物、例如磷酸酯 • 類等之含酸的化合物、或含酸基之共聚合物、含有羥基之 聚羧酸酯、聚矽氧烷、長鏈聚胺基醯胺與酸酯之鹽等。於 市售之分散劑尤宜使用者可舉例如Disperbyk (註冊商標 ’ ）-101、 -103、 -110、 -111、 -160' 及-300(任一者均爲 • B YK Chemie 公司製）。 【實施方式】 (實施例） 以下表示實施例及比較例而更具體地說明本發明，但 當然本發明不限定於下述實施例。又，在以下中「份」係 只要無特別聲明，全部爲質量基準。 實施例1 ~ 4 以表1所示之比率調配各成份，攪拌後，以3根輥硏 磨機進行分散而得到光硬化型/熱硬化型黏著劑。 -21 - (18) 1326300
〔表1〕 組成（質量份） 實施例) 編號 1 2 3 4 含羧基的感光性預聚物 156 156 156 156 環 Epikote828 18 • —— 氧 Epikote 1001之凡立水 60 - 二-— 樹 DEN483之凡立水 - 75 - ·" 一 脂 Epikote YX-4000 - - 75 TEPIC-H • - . 40 Aronix M6200 35 35 35 35 Irgacure-907 12 12 12 12 聚形 ，氧系消泡劑 1 1 1 k~-- 1 含羧基之感光性預聚物之凡立水：相對於甲酚酚醛清漆型環氧樹脂之1環氧基 當量，加成丙烯酸0_95~1.05莫耳，然後，加成四氫酞酸酐0·6莫耳所得到之含 殘基之感光性預聚物的含卡必醇乙酸酯35%的凡立水 Epikote 828 : Japan Epoxy Resin (股）製雙酚Α型環氧樹月旨 備Epikote 1001之凡立水：Japan Epoxy Resin (股）製雙酣A型環氧樹脂的含卡必 醇乙酸酯25%的凡立水
Den483之凡立水：Dow Chemical (股）製酚醛清漆型環氧樹脂之卡必醇乙酸酯 註 10%的凡立水
TEPIC-H :三（2,3-環氧基丙基）三聚異氰酸酯（曰產化學工業（股）製） Epikote YX-4000 : Japan Epoxy Resin (股）製雙苯基型環氧樹脂 AronixM6200 :東亞合成化學（股）製兩末端丙烯酸酯聚酯寡聚物 Irgacure-907 : 2-甲基-1-〔4-(甲基硫）苯基〕-2·嗎咐基丙院小嗣_ (Ciba Speciality Chemicals 公司製）
Silicon系消泡劑：信越化學工業（股）製KS-66 使如以上般所調製之各光硬化型/熱硬化型黏著劑於 1.6mm厚的玻璃環氧基基材（FR-4)全面，以網版印刷塗 佈成膜厚4〇//m，以熱風循環式乾燥爐在8〇。〇下乾燥 分鐘。其後’使線及間隙200//m之負型的光罩密接，以 金屬鹵化物燈之光源以累積光量爲4〇〇mj/cm2之條件進行 -22- (19) 1326300 * 曝光後，以30t之1 %碳酸鈉水溶液顯像，水 . 而於基材上形成黏著劑圖型。 其次，使表2所示之各材料密接於上述黏 上，以50g/cm2之壓力固定而壓接，以熱風循 ▲ 在150°C下熱硬化60分鐘，得到層合結構物。 劑圖型的形狀，可確認出任一者均膜厚約20 // 及間隙200 # m之構造並發揮接著劑的功能同 • 細的結構構件功能。 將如此做法所得到之各層合結構物的接著 果表示於表2中。 ' 又，在表2中，各材料之厚度係FR-4基:j - 、紙-酚複合基材：1.6mm、BT基材：l.6mm、 :1.6mm、銅板：0.8 mm、不銹鋼板：0.8 mm 1 2 5 /2 m。 洗、乾燥， 著劑圖型之 環式乾燥爐 此時之黏著 m、具有線 時發揮高精 性之評估結 才：1 · 6 mm 非鹵素基材 、PET 膜：
-23- (20) 1326300 〔表2〕 薄片構件 實施例編號 1 2 3 4 FR-4基材 〇 〇 〇 〇 紙-酚複合基材 〇 〇 〇 〇 ΒΤ基材η 〇 〇 〇 〇 非鹵素基材2) 〇 〇 〇 〇 1mm厚玻璃板 〇 〇 〇 〇 銅板 △ △ Δ △ 不銹鋼板 △ △ △ △ 紙 〇 〇 〇 〇 PET膜 Δ △ △ Δ 〇：很強地接著而剝離時材料破壞 △:雖接著，'但很乾淨地剝離 βΒΤ基材：雙馬來醯亞胺/三氮雜苯樹脂基材 *2)非鹵素基材：日立化成工業（股）製MCL-RO-67G (MCL爲註冊商標） 備註 從表2所示之結果可明確地確認出與各種黏著構件（ φ 結構構件）之接著性亦良好。 〔產業上之利用可能性〕 - 本發明之光硬化型/熱硬化型黏著劑係適於作爲精密 . 圖型之結構支撐部（間隙、肋或隔壁）之黏著劑圖型必須 的各種顯示裝置中之層合結構的形成，又，對於各種基板 上所形成之微細佈線圖型而使其他之佈線圖型或各種電子 零件的電極進行導電連接之層合構造、背光裝置（背面照 明裝置）的光反射部等之形成。 -24- (21) (21)1326300 【圖式簡單說明】 圖 1係用以說明一使用本發明之光硬化型/熱硬化型 黏著劑而藉光微顯法形成層合結構物之步驟的槪略部分剖 面圖° 【主要元件符號說明】 1 :基板（被黏著構件） 2 :光硬化型/熱硬化型黏著劑之塗膜 3 :光罩 4 :黏著劑圖型 5·薄片構件（黏著構件）
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Claims (1)

1326300 十、申請專利範圍 第95 1 1 8307號專利申請案 中文申請專利範圍修正本 民國99年2月12曰修正 1. 一種層合結構物之製造方法，係爲一使用於構件之 φ 間藉由以鹼顯像型微影法所形成之黏著劑圖型的硬化物而 黏合之層合結構物之製造方法，特徵在於··使由含有（A )於1分子中一倂具有羧基與乙烯性不飽和鍵，且具有酸 * 價3〇〜16 0mgKOH/g之含羧基的感光性預聚物、（B)環氧 . 樹脂及（C )光聚合起始劑作爲必須成份之光硬化型/熱硬 化型接著劑塗佈於被黏著構件表面，以活性能量束選擇性 圖型曝光後，藉顯像除去未曝光部而形成黏著劑圖型，然 後’使爲接合之黏著構件壓接於上述黏著劑圖型而使上述 φ 黏著劑圖型熱硬化。 2. 如申請專利範圍第1項之層合結構物之製造方法 ，其中前述含有羧基的感光性預聚物（A)，係於1分子 中至少具有2個環氧基之多官能環氧基化合物（a)的環 氧基，與不飽和單羧酸（b)之羧基進行酯化反應，使所 生成之2級羥基進一步與飽和或不飽和的多價酸酐（c) 進行加成反應所得到之含有羧基的感光性預聚物。 3. 如申請專利範圍第1項之層合結構物之製造方法 ，其中前述光硬化型/熱硬化型接著劑進一步含有有機溶 1326300 劑及/或光聚合性單體作爲稀釋劑。 4. 如申請專利範圍第1項之層合結構物之製造方法 ’其中前述光硬化型/熱硬化型接著劑係進一步含有至少 一種選自由顔料、導電性粒子、陶瓷微粒子、塡充劑、分 散劑、熱聚合抑制劑、增黏劑、可塑劑、流動性賦予劑、 安定劑、消泡劑、流平劑、及壓黏抑制劑所構成之群的添 加劑。 5. —種層合結構物，係爲一使用於構件之間藉由鹼 顯像型微影法所形成之黏著劑圖型的硬化物而黏合之層合 結構物，特徵在於：前述黏著劑圖型爲由含有（A)於1 分子中一倂具有羧基與乙烯性不飽和鍵，且具有酸價 30〜160mgKOH/g之含羧基的感光性預聚物、（B)環氧樹 脂及（C )光聚合起始劑作爲必須成份之光硬化型/熱硬化 型接著劑的硬化物所形成。 / -2-
TW095118307A 2005-05-31 2006-05-23 Composition for forming adhesive pattern, multilayer structure obtained by using same, and method for producing such multilayer structure TW200710570A (en)

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