CN105980931A - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device - Google Patents

Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device Download PDF

Info

Publication number
CN105980931A
CN105980931A CN201580008378.9A CN201580008378A CN105980931A CN 105980931 A CN105980931 A CN 105980931A CN 201580008378 A CN201580008378 A CN 201580008378A CN 105980931 A CN105980931 A CN 105980931A
Authority
CN
China
Prior art keywords
group
photosensitive polymer
polymer combination
alkyl
cured film
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN201580008378.9A
Other languages
Chinese (zh)
Inventor
安藤豪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
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 Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN105980931A publication Critical patent/CN105980931A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • 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
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • 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
    • G03F7/2012—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 using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Power Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Silicon Polymers (AREA)
  • Liquid Crystal (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Provided is a photosensitive resin composition which exhibits good sensitivity and can form a cured film having excellent solvent resistance. Further, provided are: a method for producing a cured film by using a photosensitive resin composition; a cured film; a liquid crystal display device; an organic EL display device; and a touch panel display device. This photosensitive resin composition contains: a polysiloxane (A) having a constituent unit (a1) which has a group obtained by protecting a carboxyl group with an acid-dissociable group and/or a group obtained by protecting a phenolic hydroxyl group with an acid-dissociable group, and a constituent unit (a2) having a crosslinkable group; a photo-acid generator (B) that generates an acid having a pKa value of 3 or lower; and a solvent (C).

Description

Photosensitive polymer combination, the manufacture method of cured film, cured film, liquid crystal display fill Put, organic EL display and touch panel display device
Technical field
The present invention relates to a kind of photosensitive polymer combination (following, to be sometimes also referred to as " compositions of the present invention ").And And, it is directed to use with the manufacture method of the cured film of above-mentioned photosensitive polymer combination, by consolidating that photosensitive composite solidifies Change film, use the various image display devices of above-mentioned cured film.
Further specifically, relate to suitably forming liquid crystal indicator, organic EL (organic electroluminescent) display device, The planarization film of electronic building brick, protecting film and the interlayers such as touch panel display device, integrated circuit component, solid-state imager are exhausted The photosensitive polymer combination of velum and use the manufacture method of cured film of this photosensitive polymer combination.
Background technology
Organic EL display, liquid crystal indicator, touch panel display device etc. are provided with the interlayer formed by pattern Dielectric film.From less for obtaining the process number of desirable pattern shape, and the angle of available sufficient flatness is set out, shape Photosensitive polymer combination is widely used when becoming this interlayer dielectric.
Recently, for the efficient activity manufactured and the high performance of display device, the display after manufacture interlayer dielectric In device manufacturing process, attempt carrying out heat treatment or masking, for layer at the highest temperature (such as about 300 DEG C) Between dielectric film, also require that the patience for the highest temperature.As the interlayer dielectric of this high-fire resistance, to poly- The use of siloxanes is studied.
Having eurymeric anti-corrosion agent composition disclosed in patent documentation 1, it contains alkali-soluble siloxane polymer and has 1, The photosensitive compounds of 2-diazido naphthoquinone base.
Having positive type photosensitive organic compound disclosed in patent documentation 2, it contains: as the polysiloxanes of (A) composition, contain There is the construction unit with the carboxylic acid by acid decomposability radical protection；Light acid producing agent as (B) composition；As (C) composition Organic solvent；And as (D) composition containing epoxy radicals silicone compounds.There is (D) composition relative described in paragraph 0093 It is preferably 1～40 mass parts in (A) composition 100 mass parts.
Having photosensitive polymer combination disclosed in patent documentation 3, it contains polysiloxane, and described polysiloxanes contains: tool There is the construction unit of protected silanol group；And there is the construction unit of epoxy radicals.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-255546 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2013-92633 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-263522 publication
Summary of the invention
The technical task that invention is to be solved
But, eurymeric anti-corrosion agent composition disclosed in patent documentation 1 is studied by the present inventor, and its result obtains Knowing, owing to having 1 used in patent documentation 1, the quantum yield of the photosensitive compounds of 2-diazido naphthoquinone base is relatively low, Therefore the sensitivity of eurymeric anti-corrosion agent composition is the most insufficient.
Further, positive type photosensitive organic compound disclosed in patent documentation 2 is studied by the present inventor, its knot Fruit learn, due to patent documentation 2 positive type photosensitive organic compound because of as cure component containing epoxy radicals silicone compound The content of thing is less, and therefore solvent tolerance is insufficient.Further, learn, if increase the silicon containing epoxy radicals to improve solvent tolerance The content of siloxane compound, then sensitivity deteriorates.
Further, photosensitive polymer combination disclosed in patent documentation 3 is studied by the present inventor, and its result obtains Knowing, although the photosensitive polymer combination sensitivity of patent documentation 3 is excellent, but solvent tolerance is insufficient.
So, present situation is to form the photosensitive polymer combination of the cured film that sensitivity is good and solvent tolerance is excellent The most known.
Therefore, it is an object of the invention to provide and a kind of can form the cured film that sensitivity is good and solvent tolerance is excellent Photosensitive polymer combination, apply the manufacture method of the cured film of this photosensitive polymer combination, cured film, organic EL aobvious Showing device, liquid crystal indicator and touch panel display device.
For solving the means of technical task
In such a case, present inventor has performed research, it is it was found that pass through and use have construction unit (a1) With the polysiloxanes of construction unit (a2) and the light acid producing agent that produces the acid that pKa is less than 3, described construction unit (a1) has Carboxyl by the acid group of decomposability radical protection and/or phenolic hydroxyl group by the group of acid decomposability radical protection, described structure list Unit (a2) has crosslinkable groups, thus available can form the photosensitive of sensitivity is good and solvent tolerance is excellent cured film Property resin combination, and complete the present invention.Below the present invention provides.
＜ 1 ＞ photosensitive polymer combination, it contains: (A) polysiloxanes, described polysiloxanes has construction unit (a1) and construction unit (a2), described construction unit (a1) has carboxyl by the group of acid decomposability radical protection and/or phenol Hydroxyl is by the group of acid decomposability radical protection, and described construction unit (a2) has crosslinkable groups；(B) light acid producing agent, produces Raw pKa is the acid of less than 3；And (C) solvent.
＜ 2 ＞ is according to the photosensitive polymer combination described in ＜ 1 ＞, and wherein, acid decomposability group is acetal radical.
＜ 3 ＞ is according to the photosensitive polymer combination described in ＜ 1 ＞ or ＜ 2 ＞, and wherein, construction unit (a1) is following logical Construction unit represented by formula (a1-1) and/or the construction unit represented by following formula (a1-2).
[chemical formula 1]
(in formula (a1-1), (a1-2), a represents 0 or 1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2In at least one represent alkyl or aryl, R3Represent alkyl or aryl, R1Or R2With R3Can connect and be formed ring-type Ether, R4Represent alkyl, aryl or aralkyl, L1Represent singly-bound or divalent linking group, L2Represent singly-bound or divalent linking group, Rx Representing alkyl or halogen atom, m1 represents the integer of 0～4.)
＜ 4 ＞ is according to any one described photosensitive polymer combination in ＜ 1 ＞ to ＜ 3 ＞, wherein, construction unit (a2) The crosslinkable groups being had is cyclic ether and/or the group with ethylenic unsaturated bond.
＜ 5 ＞ is according to any one described photosensitive polymer combination in ＜ 1 ＞ to ＜ 4 ＞, wherein, construction unit (a2) Construction unit represented by following formula (a2-1) and/or the construction unit represented by following formula (a2-2).
[chemical formula 2]
(in formula (a2-1), (a2-2), a represents 0 or 1, R5Represent alkyl, aryl or aralkyl, RYRepresent alkyl or halogen Atom, L3Representing singly-bound or divalent linking group, n represents 0 or 1, about m2, represents the integer of 0～2 when n is 0, when n is 1 Representing the integer of 0～3, m3 represents the integer of 0～6.)
＜ 6 ＞ is according to any one described photosensitive polymer combination in ＜ 1 ＞ to ＜ 5 ＞, wherein, (A) polysiloxanes Possibly together with the construction unit (a3) with acidic group.
＜ 7 ＞ is according to the photosensitive polymer combination described in ＜ 6 ＞, and wherein, construction unit (a3) has carboxyl and/or phenol Property hydroxyl is as acidic group.
＜ 8 ＞ is according to the photosensitive polymer combination described in ＜ 6 ＞ or ＜ 7 ＞, wherein, in photosensitive polymer combination In contained (A) polysiloxanes total amount, the molal quantity of construction unit (a1) and the total of the molal quantity of construction unit (a3) and knot The ratio of the molal quantity of structure unit (a2) is 10:90～90:10.
＜ 9 ＞ is according to any one described photosensitive polymer combination in ＜ 1 ＞ to ＜ 8 ＞, wherein, photoresist group Crosslinkable groups equivalent in the solid constituent of compound is less than 1500.
＜ 10 ＞ is according to any one described photosensitive polymer combination in ＜ 1 ＞ to ＜ 9 ＞, and wherein, (B) light acid produces Agent is at least one in salt compound, oxime sulfonate compounds and acid imide sulfonate compound.
The manufacture method of a ＜ 11 ＞ cured film, it comprises: by any one described photonasty in ＜ 1 ＞ to ＜ 10 ＞ Resin combination coats the operation on substrate；The work of solvent is removed from the photosensitive polymer combination coated substrate Sequence；The operation that the photosensitive polymer combination removing solvent is exposed；Exposed photosensitive polymer combination is entered The operation of row development；And the operation by developed photosensitive polymer combination heat cure.
＜ 12 ＞ cured film, it is that any one described photosensitive polymer combination in ＜ 1 ＞ to ＜ 11 ＞ is solid The cured film changed and obtain or the cured film formed for the manufacture method by the cured film described in ＜ 12 ＞.
＜ 13 ＞ is according to the cured film described in ＜ 12 ＞, and it is interlayer dielectric.
＜ 14 ＞ liquid crystal indicator, it has the cured film described in ＜ 12 ＞ or ＜ 13 ＞.
＜ 15 ＞ organic EL display, it has the cured film described in ＜ 12 ＞ or ＜ 13 ＞.
＜ 16 ＞ touch panel display device, it has the cured film described in ＜ 12 ＞ or ＜ 13 ＞.
Invention effect
The present invention can provide the photosensitive resin composition that can form the cured film that sensitivity is good and solvent tolerance is excellent Thing.And, it is possible to provide use the manufacture method of the cured film of above-mentioned photosensitive polymer combination, cured film, liquid crystal indicator, Organic EL display and touch panel display device.
Accompanying drawing explanation
Fig. 1 represents the composition concept map of an example of liquid crystal indicator.Represent the active matrix base in liquid crystal indicator The schematic cross sectional views of plate, has the cured film 17 as interlayer dielectric.
Fig. 2 is the composition concept map of another example of liquid crystal indicator.
Fig. 3 represents the composition concept map of an example of organic EL display.Represent bottom emission type organic EL display In the schematic cross sectional views of substrate, there is planarization film 4.
Detailed description of the invention
Hereinafter, present disclosure is described in detail.The explanation of constitutive requirements described below be sometimes based on The representative embodiments of the present invention and carry out, but the present invention is not limited to this embodiment.It addition, the application explanation In book, "～" it is so that the implication that numerical value described before and after it comprises as lower limit and higher limit is used.
In the statement of group (atomic group) in this manual, do not record replacement and unsubstituted statement comprises and do not has The group of substituted base, and comprise the group with substituent group.Such as, " alkyl " not only comprises the alkane without substituent group Base (unsubstituted alkyl), but also comprise the alkyl (substituted alkyl) with substituent group.
Solid component concentration in this specification refers to the concentration of the solid constituent at 25 DEG C.Further, in this specification Viscosity refers to the viscosity at 25 DEG C.
In this specification, the polystyrene that weight average molecular weight and number-average molecular weight are defined through GPC mensuration and obtain Scaled value.In this specification, weight average molecular weight (Mw) and number-average molecular weight (Mn) such as can be by using HLC-8220 (TOSOH CORPORATION system), and use TSKgel Super AWM-H (TOSOH CORPORATION system, 6.0mmID × 15.0cm) as post, 10mmol/L lithium bromide NMP (N-Methyl pyrrolidone) solution is used to obtain as eluent.
[photosensitive polymer combination]
The photosensitive polymer combination of the present invention contains: (A) polysiloxanes, has construction unit (a1) and construction unit (a2), described construction unit (a1) has carboxyl by the acid group of decomposability radical protection and/or phenolic hydroxyl group by acid decomposability The group of radical protection, described construction unit (a2) has crosslinkable groups；(B) light acid producing agent, producing pKa is less than 3 Acid；And (C) solvent.
The photosensitive polymer combination of the present invention due to containing above-mentioned (A) polysiloxanes and above-mentioned (B) light acid producing agent, because of This can form the cured film that sensitivity is good and solvent tolerance is excellent.Further, by containing (A) polysiloxanes, additionally it is possible to shape Become the cured film of excellent heat resistance.And then, it is stable that the photosensitive polymer combination of the present invention can also make cured film become preservation Property, cured film that developability is excellent.The photosensitive polymer combination of the present invention can be preferably used as chemical amplifying type photonasty tree Oil/fat composition.
The photosensitive polymer combination of the present invention is from the viewpoint of the solvent tolerance of cured film, preferably in solid constituent Crosslinkable groups equivalent is less than 1500, more preferably less than 1000.From the viewpoint of sensitivity, developability, lower limit preferably 100 Above, preferably more than 150, most preferably more than 200.
Crosslinkable groups equivalent in solid constituent refers to bridging property base in the solid constituent of photosensitive polymer combination Group is the quality (g) of solid constituent during 1mol.Crosslinkable groups equivalent in solid constituent can be a certain amount of by weighing The solid constituent of photosensitive polymer combination also measures crosslinkable groups amount contained in this solid constituent and obtains.
Such as, when crosslinkable groups is epoxy radicals, it is possible to utilize defined in JIS K7236:2001 and asphalt mixtures modified by epoxy resin The identical method that measures of the epoxide equivalent of fat is obtained.Further, in the case of other crosslinkable groups other than the above, If change volumetric solution, then it also is able to be measured by identical method.
Hereinafter, each composition of the photosensitive polymer combination of the present invention is described in more detail.
＜ (A) polysiloxanes ＞
(A) polysiloxanes used in the photosensitive polymer combination of the present invention has construction unit (a1) and structure list Unit (a2), described construction unit (a1) has carboxyl and is decomposed by acid by group and/or the phenolic hydroxyl group of acid decomposability radical protection The group of property radical protection, described construction unit (a2) has crosslinkable groups.
(A) structure of polysiloxanes is not particularly limited.Can be straight-chain, ring-type, scalariform, netted in any one Kind, it is also possible to it is they interconnective structures.From the viewpoint of cured film hardness, preferably comprise scalariform or netted knot Structure.
＜ ＜ has carboxyl by the acid group of decomposability radical protection and/or phenolic hydroxyl group by acid decomposability radical protection Construction unit (a1) the ＞ ＞ of group
In the construction unit (a1) of (A) polysiloxanes, as acid decomposability group, it is possible to use the most relatively Labile group (such as, the acetals functional group such as ester structure described later, Pentamethylene oxide. ester group or oxolane ester group) and Group (such as, three grades of Arrcostabs of carbonic acid such as three grades of alkyl such as tert-butyl ester base, t-butyl carbonate base of more difficult decomposition under the effect of acid Base).In these groups, preferably acetal radical.That is, from the basic physical properties of photosensitive polymer combination, especially sensitivity and figure Case shape, the formative of contact hole, photosensitive polymer combination storage stability from the viewpoint of, preferably carboxyl is by acetal radical The protection phenolic group that the protection carboxyl of protection, phenolic hydroxyl group are protected by acetal radical.
(A) construction unit (a1) of polysiloxanes be preferably construction unit represented by following formula (a1-1) and/or under State the construction unit represented by formula (a1-2).
[chemical formula 3]
In formula (a1-1), (a1-2), a represents 0 or 1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1 And R2In at least one represent alkyl or aryl, R3Represent alkyl or aryl, R1Or R2With R3Can connect and form cyclic ether, R4Represent alkyl, aryl or aralkyl, L1Represent singly-bound or divalent linking group, L2Represent singly-bound or divalent linking group, RxRepresent Alkyl or halogen atom, m1 represents the integer of 0～4.
R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2In at least one be alkyl or aryl.
As alkyl, the preferably alkyl of carbon number 1～10, the more preferably alkyl of carbon number 1～8, further preferred carbon number 1～6 Alkyl.Alkyl can have substituent group.Further, alkyl can be straight chain, side chain, any one of ring-type, preferably straight chain Alkyl.As alkyl, such as, can exemplify methyl, ethyl, propyl group, butyl, the tert-butyl group, amyl group, hexyl, cyclohexyl etc..
As aryl, the preferably aryl of carbon number 6～20, the more preferably aryl of carbon number 6～14, further preferred carbon number 6～ The aryl of 10.Aryl can have substituent group.As aryl, such as, can exemplify phenyl, naphthyl, anthryl etc..
The substituent group can having as alkyl and aryl, can enumerate the alkyl of carbon number 1～10, the alcoxyl of carbon number 1～10 Base, the thio alkoxy of carbon number 1～10, hydroxyl, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine) etc..These Substituent group can have substituent group further.
Among those, preferably R1And R2For hydrogen atom, alkyl, more preferably hydrogen atom, methyl, particularly preferred R1And R2 In one be methyl and another be hydrogen atom.
R3Represent alkyl or aryl.R3Represented alkyl and the implication of aryl and R1And R2In alkyl, aryl identical.R3 It is preferably methyl, ethyl, propyl group, more preferably ethyl, propyl group.
R3Can be with R1Or R2Connect and form cyclic ether.As with R1Or R2The cyclic ether connected and formed, preferably 3～6 The cyclic ether of ring, the cyclic ether of more preferably 5～6 rings.
R4Represent alkyl, aryl or aralkyl.
As alkyl, the preferably alkyl of carbon number 1～10, the more preferably alkyl of carbon number 1～8, further preferred carbon number 1～6 Alkyl.Alkyl can have substituent group.Further, alkyl can be straight chain, side chain, any one of ring-type.
As aryl, the preferably aryl of carbon number 6～20, the more preferably aryl of carbon number 6～14, further preferred carbon number 6～ The aryl of 10.Aryl can have substituent group.As aryl, such as, can exemplify, phenyl, naphthyl, anthryl etc..
It is substituted by the aryl of carbon number 6～20 as aralkyl, preferably a part for the hydrogen atom of the alkyl of carbon number 1～10 Group.Aralkyl can have substituent group.Constituting the alkyl of aralkyl can be straight chain, side chain, any one of ring-type.
The substituent group can having as alkyl, aryl, aralkyl, and at R1、R2The substituent group of middle explanation is identical.
From the viewpoint of solvent tolerance and thermostability, R4Preferably methyl, phenyl, propyl group, butyl, hexyl, more preferably first Base, phenyl.
RxRepresent alkyl or halogen atom.As alkyl, the preferably alkyl of carbon number 1～4.As halogen atom, preferably fluorine atom, Chlorine atom, bromine atoms, atomic iodine.
L1And L2Represent singly-bound or divalent linking group.As divalent linking group, can enumerate carbon number 1～12 alkylidene, The epoxy alkyl of carbon number 1～12, the arlydene of carbon number 6～12.Epoxy alkyl and epoxy alkyl can be straight chains, side chain, ring-type Any one of.Further, alkylidene, epoxy alkyl, arlydene can have substituent group.Alternatively base, and at R1、R2In The substituent group illustrated is identical.
Construction unit represented by above-mentioned formula (a1-2) is preferably the construction unit represented by following formula (a1-2-1).
[chemical formula 4]
In formula (a1-2-1), a represents 0 or 1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2 In at least one represent alkyl or aryl, R3Represent alkyl or aryl, R1Or R2With R3Can connect and form cyclic ether, R4Table Show alkyl, aryl or aralkyl, L2Represent singly-bound or divalent linking group, RxRepresent alkyl or halogen atom, m1 represent 0～4 whole Number.
As in order to obtain construction unit (a1) and the concrete example of spendable silane compound, such as, can enumerate following Shown silane compound.
[chemical formula 5]
About the ratio of the construction unit (a1) in (A) polysiloxanes, from the viewpoint of sensitivity, gather relative to (A) Preferably 10～90 moles % of all repetitives of siloxanes, more preferably 15～70 moles %, further preferred 20～60 rub You are %.
＜ ＜ has construction unit (a2) the ＞ ＞ of crosslinkable groups
(A) construction unit (a2) of polysiloxanes has crosslinkable groups.In the present invention, crosslinkable groups refers to by heat The group of cross-linking reaction can be produced.
As long as crosslinkable groups is by the group of thermally-induced cross-linking reaction, then it is not particularly limited, it is possible to use public The crosslinkable groups known.Wherein, preferably carry out, by heat and carboxyl or phenolic hydroxyl group, the crosslinkable groups that cross-links.
For example, it is possible to enumerate cyclic ether, have the group of ethylenic unsaturated bond, blocked isocyanate ester group, alkoxy methyl, Methylol, amino etc..Further, crosslinkable groups can be bonded via linking group etc..
As cyclic ether, epoxy radicals, oxetanylmethoxy can be enumerated.
As having the group of ethylenic unsaturated bond, vinyl, pi-allyl, methylallyl, metering system can be enumerated Acyl group, acryloyl group, allyloxy carbonyl, methallyl epoxide carbonyl etc..
As alkoxy methyl, "-CH can be enumerated2OR " represented by group.R represents the alkyl of carbon number 1～8, The preferably alkyl of carbon number 1～4, more preferably methyl.Alkyl can be straight chain, side chain and any one of ring-type, preferably straight chain.
Blocked isocyanate ester group can enumerate the group that can be generated NCO by heat.For example, it is possible to preference Illustrate and make block agent and NCO reaction protect the group of NCO.As block agent, oximate can be enumerated and close Thing, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, Thiolation Compound, glyoxaline compound, imide analog compounds etc..Further, blocked isocyanate ester group is preferably by 90 DEG C～250 DEG C Heat can generate the group of NCO.
As amino, can be the amino with substituent group, it is also possible to be unsubstituted amino.
As crosslinkable groups, for the reason of the solvent tolerance that can improve photoresist composition further, preferably Epoxy radicals, oxetanylmethoxy and there is the group of ethylenic unsaturated bond, more preferably epoxy radicals or oxetanylmethoxy, particularly preferred ring Epoxide.
As the concrete example of crosslinkable groups, following crosslinkable groups can be enumerated, but be not limited to these.
[chemical formula 6]
In formula, * represents the coupling part with other groups.
Construction unit (a2), as long as having at least 1 crosslinkable groups in 1 construction unit, preferably has 1～3 Individual, more preferably 1.When construction unit (a2) has multiple crosslinkable groups, identical kind can be entirely, it is also possible to It it is different kinds.When containing multiple crosslinkable groups, the most identical kind.
As construction unit (a2), the construction unit represented by following formula (a2 ') can be enumerated.
[chemical formula 7]
Formula (a2 ') in, a represents 0 or 1, R5Represent alkyl, aryl or aralkyl, L3Represent singly-bound or divalent linking group, X represents crosslinkable groups.
From the viewpoint of cured film characteristic, construction unit (a2) is preferably the structure list represented by following formula (a2-1) Construction unit represented by first and/or following formula (a2-2).Further, the construction unit represented by following formula (a2-2) is more excellent Elect the construction unit represented by following formula (a2-2-1) as.
[chemical formula 8]
In formula (a2-1), (a2-2) and (a2-2-1), a represents 0 or 1, R5Represent alkyl, aryl or aralkyl, RYRepresent Alkyl or halogen atom, L3Representing singly-bound or divalent linking group, n represents 0 or 1, about m2, represents the integer of 0～2 when n is 0, Represent the integer of 0～3 when n is 1, m3 represents the integer of 0～6.
R5Represent alkyl, aryl or aralkyl.As alkyl, aryl and aralkyl, and at above-mentioned (a1-1) and (a1-2) R4The scope of middle explanation is identical, and preferably scope is the most identical.
L3Represent singly-bound or divalent linking group.As divalent linking group, with the L at (a1-1)1And the L of (a1-2)2Middle theory Bright scope is identical, and preferably scope is the most identical.
RYRepresent alkyl or halogen atom.As alkyl and halogen atom, with the R at above-mentioned (a1-2)xThe scope phase of middle explanation With, preferably scope is the most identical.
N represents 0 or 1, preferably 0.
About m2, represent the integer of 0～2 when n is 0, represent the integer of 0～3 when n is 1.M2 preferably 0.
M3 represents the integer of 0～6, preferably 0.
As in order to obtain construction unit (a2) and the concrete example of spendable silane, 3-methacryloxypropyl can be enumerated Base hydroxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyl, 3-acryloxypropyl trimethoxy silicon Alkane, vinyltrimethoxy silane, VTES, 3-glycidoxypropyl diethoxy silane, 3- Glycidoxypropyl group triethoxysilane etc..And, it is possible to use silane compound shown below.
[chemical formula 9]
About the ratio of the construction unit (a2) in (A) polysiloxanes, from the viewpoint of cured film characteristic, relative to (A) preferably 10～90 moles % of all repetitives of polysiloxanes, more preferably 15～70 moles %, further preferred 25～65 Mole %.
＜ ＜ has construction unit (a3) the ＞ ＞ of acidic group
(A) polysiloxanes can be containing the construction unit (a3) with acidic group.Acidic group in the present invention refers to silicon poly-to (A) Oxygen alkane gives or improves the deliquescent group in alkaline-based developer.As concrete acidic group, carboxyl, sulphonyl can be exemplified Amido, phosphono, sulfonyl, phenolic hydroxyl group, sulfoamido, sulfimide base, as preferred acidic group, can enumerate carboxyl and Phenolic hydroxyl group.
As having the construction unit (a3) of acidic group, such as can enumerate the structure represented by below general formula (a3-1) and/ Or the structure represented by formula (a3-2) is as preferred concrete example.
[chemical formula 10]
(in formula (a3-1), (a3-2), a represents 0 or 1, R6Represent alkyl, aryl or aralkyl, L4Represent singly-bound or divalent Linking group, L5Represent singly-bound or divalent linking group, RzRepresenting alkyl or halogen atom, m4 represents the integer of 0～4.)
R6Represent alkyl, aryl or aralkyl.As alkyl, aryl and aralkyl, and at above-mentioned (a1-1) and (a1-2) R4The scope of middle explanation is identical, and preferably scope is the most identical.
L4Represent singly-bound or divalent linking group.As divalent linking group, with the L at (a1-1)1The scope phase of middle explanation With, preferably scope is the most identical.
L5Represent singly-bound or divalent linking group.As divalent linking group, with the L at (a1-2)2The scope phase of middle explanation With, preferably scope is the most identical.
RzRepresent alkyl or halogen atom.As alkyl and halogen atom, with the R at above-mentioned (a1-2)xThe scope phase of middle explanation With, preferably scope is the most identical.
Construction unit represented by above-mentioned formula (a3-2) is preferably the construction unit represented by following formula (a3-2-1).
[chemical formula 11]
In formula (a3-2-1), a represents 0 or 1, R6Represent alkyl, aryl or aralkyl, L5Represent singly-bound or divalent linker Group, RzRepresenting alkyl or halogen atom, m4 represents the integer of 0～4.
As in order to obtain construction unit (a3) and spendable silane compound, it is possible to use with in order to obtain structure list Unit (a1) and the identical silane compound of spendable silane compound.
About the ratio of the construction unit (a3) in (A) polysiloxanes, from the viewpoint of sensitivity, gather relative to (A) Preferably 0～50 mole % of all repetitives of siloxanes, more preferably 1～40 mole %, particularly preferred 5～25 moles of %.
＜ ＜ other construction units (a4) ＞ ＞
(A) polysiloxanes can be containing the construction unit (a4) in addition to said structure unit (a1)～(a3).
About the ratio of the construction unit (a4) in polysiloxanes (a), from the viewpoint of developability and cured film characteristic, Relative to (A) polysiloxanes preferably 0～40 mole % of all repetitives, more preferably 0～25 mole %, particularly preferred 1～ 20 moles of %.
As construction unit (a4), such as, can enumerate the structure represented by below general formula (a4-1) as the most concrete Example.
[chemical formula 12]
In formula (a4-1), a represents the integer of 0～3, and b represents the integer of 0～3.Wherein, 0≤a+b≤3.R7And R8Respectively Represent alkyl, aryl or aralkyl independently.
As R7、R8Represented alkyl, aryl and aralkyl, and at above-mentioned (a1-1) and the R of (a1-2)4Middle explanation Scope is identical, and preferably scope is the most identical.
As in order to obtain construction unit (a4) and spendable silane compound, alkoxy silane chemical combination can be enumerated Thing, chlorosilane cpd etc..Specifically, MTES, dimethyldiethoxysilane, phenyl three can be enumerated Ethoxysilane, hexyl triethoxysilane, decyl trimethoxy silane, trifluoro propyl trimethoxy silane etc..And, it is possible to To use silane compound shown below.
[chemical formula 13]
About (A) polysiloxanes used in the present invention, (A) polysiloxanes contained in photosensitive polymer combination In total amount, the total of the molal quantity of construction unit (a1) and the molal quantity of construction unit (a3) and the molal quantity of construction unit (a2) Ratio be preferably 10:90～90:10, more preferably 30:70～70:30, more preferably 40:60～60:40.If structure list The ratio of the molal quantity of the molal quantity of unit (a1) and the total of the molal quantity of construction unit (a3) and construction unit (a2) is at above-mentioned model In enclosing, then can form the cured film that solvent tolerance is excellent.
The silanol group that (A) polysiloxanes used in the present invention is remained when can contain polysiloxane polymerization.(A) The number of the silanol group in polysiloxanes total amount is preferably 0～0.5 times relative to the Si atomic number in (A) polysiloxanes, preferably It is 0～0.2 times, most preferably 0～0.05 times.If the number of silanol group is within the above range, then photosensitive polymer combination Storage stability is good.It addition, the number of the silanol group in (A) said here polysiloxanes total amount refers to (A) polysiloxanes The aggregate values of the number of silanol group contained in total amount.The most identical about Si atomic number.
(A) polysiloxanes is mixed by the silane compound or oligosiloxane making corresponding each construction unit and reacts and obtain Arrive.Such as, trimethoxy silane or dimethoxysilane by making correspondence hydrolyze, are condensed and obtain.Hydrolysis, condensation can be in order to Suitably carry out by known method, condition.For example, it is possible to reference to (especially 0085 section of Japanese Unexamined Patent Publication 10-324748 publication Fall～0087 paragraph), Japanese Unexamined Patent Publication 2005-283991 publication (especially 0052 paragraph～054 paragraph), Japanese Unexamined Patent Publication Step By Condition described in 2006-276598 publication (especially 0009 paragraph～0030 paragraph) etc..
The sour decomposability group of said structure unit (a1) can use protected silane compound to import, it is also possible to Imported by high molecular weight reactive.
It addition, as described in Japanese Unexamined Patent Publication 10-324748 publication (especially 0085 paragraph～0087 paragraph), when (A), when importing the construction unit containing carboxyl in polysiloxanes, the silane that the Arrcostab with corresponding carboxylic acid is preferably used closes Become polysiloxanes, and obtained the construction unit with carboxyl by usual way hydrolysis Arrcostab.
Further, in order to import the knot that there is phenolic hydroxyl group by the group of acid decomposability radical protection in (A) polysiloxanes Structure unit, preferably after synthesis has the polysiloxanes of phenolic hydroxyl group, imports acid decomposability by so-called high molecular weight reactive Group protects phenolic hydroxyl group.
In the photosensitive polymer combination of the present invention, (A) polysiloxanes solid in photosensitive polymer combination becomes 50～99.9 mass %, more preferably 60～99 mass %, more preferably 70～98 mass % it is preferably in Fen.(A) poly- Siloxanes can also and with two or more.When and when using two or more, preferably its always metering is within the above range.
＜ other polysiloxanes ＞
The photosensitive polymer combination of the present invention can add the polysiloxanes beyond above-mentioned (A) polysiloxanes (below, It is referred to as other polysiloxanes).
As other polysiloxanes, can enumerate containing said structure unit (a1) and without said structure unit (a2) Polysiloxanes, containing said structure unit (a2) and without the polysiloxanes etc. of said structure unit (a1).Can without departing from Containing them in the range of present inventive concept.
Further, as other polysiloxanes, containing said structure unit (a2) and gathering without said structure unit (a1) The content of siloxanes relative to (A) polysiloxanes 100 mass parts preferably 5 mass parts below, below more preferably 3 mass parts, it is possible to To be set to the composition contained substantially no.By being set to this composition, it is possible to improve the solvent tolerance of cured film further.Separately Outward, contain substantially no to refer to be such as below 1 mass parts relative to (A) polysiloxanes 100 mass parts.
In the photosensitive polymer combination of the present invention, (A) polysiloxanes always measures photosensitive with other polysiloxanes Property resin combination in solid constituent in be preferably 50～99.9 mass %, more preferably 60～99 mass %, the most excellent Elect 70～98 mass % as.
＜ (B) light acid producing agent ＞
The photosensitive polymer combination of the present invention contains (B) light acid producing agent.(B) light acid used in the present invention produces Agent is the light acid producing agent producing the acid that pKa is less than 3, more preferably produces the light acid producing agent of the acid that pKa is less than 2.Separately Outward, the pKa during the pKa of the present invention refers to the water of 25 DEG C substantially.In water, unmeasured pKa refers to change into and is suitable to mensuration The pKa measured after solvent.Specifically, pKa described in Chemical manual etc. it is referred to.It is the acid of less than 3 as pKa, It is preferably sulfonic acid or phosphoric acid, more preferably sulfonic acid.
(B) light acid producing agent is preferably the active ray of sensing more than wavelength 300nm, preferably sensing wavelength 300～450nm Active ray and produce the compound of acid, but be not limited to its chemical constitution.Further, about the most directly sensing wavelength The light acid producing agent of the active ray of more than 300nm, as long as by with sensitizer and with and sense the work of more than wavelength 300nm Property light and produce acid compound, then can with sensitizer combination and be preferably used.
As the example of (B) light acid producing agent, salt compound, trichloromethyl-s-triazine, Azimethylene. can be enumerated Compound, acid imide sulfonate compound, oxime sulfonate compounds and acid imide sulfonate compound etc..Among those, from From the viewpoint of sensitivity, developability, it is preferably selected from salt compound, oxime sulfonate compounds and acid imide sulfonate compound In more than one, be more preferably selected from oxime sulfonate compounds and acid imide sulfonate compound more than one.These light Acid producing agent can be used alone one or is applied in combination two or more.As trichloromethyl-s-triazine, Diaryl iodonium Salt, triaryl sulfonium salts class, quaternary ammonium salt and the concrete example of diazomethane derivative, can exemplify Japanese Unexamined Patent Publication 2011- Compound described in the paragraph 0083～0088 of No. 221494 publications.
As salt compound, preferably sulfosalt or iodine salt, quaternary ammonium salt.Further, the most following formula (1) And/or the light acid producing agent represented by formula (2).
[chemical formula 14]
(in formula, R5、R6And R7Separately represent alkyl or aryl, when representing alkyl, can be connected with each other and shape Cyclization, it is also possible to form ring via hetero atom.R8And R9Separately represent aryl, X-Represent conjugate base.)
R5、R6And R7Separately representing alkyl or aryl, alkyl or aryl can have substituent group.Alternatively base, The aryl of carbon number 1～10, the thioaryl of carbon number 1～10, the alkyl of carbon number 1～10, the alcoxyl of carbon number 1～10 can be enumerated Base, the thio alkoxy of carbon number 1～10, hydroxyl, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine) etc..These Substituent group can have substituent group further.
In formula (1), as R5、R6And R7Alkyl represented by Fen Bie, the preferably alkyl of carbon number 1～10, more preferably carbon number The alkyl of 1～6, the alkyl of further preferred carbon number 1～4.As alkyl, such as, can enumerate methyl, ethyl, the tert-butyl group etc.. Further, in formula (1), R5、R6And R7When middle two or more is alkyl, this plural alkyl can be interconnected to form Ring, it is also possible to form ring via hetero atom (such as oxygen atom, sulphur atom etc.).As this loop type, it is preferably containing sulfur former Son form and be 5 rings (tiacyclopentane) or 6 rings (thia hexamethylene).Alkyl can have substituent group.
In formula (1), as R5、R6And R7Aryl represented by Fen Bie, the preferably aryl of carbon number 6～15, more preferably carbon number The aryl of 6～10.Aryl can have substituent group.As aryl, phenyl, naphthyl, 4-methoxyphenyl, 4-chlorobenzene can be enumerated Base, 4-aminomethyl phenyl, 4-tert-butyl-phenyl, 4-Phenylsulfanylphenyl, 2,4,6-trimethylphenyl, 4-methoxy-1-naphthyl.Its In, preferably phenyl, 4-methoxyphenyl, 4-chlorphenyl.
R5、R6And R7It is preferably aryl, preferably represents identical group.
In formula (1), X-Represent conjugate base.Conjugate base represents the conjugate base of alkyl sulfonic acid, the conjugate base of aryl sulfonic acid, double The conjugate base of perfluor sulfonyl amine, particularly preferred alkyl sulfonic acid and the conjugate base of aryl sulfonic acid.As this conjugate base, preferably carbon number The conjugate base of the alkyl sulfonic acid of 1～7, even more preferably the conjugate base of carbon number 1～4, if stating as the acid, the most outstanding Its preferred methanesulfonic acid, trifluoromethanesulfonic acid, positive propane sulfonic acid, sulfonic acid in heptan.As the conjugate base of aryl sulfonic acid, if table as the acid State, the most particularly preferably benzenesulfonic acid, chlorobenzenesulfonic acid, p-methyl benzenesulfonic acid.
In formula (2), by R8And R9The implication of the aryl separately represented and the R in formula (1)5、R6And R7Institute's table The aryl shown is identical, and preferably scope is the most identical.
Specifically, R8And R9Particularly preferably phenyl, 4-methoxyphenyl, 4-chlorphenyl.Further, R8And R9Preferably represent Identical group.
In formula (1), X-The implication of represented conjugate base and the X in formula (1)-Identical, preferably scope is the most identical.
As the concrete example of salt compound, 4 can be enumerated, 7-bis--n-butoxy-1-naphthyl Tetramethylene sulfide fluoroform Sulphonic acid ester etc..And it is possible to enumerate following compound.
[chemical formula 15]
As oxime sulfonate compounds be as the compound with oxime sulfonates structure, it may be preferred to exemplify containing under State the compound of oxime sulfonates structure represented by formula (B1).
[chemical formula 16]
(in formula (B1), R21Represent alkyl or aryl.Wave represents and being bonded of other groups.)
R21In alkyl, any one group in aryl can be replaced.R21In alkyl can be straight-chain or Branched or ring-type.The substituent group that following description is allowed.
As R21Alkyl, the preferably straight-chain of carbon number 1～10 or branched-chain alkyl.R21Alkyl can by halogen atom, The aryl of carbon number 6～11, the alkoxyl of carbon number 1～10 or cycloalkyl (comprise the bridges such as 7,7-dimethyl-2-oxo norborny Ring type alcyl, preferably bicyclic alkyl etc.) replaced.
As R21Aryl, the preferably aryl of carbon number 6～11, more preferably phenyl or naphthyl.R21Aryl can be rudimentary Alkyl, alkoxyl or halogen atom are replaced.
As an example of the optimal way of oxime sulfonate compounds, Japanese Unexamined Patent Publication 2013-190507 public affairs can be exemplified The record of the paragraph 0108～0141 of report, these contents are introduced in present specification.
As the optimal way of the above-mentioned compound containing the oxime sulfonates structure represented by formula (B1), for following formula (B1-1) oxime sulfonate compounds represented by.
Formula (B1-1)
[chemical formula 17]
(in formula (B1-1), R42The alkyl or aryl that expression can be replaced, X represents alkyl, alkoxyl or halogen atom, m4 Representing the integer of 0～3, when m4 is 2 or 3, multiple X can be the same or different.)
As R42Preferred scope, with above-mentioned R21Preferred scope identical.
The straight-chain of the preferred carbon number of alkyl 1～4 or branched-chain alkyl as X.
The straight-chain of the preferred carbon number of alkoxyl 1～4 or branched alkoxyl as X.
Halogen atom preferred chlorine atom or fluorine atom as X.
M4 preferably 0 or 1.In above-mentioned formula (B1-1), especially preferably m4 is 1, X is methyl, the position of substitution of X is neighbour Position, R42Straight-chain alkyl, 7,7-dimethyl-2-oxo norbornylmethyl or the change to toluyl groups for carbon number 1～10 Compound.
As the concrete example of the oxime sulfonate compounds represented by formula (B1-1), such as, can exemplify following chemical combination Thing.
[chemical formula 18]
As other optimal ways of the above-mentioned compound containing the oxime sulfonates structure represented by formula (B1), for following Oxime sulfonate compounds represented by formula (B1-2).
Formula (B1-2)
[chemical formula 19]
(in formula (B1-2), R43Implication and formula (B1-1) in R42Identical, X1Represent halogen atom, hydroxyl, carbon number 1～4 Alkyl, alkoxyl, cyano group or the nitro of carbon number 1～4, n4 represents the integer of 0～5.)
As the R in above-mentioned formula (B1-2)43, preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, Pentafluoroethyl group, perfluor-n-pro-pyl, perfluor-normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, particularly preferred n-octyl.
As X1, the preferably alkoxyl of carbon number 1～5, more preferably methoxyl group.
As n4, preferably 0～2, particularly preferred 0～1.
Concrete as the concrete example of the compound represented by above-mentioned formula (B1-2) and preferred oxime sulfonate compounds Example, such as, can exemplify following compound.Further, in addition to compound illustrated below, it is also possible to reference to Japanese Unexamined Patent Publication The record of the paragraph 0080～0082 of 2012-163937 publication, its content is introduced in present specification.
[chemical formula 20]
As other optimal ways of the above-mentioned compound containing the oxime sulfonates structure represented by formula (B1), for following Compound represented by formula (OS-1).
[chemical formula 21]
In above-mentioned formula (OS-1), R101Represent hydrogen atom, alkyl, thiazolinyl, alkoxyl, alkoxy carbonyl, acyl group, ammonia first Acyl group, sulfamoyl, sulfo group, cyano group, aryl or heteroaryl.R102Represent alkyl or aryl.
X101Represent-O-,-S-,-NH-,-NR105-、-CH2-、-CR106H-or-CR105R107-, R105～R107Represent alkyl Or aryl.
R121～R124Separately represent hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxyl, amino, alkoxy carbonyl, Alkyl-carbonyl, aryl carbonyl, amide groups, sulfo group, cyano group or aryl.R121～R124In two can be mutually bonded and shape respectively Cyclization.
As R121～R124, preferably hydrogen atom, halogen atom and alkyl, and can also preferably enumerate R121～R124In extremely Few two are mutually bonded and form the form of aryl.Wherein, from the viewpoint of sensitivity, preferably R121～R124It is hydrogen atom Form.
The functional group described all can have substituent group further.
Compound represented by above-mentioned formula (OS-1) is such as preferably the paragraph of Japanese Unexamined Patent Publication 2012-163937 publication The compound represented by formula (OS-2) described in number 0087～0089, its content is introduced in present specification.
As the concrete example of the compound can being suitably used in represented by the above-mentioned formula (OS-1) of the present invention, can enumerate Compound (exemplary compounds b-1～b-described in the paragraph 0128～0132 of Japanese Unexamined Patent Publication 2011-221494 publication 34), but the present invention is not limited to this.
Below, it is shown that the concrete example (exemplary compounds b-1～b-34) of the compound represented by formula (OS-1), but this Bright it is not limited to this.It addition, in concrete example, Me represents that methyl, Et represent that ethyl, Bn represent that benzyl, Ph represent phenyl.
[chemical formula 22]
[chemical formula 23]
[chemical formula 24]
[chemical formula 25]
In the present invention, as other optimal ways of the compound containing the oxime sulfonates structure represented by formula (B1), For following formula (OS-3), following formula (OS-4) or the oxime sulfonate compounds represented by following formula (OS-5).
[chemical formula 26]
In formula (OS-3)～formula (OS-5), R22、R25And R28Separately represent alkyl, aryl or heteroaryl, R23、R26And R29Separately represent hydrogen atom, alkyl, aryl or halogen atom, R24、R27And R30Separately represent that halogen is former Son, alkyl, alkoxyl, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X1～X3Separately represent oxygen atom or sulfur Atom, n1～n3 separately represents 1 or 2, m1～m3 separately represents the integer of 0～6.
About formula (OS-3)～(OS-5), such as, it is referred to the paragraph of Japanese Unexamined Patent Publication 2012-163937 publication The record of 0098～0115, its content is introduced in present specification.About the compound represented by formula (OS-3), such as Can exemplify following.
[chemical formula 27]
Further, the compound containing the oxime sulfonates structure represented by formula (B1) is such as especially preferably Japanese Unexamined Patent Publication Represented by any one in formula (OS-6) described in the paragraph 0117 of 2012-163937 publication～(OS-11) Compound, its content is introduced in present specification.
Preferred scope in formula (OS-6)～(OS-11) and the paragraph of Japanese Unexamined Patent Publication 2011-221494 publication The preferred scope of (OS-6)～(OS-11) described in 0110～0112 is identical.
As the concrete example of the oxime sulfonate compounds represented by formula (OS-3)～formula (OS-5), Japan can be enumerated Compound described in the paragraph 0114～0120 of JP 2011-221494 publication, but the present invention is not limited to this A bit.
As other optimal ways of the compound containing the oxime sulfonates structure represented by formula (B1), for following formula (B1-3) oxime sulfonate compounds represented by.
Formula (B1-3)
[chemical formula 28]
In formula (B1-3), R1Represent alkyl or aryl, R2Represent alkyl, aryl or heteroaryl.R3～R6Represent hydrogen respectively Atom, alkyl, aryl, halogen atom.Wherein, R3With R4、R4With R5, or R5With R6Can be bonded and form alicyclic ring or aromatic rings.X table Show-O-or-S-.
R1Represent alkyl or aryl.Alkyl preferably has the alkyl of branched structure or the alkyl of circulus.
The carbon number of alkyl is preferably 3～10.Especially, when alkyl has branched structure, the preferably alkyl of carbon number 3～6, when When there is circulus, the preferably alkyl of carbon number 5～7.
As alkyl, such as, can enumerate propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, amyl group, different Amyl group, neopentyl, 1,1-dimethyl propyl, hexyl, 2-ethylhexyl, cyclohexyl, octyl group etc., preferably isopropyl, the tert-butyl group, Neopentyl, cyclohexyl.
The carbon number of aryl is preferably 6～12, more preferably 6～8, and more preferably 6～7.As aryl, can enumerate Phenyl, naphthyl etc., preferably phenyl.
R1Represented alkyl and aryl can have substituent group.Alternatively base, (fluorine is former such as can to enumerate halogen atom Son, chlorine atom, bromine atoms, atomic iodine), straight chain, side chain or cyclic alkyl (such as methyl, ethyl, propyl group etc.), thiazolinyl, alkynyl, Aryl, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, cyano group, carboxyl, hydroxyl, alkoxyl, aryloxy, alkane sulfur Base, arylthio, heterocyclic oxy group, acyloxy, amino, nitro, diazanyl, heterocyclic radical etc..And it is possible to taken further by these groups Generation.It is preferably halogen atom, methyl.
In the photosensitive polymer combination of the present invention, from the viewpoint of the transparency, R1Preferably alkyl is steady from taking into account preservation From the viewpoint of qualitative and sensitivity, R1Preferably carbon number 3～6 has the alkyl of branched structure, the circulus of carbon number 5～7 Alkyl or the alkyl of circulus of the alkyl with branched structure of phenyl, more preferably carbon number 3～6 or carbon number 5～7.Logical Cross and use the group (especially, the alkyl of large volume) of this large volume as R1, it is possible to improve the transparency further.
In the substituent group of large volume, preferably isopropyl, the tert-butyl group, neopentyl, cyclohexyl, the more preferably tert-butyl group, hexamethylene Base.
R2Represent alkyl, aryl or heteroaryl.As R2Represented alkyl, preferably the straight chain of carbon number 1～10, side chain or Cyclic alkyl.As alkyl, such as can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, amyl group, new penta Base, hexyl, cyclohexyl etc., preferably methyl.
As aryl, the preferably aryl of carbon number 6～10.As aryl, can enumerate phenyl, naphthyl, to toluyl groups (p-methylphenyl) etc., preferably phenyl, to toluyl groups.
As heteroaryl, such as, can enumerate pyrrole radicals, indyl, carbazyl, furyl, thienyl etc..
R2Represented alkyl, aryl and heteroaryl can have substituent group.Alternatively base, implication and R1Represented The substituent group that alkyl and aryl can have is identical.
R2Preferably alkyl or aryl, more preferably aryl, more preferably phenyl.As the substituent group of phenyl, preferably methyl.
R3～R6Represent hydrogen atom, alkyl, aryl or halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine) respectively.Make For R3～R6Represented alkyl, implication and R2Represented alkyl is identical, and preferably scope is the most identical.Further, as R3～R6Institute The aryl represented, implication and R1Represented aryl is identical, and preferably scope is the most identical.
R3～R6In, R3With R4、R4With R5, or R5With R6Can be bonded and form ring, as ring, be preferably formed as alicyclic ring or virtue Fragrant ring, more preferably phenyl ring.
About R3～R6, preferably hydrogen atom, alkyl, halogen atom (fluorine atom, chlorine atom, bromine atoms) or R3With R4、R4With R5, or R5With R6It is bonded and constitutes phenyl ring, more preferably hydrogen atom, methyl, fluorine atom, chlorine atom, bromine atoms or R3With R4、R4With R5, or R5With R6It is bonded and constitutes phenyl ring.
R3～R6Optimal way following.
(mode 1) at least two is hydrogen atom.
The number of (mode 2) alkyl, aryl or halogen atom is less than one.
(mode 3) R3With R4、R4With R5, or R5With R6It is bonded and constitutes phenyl ring.
(mode 4) meets the mode of aforesaid way 1 and 2 and/or meets the mode of aforesaid way 1 and 3.
X represents-O-or-S-.
As the concrete example of above-mentioned formula (B1-3), following compound can be enumerated, but the present invention is not particularly limited In this.It addition, in exemplary compounds, Ts represents tosyl (p-toluenesulfonyl), Me represents that methyl, Bu represent positive fourth Base, Ph represents phenyl.
[chemical formula 29]
As acid imide sulfonate compound, it may be preferred to use the acyl with the structure represented by following formula (B2) sub- Amine sulfonate compound.
[chemical formula 30]
(in formula (B2), R200Represent 1 valency organic group of carbon number less than 16.Wave represents and other groups Bonding.)
R200Represent 1 valency organic group of carbon number less than 16.R200Preferably without the element beyond C, H, O, F.As R200, such as, can enumerate methyl, trifluoromethyl, propyl group, phenyl, tosyl etc..
As the optimal way of the compound containing the structure represented by formula (B2), represented by following logical formula (I) Acid imide sulfonate compound.
[chemical formula 31]
In formula, R01、R04、R05And R06Represent hydrogen atom, R02、R03In any one represent can by ester ring type alkyl, Heterocyclic radical or halogen atom replace and can have the alkoxyl of carbon number 4～18 of side chain；Alkoxyl not adjacent with oxygen atom The methylene of optional position is by-C (=O)-substituted group of base；Alkoxyl is near the side of naphthalene nucleus quilt-O-C (=O)-key Or the group that-OC (=O)-NH-key interrupts；Can be replaced by ester ring type alkyl, heterocyclic radical or halogen atom and can have side chain The alkylthio group of carbon number 4～18；The methylene of not adjacent with the sulphur atom optional position of alkylthio group is replaced by-C (=O)-base Group；Alkylthio group is from the group interrupted by-O-C (=O)-key or-OC (=O)-NH-key near the side of naphthalene nucleus；Or it is following Group represented by formula (A), R02、R03In remaining one represent hydrogen atom, R07Expression can be by halogen atom and/or alkane The aliphatic alkyl of the substituted carbon number of sulfenyl 1～18；Can be replaced by halogen atom and/or ester ring type alkyl and can have side chain The alkyl of carbon number 1～18；The ester ring type alkyl of the carbon number 3～18 that can be replaced by halogen atom；Can be by halogen atom and/or carbon The aryl of the substituted carbon number of alkylthio group 6～20 of several 1～18；Can be replaced by the alkylthio group of halogen atom and/or carbon number 1～18 The aryl alkyl of carbon number 7～20；The alkylaryl of the carbon number 7～20 that can be replaced by halogen atom；The carbon that can be replaced by acyl group The aryl of several 7～20；10-camphoryl；Or the group represented by following formula (B).
[chemical formula 32]
In formula, X1Represent oxygen atom or sulphur atom, Y1Represent singly-bound or the alkane diyl (alkanediyl of carbon number 1～4 Group), R11Represent the alkyl of carbon number 1～12, R12Represent the alkane diyl of carbon number 1～4, R13Represent that hydrogen atom maybe can have to prop up The alkyl of the carbon number 1～4 of chain or the ester ring type alkyl of carbon number 3～10 or heterocyclic radical, m represents 0～5, when m is 2～5, exists Multiple R12Can be the same or different.
[chemical formula 33]
In formula, Y2Represent singly-bound or the alkane diyl of carbon number 1～4, R21Represent the alkane diyl of carbon number 2～6, the halogen of carbon number 2～6 For alkane diyl, the arlydene of carbon number 6～20 or the halo arlydene of carbon number 6～20, R22Represent singly-bound, the alkane two of carbon number 2～6 Base, the alkyl halide diyl of carbon number 2～6, the arlydene of carbon number 6～20 or the halo arlydene of carbon number 6～20, R23Expression can have The alkyl having the carbon number 1～18 of side chain, the haloalkyl of carbon number 1～18 can with side chain, the ester ring type hydrocarbon of carbon number 3～12 The halo virtue of base, the aryl of carbon number 6～20, the halogenated aryl of carbon number 6～20, the aryl alkyl of carbon number 7～20 or carbon number 7～20 Base alkyl, a, b represent 0 or 1, and any one in a, b is 1.
About logical formula (I), such as, it is referred to the paragraph 0019～0063 of International Publication WO11/087011 publication Recording, its content is introduced in present specification.As the compound represented by logical formula (I), such as, can exemplify following. Further, in addition to compound illustrated below, it is also possible to reference to the paragraph 0065 of International Publication WO11/087011 publication ～the record of 0075, its content is introduced in present specification.
[chemical formula 34]
In the photosensitive polymer combination of the present invention, (B) light acid producing agent is relative in photosensitive polymer combination All resinous principles (preferably solid constituent, the more preferably total of (A) polysiloxanes) 100 mass parts, are preferably used 0.1～10 matter Amount part, more preferably uses 0.5～10 mass parts, further preferred 1.0～5.0 mass parts.(B) light acid producing agent can also and be used Two or more.When and when using two or more, preferably its always metering is within the above range.
In the photosensitive polymer combination of the present invention, from the viewpoint of sensitivity and light resistance, (B) light acid producing agent Relative to solid constituent 100 mass parts in photosensitive polymer combination, 0.1～10 mass parts are preferably used, more preferably use 0.5～10 mass parts, further preferably use 1.0～5.0 mass parts.(B) light acid producing agent can also and with two or more.When And when using two or more, preferably its always metering is within the above range.
＜ (C) solvent ＞
The photosensitive polymer combination of the present invention contains (C) solvent.The photosensitive polymer combination of the present invention is preferably prepared Become the essential component of the present invention and further any composition described later is dissolved in (C) solvent the solution obtained.As Solvent used in the preparation of the photosensitive polymer combination of the present invention, uses and dissolves essential component and any composition equably And the solvent reacted is not carried out with each composition.
(C) solvent used in photosensitive polymer combination as the present invention, it is possible to use known solvent, permissible Exemplify ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether Class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl Ether acetic acid esters, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, ester Class, ketone, amide-type, lactone etc..Further, the solvent used in the photosensitive polymer combination as the present invention is concrete Example, it is also possible to enumerate solvent described in the paragraph 0174～0178 of Japanese Unexamined Patent Publication 2011-221494 publication, Japanese spy Opening solvent described in the paragraph 0167～0168 of 2012-194290 publication, these contents are introduced into present specification In.Such as, as an example of the concrete example of solvent, propylene glycol 1-monomethyl ether 2-acetas, Methylethyl diethylene glycol can be enumerated (Methyl Ethyl Diglycol) etc..
Further, these solvents can also add as required benzyl ether, two hexyl ethers, ethyleneglycol monophenylether acetas, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1-capryl alcohol, 1 nonyl alcohol, benzylalcohol, methyl phenyl ethers anisole, second Acid benzyl ester, ethyl benzoate, ethyl oxalate, ethyl maleate., ethylene carbonate, Allyl carbonate equal solvent.These are molten Agent can be used alone one or is used in mixed way two or more.In the present invention spendable solvent be preferably individually a kind of or And with two kinds, more preferably and with two kinds, further preferably and with propylene-glycol monoalky lether acetate esters or dialkyl ether, diethyl Esters of gallic acid and diethylene glycol dialkyl ether class or esters and butanediol alkylether acetates class.
Further, as (C) solvent, preferably boiling point be 130 DEG C less than 160 DEG C solvent, boiling point be 160 DEG C with On solvent or their mixture.
As boiling point be 130 DEG C less than the solvent of 160 DEG C, propylene glycol methyl ether acetate (boiling can be exemplified Point 146 DEG C), propylene glycol monoethyl ether acetate (boiling point 158 DEG C), propylene glycol methyl n-butyl ether (boiling point 155 DEG C), propylene glycol methyl Positive propyl ether (boiling point 131 DEG C).
As the solvent that boiling point is more than 160 DEG C, 3-ethoxyl ethyl propionate (boiling point 170 DEG C), diethyl can be exemplified Glycol methyl ethyl ether (boiling point 176 DEG C), propylene glycol monomethyl ether propionate (boiling point 160 DEG C), (boiling of dipropylene glycol methyl ether acetas Point 213 DEG C), 3-methoxyl group butyl ether acetas (boiling point 171 DEG C), diethylene glycol diethyl ether (boiling point 189 DEG C), diethylene glycol diformazan Ether (boiling point 162 DEG C), propylene-glycol diacetate (boiling point 190 DEG C), diethylene glycol monoethyl ether acetas (boiling point 220 DEG C), dipropyl Glycol dimethyl ether (boiling point 175 DEG C), 1,3 butylene glycol diacetate esters (boiling point 232 DEG C).
From the viewpoint of coating and dissolubility, particularly preferred propylene glycol methyl ether acetate and diethylene glycol methyl second The combination of base ether.Preferred 10:90～90:10 of its mixing ratio, more preferably 30:70～70:30.Further preferably at this mixed solvent 100 The solvent that boiling point is more than 200 DEG C 1 part of mixing such as 1,3 butylene glycol diacetate esters etc～10 parts of solvents obtained in Fen.
The content of (C) solvent in the photosensitive polymer combination of the present invention is relative to the institute in photosensitive polymer combination Composition 100 mass parts is had to be preferably 50～95 mass parts, more preferably 60～90 mass parts.
＜ other compositions ＞
In the photosensitive polymer combination of the present invention, in addition to mentioned component, it is also possible to be preferably added to (D) as required Sensitizer, (E) cross-linking agent, (F) alkali compounds, (G) surfactant, (H) antioxidant.
The photosensitive polymer combination of the present invention can add acid proliferation generator, development accelerant, plasticizer, heat further Add known to the suspending agent of free-radical generating agent, thermal acid generator, UV absorbent, thickening agent and organic or inorganic etc. Add agent.Further, as these compounds, such as can also with reference to the paragraph 0201 of Japanese Unexamined Patent Publication 2012-88459 publication～ The record of 0224, these contents are introduced in present specification.
Further, in order to improve the adhesiveness with substrate, the photosensitive polymer combination of the present invention can add alkoxyl Silane compound.
＜ (D) sensitizer ＞
The photosensitive polymer combination of the present invention with the combination of (B) light acid producing agent in order to promote that it decomposes, preferably Containing sensitizer.Sensitizer absorbing activity light or lonizing radiation and become electron excitation state.Become the quick of electron excitation state Agent contacts with light acid producing agent and produces the effects such as electronics moves, energy moves, heating.Thus, causing of light acid producing agent Learn change and decompose, thus generate acid.As the example of preferred sensitizer, can enumerate belong to following compounds and Any region in the wavelength region of 350nm to 450nm has the compound of absorbing wavelength.
The polynuclear aromatic same clan (such as, pyrene, benzophenanthrene, anthracene, 9,10-dibutoxy anthracene, 9,10-diethoxy anthracene, 3, 7-dimethoxy anthracene, 9,10-dipropoxy anthracene), ton class (such as, fluorescein, eosin, erythrosine, rhodamine B, rose-red), Xanthone (such as, xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class are (such as Thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (such as, merocyanine, carbonyl merocyanine) if red cyanines class, oxonols class, thiazine Class (such as, thionine, methylene blue, toluidine blue), acridine (such as, acridine orange, chloroflavin, acriflavine), acridine ketone (such as, acridone, 10-butyl-2-chloro-acridine ketone), Anthraquinones (such as, anthraquinone), Squarylium type (such as, side's acid cyanines), benzene second Thiazolinyl class, basicity styrene base class (such as, 2-[2-[4-(dimethylamino) phenyl] vinyl] benzothiazole), Coumarins (such as, 7-diethylamino 4-methylcoumarin, 7-hydroxyl 4-methylcoumarin, 2,3,6,7-tetrahydrochysene-9-methyl isophthalic acid H, 5H, 11H [1] .alpha.-5:6-benzopyran also [6,7,8-ij] quinolizine-11-ketone).
In these sensitizers, the preferably polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, perfume (or spice) Legumin class, more preferably the polynuclear aromatic same clan.In the polynuclear aromatic same clan, most preferably anthracene derivant.
The addition of the sensitizer in the photosensitive polymer combination of the present invention is relative to the light of photosensitive polymer combination Acid producing agent 100 mass parts is preferably 0～1000 mass parts, more preferably 10～500 mass parts, more preferably 50～ 200 mass parts.
Can also and with two or more.
(E) cross-linking agent
The photosensitive polymer combination of the present invention preferably comprises cross-linking agent as required.By adding cross-linking agent, it is possible to The cured film obtained by the photosensitive polymer combination of the present invention is made to become firmer film.
Cross-linking agent is the compound containing at least two crosslinked group in intramolecular.Crosslinked group refer to by heat with (A) more than one in crosslinkable groups, phenyl ring, hydroxyl and carboxyl of polysiloxanes carry out the group reacted.As friendship Symbasis group, preferably methylol, epoxy radicals, oxetanylmethoxy, alkoxy methyl, blocked isocyanate ester group, methylacryloyl and Acryloyl group, more preferably methylol, epoxy radicals, alkoxy methyl, blocked isocyanate ester group, methylacryloyl and acryloyl Base.
Further, the quantity of the crosslinked group in one molecule of cross-linking agent is preferably more than 3, and more preferably more than 4.
Crosslinked group can have the crosslinked group of two or more identical type in intramolecular, it is also possible to has in intramolecular The different types of crosslinked group of two or more.
The molecular weight of the cross-linking agent used in the present invention preferably 150～30000, more preferably 200～10000.By setting For this scope, can more effectively play the effect of the present invention.
The addition of the cross-linking agent in the photosensitive polymer combination of the present invention is relative to the institute of photosensitive polymer combination Solid constituent 100 mass parts is had to be preferably 0.01～50 mass parts, more preferably 0.1～30 mass parts, more preferably 0.5 ～20 mass parts.By adding within the range, mechanical strength and the cured film of solvent tolerance excellence can be obtained.Can also be also Using multiple cross-linking agent, now, all cross-linking agent that adds are to calculate content.
Further, the photosensitive polymer combination of the present invention can also be set to be substantially free of the structure of cross-linking agent.Substantially The structure not contained refers to below such as 1 mass % of the solid constituent that cross-linking agent is photosensitive polymer combination.
＜ ＜ has the compound ＞ ＞ of plural epoxy radicals in intramolecular
In the photosensitive polymer combination of the present invention, as cross-linking agent, it is possible to use have plural in intramolecular The compound of epoxy radicals.As the concrete example of the compound in intramolecular with plural epoxy radicals, bisphenol-A can be enumerated Type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, fat Race's epoxy resin, there is the acrylic resin etc. containing epoxy radicals construction unit.
These can obtain as commercially available product.Such as can enumerate JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (Mitsubishi Chemical Holdings Corporation system) etc., Japanese Unexamined Patent Publication Commercially available product etc. described in the paragraph 0189 of 2011-221494 publication, in addition, can enumerate Denacol EX- 611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、 EX-321、EX-321L、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX- 832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-850L、DLC- 201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above Nagase ChemteX Corporation system), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above NIPPON STEEL CHEMICAL CO., LTD. system), Celloxide 2021P, Celloxide 2081, EHPE3150, EHPE3150CE (more than Daicel Corporation) etc..They can be used alone one or are applied in combination two or more.
Among those, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolacs can more preferably be enumerated Type epoxy resin and aliphatic epoxy resin, particularly preferably can enumerate bisphenol A type epoxy resin.
＜ ＜ contains the cross-linking agent ＞ ＞ of plural alkoxy methyl or methylol in intramolecular
In the photosensitive polymer combination of the present invention, as cross-linking agent, it is possible to use containing alkoxy methyl or methylol Cross-linking agent.As containing the cross-linking agent of plural alkoxy methyl or methylol in intramolecular, for having in intramolecular The cross-linking agent of the structure represented by the following formula of two or more (1) or formula (2), amounts to containing two or more alcoxyl in intramolecular Any one or both in ylmethyl and methylol.
-CH2OR1(1)
(in formula, R1Represent the alkyl of carbon number 1～8, the preferably alkyl of carbon number 1～4, more preferably methyl.)
-CH2OH(2)
Alkoxy methyl or methylol are preferably bonded on the carbon atom of nitrogen-atoms or formation aromatic ring.
The cross-linking agent being bonded on nitrogen-atoms as alkoxy methyl or methylol, the most aikoxymethytated melamine Amine, methylolated melamine, aikoxymethytated benzoguanamine, methylolation benzoguanamine, aikoxymethytated glycolurils, hydroxyl Methylate glycoluril, aikoxymethytated carbamide and methylolated urea etc..Alkoxymethylated melamine, aikoxymethytated Benzoguanamine, aikoxymethytated glycolurils, aikoxymethytated carbamide are by respectively by methylolated melamine, methylolation The methylol of benzoguanamine, methylolation glycoluril or methylolated urea is converted into alkoxy methyl and obtains.About this alcoxyl The kind of ylmethyl, can enumerate methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl etc., from ease gas (out Gas) from the viewpoint of generation amount, particularly preferred methoxy.
In these cross-linked compounds, as preferred cross-linked compound, aikoxymethytated trimerization can be enumerated Cyanamide, methylolated melamine, aikoxymethytated benzoguanamine, methylolation benzoguanamine, aikoxymethytated glycolurils, Methylolation glycoluril, from the viewpoint of the transparency, particularly preferred aikoxymethytated glycolurils and methylolation glycoluril.
In the present invention, it may be preferred to use described containing in the paragraph 0107 of Japanese Unexamined Patent Publication 2012-8223 publication The cross-linking agent of alkoxy methyl, these contents are introduced in present specification.
As the preferred structure of the cross-linking agent containing plural alkoxy methyl or methylol in intramolecular, Ke Yiju Go out the compound represented by following formula (8-1)～(8-4).
[chemical formula 35]
(in above-mentioned formula (8-1)～(8-4), R7And R separately represents hydrogen atom or the alkyl of carbon number 1～8, R8~ R11Separately represent hydrogen atom, hydroxyl, alkyl or alkoxyl, X2Represent singly-bound, methylene or oxygen atom.)
R7And the carbon number of the alkyl represented by R is 1～8, more preferably carbon number is 1～4, such as can enumerate methyl, ethyl, Propyl group.R8～R11The represented preferred carbon number of alkyl is 1～8, and more preferably carbon number is 1～4, such as can enumerate methyl, ethyl, Propyl group.R8～R11The represented preferred carbon number of alkoxyl is 1～8, and more preferably carbon number is 1～4, such as can enumerate methoxyl group, Ethyoxyl, propoxyl group.X2It is preferably singly-bound or methylene.R7～R11、X2Can be taken by the alkyl such as methyl, ethyl, halogen atom etc. Generation.Multiple R7、R、R8～R11Can distinguish identical can also be different.
As the compound represented by formula (8-1), specifically, compound shown below etc. can such as be enumerated.
[chemical formula 36]
[chemical formula 37]
As the compound represented by formula (8-2), specifically, such as, can enumerate N, N, N, N-tetramethylol glycoluril, The methylol of N, N, N, N-tetramethylol glycoluril carries out 1～4 methoxymethylated compound, N, and N, N, N-tetra methylol is sweet The methylol of urea carries out the compound of 1～4 ethoxyl methyl, N, and the methylol of N, N, N-tetramethylol glycoluril carries out 1～4 The compound of individual n-propoxymethyl, N, the methylol of N, N, N-tetramethylol glycoluril carries out 1～4 i-propoxymethyl Compound, N, the methylol of N, N, N-tetramethylol glycoluril carries out 1～4 the methylated compound of n-butoxy, N, N, N, The methylol of N-tetramethylol glycoluril carries out the compound etc. of 1～4 t-butoxymethyl.Wherein, particularly preferred N, N, N, The methylol of N-tetramethylol glycoluril carries out 1～4 methoxymethylated compound.
As the compound represented by formula (8-3), specifically, compound shown below etc. can such as be enumerated.
[chemical formula 38]
As the compound represented by formula (8-4), specifically, N, N, N, N, N, N-hexamethylol three can such as be enumerated Poly cyanamid, N, the methylol of N, N, N, N, N-hexakis(hydroxymethyl)melamine carries out 1～6 methoxymethylated compound, N, The methylol of N, N, N, N, N-hexakis(hydroxymethyl)melamine carries out the compound of 1～6 ethoxyl methyl, N, N, N, N, N, N- The methylol of hexakis(hydroxymethyl)melamine carries out the compound of 1～6 n-propoxymethyl, N, N, N, N, N, N-hexamethylol The methylol of tripolycyanamide carries out the compound of 1～6 i-propoxymethyl, N, N, N, N, N, N-hexakis(hydroxymethyl)melamine Methylol carry out 1～6 the methylated compound of n-butoxy, N, the methylol of N, N, N, N, N-hexakis(hydroxymethyl)melamine Carry out the compound etc. of 1～6 t-butoxymethyl.And it is possible to enumerate the compound represented by following formula.Wherein, especially The preferably compound represented by following formula.
[chemical formula 39]
It is bonded to be formed the example of the cross-linking agent on the carbon atom of aromatic ring as alkoxy methyl or methylol, such as The compound represented by following formula (4)～(5) can be enumerated.
[chemical formula 40]
(in formula (4), X represents singly-bound or 1～4 valency organic groups, R11、R12Represent that hydrogen atom or monovalence have independently of one another Machine group, n is the integer of 1～4, p and q is each independently the integer of 0～4.)
[chemical formula 41]
(in formula (5), two Y are each independently hydrogen atom or for the alkyl of carbon number 1～10 and can to contain aerobic former Son, fluorine atom, R13～R16Represent hydrogen atom or monovalent organic group independently of one another, m and n be each independently 1～3 whole Number, p and q is each independently the integer of 0～4.)
As the concrete compound represented by formula (4)～(5), such as, can enumerate compound shown below.Me Represent methyl.
[chemical formula 42]
These contain the cross-linking agent of plural alkoxy methyl or methylol in intramolecular can also be as commercially available product And obtain, such as can be preferably used CYMEL 300,301,303,370,325,327,701,266,267,238,1141, 272,202,1156,1158,1123,1170,1174, UFR65,300 (they being Mitsui Cyanamid Co. above, Ltd. system), NIKALAC MX-750、-032、-706、-708、-40、-31、-270、-280、-290、-750LM、NIKALAC MS-11、 NIKALAC MW-30HM ,-100LM ,-390 (being Sanwa Chemical Co. above, Ltd. system) etc..They can individually make With a kind of or be applied in combination two or more.
＜ ＜ contains the compound ＞ ＞ of plural blocked isocyanate ester group in intramolecular
In the photosensitive polymer combination of the present invention, as cross-linking agent, it is possible to use contain plural in intramolecular The compound of blocked isocyanate ester group.
Blocked isocyanate ester group in the present invention refers to the group by being thermally generated NCO, such as can be excellent Choosing exemplifies protects the group of NCO by making block agent and NCO carry out reacting.Further, above-mentioned block NCO is preferably capable the group being thermally generated NCO by 90 DEG C～250 DEG C.
Further, as block isocyanate compound, its skeleton is not particularly limited, as long as having in 1 molecule Two or more NCO, then can be any skeleton, can be aliphatic, alicyclic or aromatic polyisocyanate, Such as can suitably use 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, 1,6- Hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-nine methylene diisocyanate, 1, 10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenyl-methane-4, 4'-diisocyanate, o-Dimethylbenzene diisocyanate, m xylene diisocyanate, xylol diisocyanate, methylene Double (cyclohexyl isocyanates), hexamethylene-1,3-dimethylene diisocyanate, hexamethylene-1,4-dimethylene two Carbimide. Ester, 1,5-naphthalene diisocyanate, to phenylene vulcabond, 3,3'-xylene-4,4'-diisocyanate, 4, 4'-diphenyl ether diisocyanate, tetrachloro phenylene vulcabond, norbornene alkyl diisocyanate, hydrogenation 1,3-Asia dimethylbenzene The isocyanate compounds such as diisocyanate, hydrogenation 1,4-Asia XDI and the pre-polymerization derived by these compounds The compound of thing type skeleton.Among those, particularly preferred toluene di-isocyanate(TDI) (TDI) or '-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).
As the parent structure of the block isocyanate compound in the photosensitive polymer combination of the present invention, contracting can be enumerated Two urea types, isocyanurate type, adduct type, 2 functional prepolymer types etc..
As forming the block agent of block structure of above-mentioned block isocyanate compound, oxime compound, interior can be enumerated Amide compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, Glyoxaline compound, imide analog compounds etc..Among those, particularly preferably selected from oxime compound, lactam compound, phenol Block agent in compound, alcoholic compound, amines, activity methene compound, pyrazole compound.
As above-mentioned oxime compound, oxime and ketoxime can be enumerated, specifically, acetone oxime, formaldoxime, ring can be exemplified Hexane oxime, methyl ethyl ketoxime, cyclohexanone-oxime, diphenyl-ketoxime etc..
As above-mentioned lactam compound, epsilon-caprolactams, butyrolactam etc. can be exemplified.
As above-mentioned phenolic compounds, the phenol etc. of phenol, naphthols, cresol, xylenol, halogen substiuted can be exemplified.
As above-mentioned alcoholic compound, can exemplify methanol, ethanol, propanol, butanol, Hexalin, ethylene glycol monoalkyl ether, Propylene-glycol monoalky lether, lactic acid alkyl ester etc..
As above-mentioned amines, primary amine and secondary amine can be enumerated, can be aromatic amine, aliphatic amine, cycloaliphatic amines Any one of, aniline, diphenylamine, aziridine (ethyleneimin), polymine etc. can be exemplified.
As above-mentioned activity methene compound, diethyl malonate, dimethyl malenate, acetoacetic acid can be exemplified Ethyl ester, methyl acetoacetate etc..
As above-mentioned pyrazole compound, pyrazoles, methylpyrazole, dimethyl pyrazole etc. can be exemplified.
As above-mentioned mercaptan compound, alkyl hydrosulfide, aryl mercaptan etc. can be exemplified.
In the photosensitive polymer combination of the present invention, spendable block isocyanate compound can be as commercially available product Obtain, such as can be preferably used Coronate AP stable M, Coronate 2503,2515,2507,2513,2555, Millionate MS-50 (being Nippon Polyurethane Industry Co. above, Ltd. system), Takenate B- 830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (are Mitsui above Chemicals.Incorporated system), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF- B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (are Asahi above Kasei Chemicals Corporation system), Desmodule BL1100, BL1265MPA/X, BL3575/1, BL3272MPA、BL3370MPA、BL3475BA/SN、BL5375MPA、VPLS2078/2、BL4265SN、PL340、PL350、 Sumidule BL3175 (being Sumika Bayer Urethane Co. above, Ltd. system) etc..
＜ ＜ contains the compound ＞ ＞ of plural methylacryloyl or acryloyl group in intramolecular
In the photosensitive polymer combination of the present invention, as cross-linking agent, it is possible to use containing methylacryloyl or propylene The compound of acyl group.Compound containing methylacryloyl or acryloyl group is choosing free acrylate, methacrylate Compound in the group constituted.Be preferably there are in 1 molecule two or more, more preferably 3 officials can above propylene Acyl group, the compound of methylacryloyl.
As 2 officials can (methyl) acrylate, such as can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, 1,6-hexanediol Two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, TEG Two (methyl) acrylate, double phenyl phenol fluorenes diacrylate, double phenyl phenol fluorenes diacrylates etc..
As 3 officials can above (methyl) acrylate, such as can enumerate trimethylolpropane tris (methyl) acrylic acid Ester, tetramethylolmethane three (methyl) acrylate, three ((methyl) acryloyl-oxyethyl) phosphate ester, tetramethylolmethane four (methyl) third Olefin(e) acid ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..
As preferred commercially available product, Nippon Kayaku Co., Ltd KAYARAD DPHA, Shin-can be enumerated Nakamura Chemical Co., Ltd. NK ester series and A-200, A-400, A-600, A-1000, ABE-of two senses 300、A-BPE-4、A-BPE-10、A-BPE-20、A-BPE-30、A-BPP-3、A-DOD、A-DCP、A-IBD-2E、A-NPG、 701A、A-B1206PE、A-HD-N、A-NOD-N、APG-100、APG-200、APG-400、APG-700、1G、2G、3G、4G、9G、 14G、23G、BG、BD、HD-N、NOD、IND、BPE-100、BPE-200、BPE-300、BPE-500、BPE-900、BPE-1300N、 NPG, DCP, 1206PE, 701,3PG, 9PG, 3 officials can A-9300, AT-30E, A-TMPT-3EO, A-TMPT-9EO, A-TMPT- 3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, TMPT, TMPT-9EO, 4 officials can above ATM-35E, ATM-4E, AD- TMP, AD-TMP-L, ATM-4P, A-TMMT, A-DPH etc..
＜ ＜ contains the compound ＞ ＞ of plural oxetanylmethoxy in intramolecular
In the photosensitive polymer combination of the present invention, as cross-linking agent, it is possible to use containing the compound of oxetanylmethoxy. In intramolecular, preferably there is two or more oxetanylmethoxy.As the chemical combination in intramolecular with plural oxetanylmethoxy Thing, can enumerate compound described in the paragraph 0134～0145 of Japanese Unexamined Patent Publication 2008-224970 publication, its content quilt Introduce in this specification.As concrete example, it is possible to use Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (with Upper for TOAGOSEI CO., LTD. system).
(F) alkali compounds
The photosensitive polymer combination of the present invention can contain (F) alkali compounds.As (F) alkali compounds, permissible Compound used in resist arbitrarily selects use from amplifying at chemistry.For example, it is possible to enumerate aliphatic amine, aromatic series Amine, hetero ring type amine, quaternary ammonium hydroxide, the quaternary ammonium salt etc. of carboxylic acid.As their concrete example, Japanese Unexamined Patent Publication 2011-can be enumerated Compound described in the paragraph 0204～0207 of No. 221494 publications, these contents are introduced in present specification.
Specifically, as aliphatic amine, such as, can enumerate trimethylamine, diethylamine, triethylamine, di-n-propylamine, three just Propylamine, tri-n-butylamine, two n-amylamines, tri-n-amyl amine, diethanolamine, triethanolamine, hexanamine, dicyclohexylmethylamine etc..
As aromatic amine, such as, can enumerate aniline, benzyl amine, DMA, diphenylamines etc..
As hetero ring type amine, such as, can enumerate pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethyl Pyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2,4,5-triphenylimidazolyl, nicotine, nicotinic acid, nicotiamide, quinoline, 8-hydroxyl quinoline Quinoline, pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, piperidines, pyrazine, morpholine, 4-methyl morpholine, N-cyclohexyl-N '-[2-(4- Quinoline base) ethyl] thiourea, 1,5-diazabicyclo [4.3.0]-5-nonene, 1,8-diazabicyclo [5.3.0]-7-hendecene etc..
As quaternary ammonium hydroxide, such as, can enumerate Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetra-n-butyl hydrogen-oxygen Change ammonium, four n-hexyl ammonium hydroxide etc..
As the quaternary ammonium salt of carboxylic acid, such as, can enumerate tetramethyl ammonium acetate, durol ammonium formate, tetra-n-butyl acetic acid Ammonium, tetra-n-butyl ammonium benzoate etc..
In the present invention, spendable alkali compounds can be used alone one, it is also possible to and with two or more.
The content of (F) alkali compounds in the photosensitive polymer combination of the present invention is relative to photosensitive polymer combination In all solids composition 100 mass parts be preferably 0.001～3 mass parts, more preferably 0.005～1 mass parts.
(G) surfactant
The photosensitive polymer combination of the present invention can contain (G) surfactant.As (G) surfactant, permissible Use any one of anionic species, cationic, nonionic class or both sexes, but preferably surfactant is nonionic table Face activating agent.Surfactant used in compositions as the present invention, such as, can use Japanese Unexamined Patent Publication 2012- Surfactant described in the paragraph 0201～0205 of No. 88459 publications, Japanese Unexamined Patent Publication 2011-215580 publication Surfactant described in paragraph 0185～0188, these records are introduced in present specification.
As the example of nonionic class surfactant, polyoxyethylene higher alkyl ether, polyoxyethylene higher alkylbenzene Base ethers, the higher aliphatic acid diesters class of polyoxyethylene glycol, silicone, fluorine class surfactant.And it is possible to enumerate following business The name of an article i.e. FA-630, KP-341, X-22-822 (Shin-Etsu Chemical Co., Ltd. system), Polyflow No.99C (Kyoeisha chemical Co., Ltd. system), Eftop (MITSUBISHI MATERIALS CHEMICALS Corporation system), Megafac (DIC CORPORATION system), Fluorad Novec FC-4430 (Sumitomo 3M Limited system), Surflon S-242 (AGC SEIMI CHEMICAL CO., LTD. system), PolyFox PF-6320 (OMNOVA Solutions Inc. system), SH-8400 (Toray-Dow Corning Silicone Co., Ltd.), Ftergent FTX-218G (Neos Corporation system) etc..
Further, as surfactant, can enumerate containing the construction unit A represented by following formula (I-1-1) and knot The weight of the polystyrene conversion that oxolane (THF) is measured by structure unit B and utilization as gel permeation chromatography during solvent Average molecular weight (Mw) is that the copolymer of more than 1,000 and less than 10,000 is as preference.
Formula (I-1-1)
[chemical formula 43]
(in formula (I-1-1), R401And R403Separately represent hydrogen atom or methyl, R402Represent carbon number more than 1 and 4 with Under straight-chain alkyl-sub-, R404Representing hydrogen atom or the alkyl of carbon number more than 1 and less than 4, L represents carbon number more than 3 and less than 6 Alkylidene, p and q is the quality percentage representing polymerization ratio, and p represents the numerical value of below more than 10 mass % and 80 mass %, q table Showing the numerical value of below more than 20 mass % and 90 mass %, r represents the integer of more than 1 and less than 18, s represent more than 1 and 10 with Under integer.)
Above-mentioned L is preferably the branched alkylidene represented by following formula (I-1-2).R in formula (I-1-2)405Represent carbon The alkyl of several more than 1 and less than 4, from the viewpoint of intermiscibility and the wettability to applied, preferably carbon number more than 1 and 3 Following alkyl, the more preferably alkyl of carbon number 2 or 3.P Yu q sum (p+q) is preferably p+q=100 that is 100 mass %.
Formula (I-1-2)
[chemical formula 44]
The weight average molecular weight (Mw) more preferably more than 1,500 and less than 5,000 of above-mentioned copolymer.
These surfactants can be used alone one or are used in mixed way two or more.
The addition of (I-1) surfactant in the photosensitive polymer combination of the present invention is relative to photoresist group All solids composition 100 mass parts in compound is preferably below 10 mass parts, more preferably 0.001～10 mass parts, enters one Step is preferably 0.01～3 mass parts.
(H) antioxidant
The photosensitive polymer combination of the present invention can contain (H) antioxidant.As antioxidant, can be containing known Antioxidant.By adding antioxidant, have and be prevented from the coloring of cured film, maybe can reduce the film caused by decomposition Thick minimizing and the advantage of heat resistant transparent excellence.
As this antioxidant, such as, can enumerate phosphorus antioxidants, amide-type, hydrazides class, hindered amines antioxygen Agent, sulfur class antioxidant, phenol antioxidant, Vitamin C acids, zinc sulfate, saccharide, nitrite, sulphite, sulfur generation Sulfate, hydroxylamine derivative etc..Among those, from the viewpoint of the coloring of cured film, thickness reduce, particularly preferred phenols Antioxidant, amide-type antioxidant, hydrazides class antioxidant, sulfur class antioxidant, most preferably phenol antioxidant.They can To be used alone one, it is also possible to mix two or more.
As concrete example, can enumerate in the paragraph 0026～0031 of Japanese Unexamined Patent Publication 2005-29515 publication described Compound, Japanese Unexamined Patent Publication 2011-227106 publication paragraph 0106～0116 in described compound, these content quilts Introduce in present specification.
As preferred commercially available product, Adekastab AO-60, Adekastab AO-80, Irganox can be enumerated 1726、Irganox 1035、Irganox 1098。
The content of antioxidant is preferably 0.1～10 matter relative to all solids composition of photosensitive polymer combination Amount %, more preferably 0.2～5 mass %, especially preferably 0.5～4 mass %.By being set to this scope, the film formed can To obtain the sufficient transparency, and sensitivity when forming pattern also becomes good.
Further, as the additive beyond antioxidant, can be by " the new of polymeric additive launches (NIKKAN KOGYO SHIMBUN, LTD.) " in described various UV absorbent, matal deactivator etc. add the photosensitive of the present invention to In property resin combination.
(acid proliferation generator)
For the purpose of improving sensitivity, the photosensitive polymer combination of the present invention can use acid proliferation generator.
In the present invention, spendable acid proliferation generator makes reactant for producing acid further by acid catalyst reaction The compound that acid concentration in system rises, is the compound stably existed when there is not acid.
As the concrete example of this acid proliferation generator, can enumerate Japanese Unexamined Patent Publication 2011-221494 paragraph 0226～ Acid proliferation generator described in 0228, its content is introduced in present specification.
(development accelerant)
The photosensitive polymer combination of the present invention can contain development accelerant.
As development accelerant, it is referred in the paragraph 0171～0172 of Japanese Unexamined Patent Publication 2012-042837 publication Described development accelerant, its content is introduced in present specification.
Development accelerant can be used alone one, it is also possible to and with two or more.
From the viewpoint of sensitivity and residual film ratio, adding of the development accelerant in the photosensitive polymer combination of the present invention Dosage is preferably 0～30 mass parts relative to all solids composition 100 mass parts of photosensitive composite, more preferably 0.1～ 20 mass parts, most preferably 0.5～10 mass parts.
Further, as other additives, it is possible to use the paragraph 0120 of Japanese Unexamined Patent Publication 2012-8223 publication～ Described nitrogen-containing compound and thermal acid generator in hot radical producing agent described in 0121, WO2011/136074A1, These contents are introduced in present specification.
[alkoxysilane compound containing trialkylsilyl group in molecular structure]
The photosensitive polymer combination of the present invention can contain alkoxysilane compound containing trialkylsilyl group in molecular structure.
As alkoxysilane compound containing trialkylsilyl group in molecular structure, preferably dialkoxysilane compounds or trialkoxy silane compound, more excellent Select trialkoxy silane compound.The carbon number of the alkoxyl that alkoxysilane compound containing trialkylsilyl group in molecular structure is had is preferably 1～5.
In the photosensitive polymer combination of the present invention, the preferably raising of spendable alkoxysilane compound containing trialkylsilyl group in molecular structure becomes base material The adhesiveness of the metal such as the inorganic matter such as silicon compound such as silicon, silicon oxide, silicon nitride, gold, copper, molybdenum, titanium, aluminum and dielectric film Compound.Specifically, known silane coupler etc. are also effective.
[inorganic particulate]
The photoresist compositions of the present invention can contain inorganic particulate.By containing inorganic particulate, cured film Hardness is more excellent.
The mean diameter of the inorganic particulate used in the present invention preferably 1～200nm, more preferably 5～100nm, most preferably 5 ～50nm.Mean diameter refers to its arithmetic average during particle diameter by any 200 particles of determination of electron microscopy.Further, When being shaped as aspherical of particle, using the longest limit as diameter.
Further, from the viewpoint of the hardness of cured film, the porosity of inorganic particulate is preferably smaller than 10%, more preferably less than 3%, most preferably imporosity.On the other hand, from the viewpoint of low-k, the porosity of inorganic particulate is preferably 10% Less than 80%, more preferably 12% less than 50%.The porosity of particle is with cuing open that ultramicroscope obtains The arithmetic average of 200 of the area ratio that the aperture sections of visible image is overall with particle.
As inorganic particulate, preferably comprise Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, The equiatomic metal oxide particle of Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, more preferably silicon oxide, oxygen Change titanium, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin-oxide, antimony/tin-oxide, more preferably silicon oxide, titanium oxide, Titanium composite oxide, zirconium oxide, from the stability of particle, accessibility, the hardness of cured film, the transparency, refractive index adjustment etc. From the viewpoint of, particularly preferred silicon oxide, zirconium oxide or titanium oxide.
These particles can also carry out the modification of various surfaces.For example, it is possible to import reactive group on surface.
In the present invention, inorganic particulate can also be as by using ball mill, rod in suitable dispersant and solvent The mixing arrangements such as grinding machine carry out mixing, disperse and the dispersion liquid prepared and for.
About the content of inorganic particulate, when coordinating inorganic particulate, from the viewpoint of hardness and refractive index, relative to sense All solids composition 100 mass parts of photosensitive resin composition, more than preferably 1 mass parts, more than more preferably 5 mass parts, enters one More than step preferably 10 mass parts.Further, below preferably 80 mass parts, below more preferably 50 mass parts, further preferred 40 mass Below Fen.
Inorganic particulate can contain only one, it is also possible to containing two or more.For example, it is possible to and with Zirconia particles and oxygen Change titanium particle.When containing time two or more, preferably its always metering is within the above range.
[preparation method of photosensitive polymer combination]
The photosensitive polymer combination of the present invention can be by with the ratio of regulation and mixing each composition also with any means It is stirred dissolving and prepares.Such as, it is also possible to after each composition is respectively prepared the solution being dissolved in advance in solvent, They are prepared with the ratio mixing of regulation the photosensitive polymer combination of the present invention.Composition solution produced above can also The filter etc. enough using such as aperture 0.2 μm uses after filtering.
The photosensitive polymer combination of present invention solid component concentration at 25 DEG C preferably 1～60 mass %, more preferably 3 ～40 mass %, further preferred 5～30 mass %, particularly preferred 5～17 mass %.Further, when carrying out slot coated, Gu Body constituent concentration preferably 7～30 mass %.
Viscosity at 25 DEG C preferably 1～100mPa s, more preferably 2～60mPa s, most preferably 3～40mPa s.And And, when carrying out slot coated, preferably 2～20mPa s.
Further, the surface tension at 25 DEG C preferably 15～35mN/m, more preferably 15～30mN/m.
By solid component concentration, viscosity, surface tension are set to above-mentioned scope, it is possible to carry out the coating of high-quality.Viscous Degree such as can use TOKI SANGYO CO., LTD viscometer RE85L (rotor: 1 ° of 34 ' × R24 measurement range 0.6～ 1200mPa s) it is measured when temperature is adjusted to 25 DEG C.Surface tension is for using Kyowa Interface The surface tensiometer CBVP-A3 of Science Co., Ltd., utilizes at 25 ± 0.2 DEG C and the lower end of platinum sheet be impregnated in mensuration The value that method in sample measures.It addition, platinum sheet use utilize before the assay alcohol burner burn red and by the platinum sheet of clean surface.
[manufacture method of cured film]
Then, the manufacture method of the cured film of the present invention is illustrated.
The manufacture method of the cured film of the present invention comprises following (1)～the operation of (5).
(1) photosensitive polymer combination of the present invention is coated the operation on substrate；
(2) from the photosensitive polymer combination coating substrate, remove the operation of solvent；
(3) operation that the photosensitive polymer combination removing solvent is exposed；
(4) operation that exposed photosensitive polymer combination is developed；
(5) by the operation of developed photosensitive polymer combination heat cure；
Hereinafter, successively each operation is illustrated.
In the operation (also referred to as painting process) of (1), preferably the photosensitive polymer combination of the present invention is coated base The moistening film containing solvent is made on plate.Preferably carried out before photosensitive polymer combination is coated substrate alkali cleaning or The cleaning of the substrate of plasma clean etc, more preferably processes base further with hexamethyldisiloxane after base-plate cleaning Plate surface.By carrying out this process, there is the tendency that the adhesiveness of substrate is improved by photosensitive polymer combination.As utilization Hexamethyldisiloxane processes the method for substrate surface and is not particularly limited, such as, can enumerate and substrate is exposed to hexamethyl Method etc. in disilazane steam.
As aforesaid substrate, inorganic substrate, resin substrate, resin composite materials substrate etc. can be enumerated.
As inorganic substrate, such as, can enumerate glass substrate, quartz base plate, silicone substrate, silicon nitride board and at this The composite base plate of molybdenum, titanium, aluminum, copper etc. it has been deposited with on a little substrates.
As resin substrate, can enumerate by polybutylene terephthalate, polyethylene terephthalate, poly-naphthalene diformazan Acid second diester, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, Merlon, polysulfones, polyether sulfone, polyarylate, allyl diglycol carbon Acid esters, polyamide, polyimides, polyamidoimide, Polyetherimide, polybenzoxadiazole (Polybenzazole), polyphenyl Fluororesin, liquid crystal polymer, acrylic resin, the asphalt mixtures modified by epoxy resin such as thioether, polycyclic alkene, norbornene resin, polychlorotrifluoroethylene Fat, silicone resin, ionomer resin, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic ether, maleimide The substrate that the synthetic resin such as amine-ene hydrocarbon, cellulose, ring vulcanizing compounds are constituted.These substrates directly use with above-mentioned form Situation is less, is generally formed with the multilayer laminate constructions of such as TFT element etc with the form of final products.
The coating process of substrate is not particularly limited, such as can use ink-jet method, slot coated method, spraying process, The methods such as rolling method, spin-coating method, cast coating method, slit and circumgyration.
In the case of slot coated method, preferably the relative moving speed of substrate Yu slit die is set to 50～120mm/ sec。
Moistening thickness when being coated is not particularly limited, and can be coated with the thickness corresponding with purposes, Generally use with the scope of 0.5～10 μm.
Alternatively, it is also possible to be suitable for Japanese Unexamined Patent Publication 2009-before being coated with the compositions used in the present invention on substrate So-called pre-wet method described in No. 145395 publications.
Further, when the photosensitive polymer combination of the present invention is coated large substrate, from the coating to large substrate From the viewpoint of adaptability, particularly preferred slot coated.Large substrate refers to 0.9m × more than 0.9m and 3.0m × below 3.0m The substrate of size.
When the photosensitive polymer combination of the slot coated present invention, the solid component concentration of compositions is preferably 7～30 Quality %.Further, the viscosity at 25 DEG C is preferably 2.0～20mPa s.Further, the surface tension at 25 DEG C be preferably 15～ 35mN/m。
It addition, solid component concentration, viscosity, surface tension can be adjusted by solvent, the kind of surfactant and amount Whole.
In the operation (also referred to as solvent removing step) of (2), by decompression (vacuum) and/or heating etc. from being coated with Above-mentioned moistening film removes solvent and on substrate, forms dry coating.The heating condition of solvent removing step be preferably 70～ Carry out at 130 DEG C about 30～300 seconds.When temperature and time is in above-mentioned scope, has figuratum adhesiveness and more well and go back The tendency of residue can be reduced further.
In the operation (also referred to as exposure process) of (3), the substrate being provided with film is irradiated the active ray of predetermined pattern. In this operation, light acid producing agent decomposes and produces acid.By the catalytic action of produced acid, it is coated with acid contained in film component Decomposability group hydrolyzes and generates carboxyl or phenolic hydroxyl group.
Exposure light source as active ray, it is possible to use low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, LED light source, excimer laser generator etc., it may be preferred to use i ray (365nm), h ray (405nm), g ray (436nm) etc. there is the active ray of the wavelength of more than wavelength 300nm and below 450nm.Further, as required, it is also possible to logical Cross the light splitting wave filter of long wavelength cutoff wave filter, short wavelength's cut-off filter, band filter etc to adjust irradiation light.Expose Light quantity is preferably 1～500mJ/cm2。
As exposure device, it is possible to use mirror surface projection alignment exposer, step-by-step movement, scanning device, proximity, contact, The exposure machine of the various modes such as microlens array, lens scan device, laser explosure.And, additionally it is possible to it is set to use so-called surpassing The exposure of resolution techniques.As super resolution technology, the multiple-exposure that multiexposure, multiple exposure can be enumerated, the method using phase shifting mask, Deformation illumination method etc. with annular illumination method as representative.By using these super resolution technologies, it is possible to form the pattern of high-resolution, The most preferred.
In the formation zone of acid catalyst, in order to accelerate said hydrolyzed reaction, post-heating can be exposed and process: Post Exposure Bake is (hereinafter also referred to as " PEB ".).Pass through PEB, it is possible to promote to generate carboxyl or phenol from acid decomposability group Hydroxyl.Temperature when carrying out PEB is preferably more than 30 DEG C and less than 130 DEG C, more preferably more than 40 DEG C and less than 110 DEG C, especially It is preferably more than 50 DEG C and less than 100 DEG C.
In the operation (also referred to as developing procedure) of (4), use alkaline-based developer, to having free carboxyl or phenol hydroxyl The copolymer of base develops.By by containing the resin group with the carboxyl being easily soluble in alkaline-based developer or phenolic hydroxyl group The exposure portion region of compound is removed and is formed eurymeric image.
Developer solution used in developing procedure preferably comprises the aqueous solution of alkali compounds.As alkali compounds, Such as can use the alkali metal hydroxides such as Lithium hydrate, sodium hydroxide, potassium hydroxide；Sodium carbonate, potassium carbonate, cesium carbonate Deng alkali carbonate class；The alkali metal hydrogencarbonate class such as sodium bicarbonate, potassium bicarbonate；Tetramethylammonium hydroxide, tetraethyl hydrogen The tetra-alkyl ammonium hydroxide classes such as amine-oxides, TPAOH, TBAH, diethyl-dimethyl ammonium hydroxide: Choline etc. (hydroxy alkyl) trialkylammonium hydroxides class；The silicates such as sodium silicate, sodium metasilicate；Ethamine, propylamine, diethylamine, The alkanamine classes such as triethylamine；The alcamines such as dimethylethanolamine, triethanolamine；1,8-diazabicyclo-[5.4.0]-7-hendecene, The ester ring type amine of 1,5-diazabicyclo-[4.3.0]-5-nonene etc..
Among those, preferably sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl Ammonium hydroxide, TBAH, choline (2-hydroxyethyl trimethylammonium hydroxide).
And, it is also possible to by add in above-mentioned bases aqueous solution the water-miscible organic solvents such as appropriate methanol or ethanol or Surfactant and the aqueous solution that obtains is used as developer solution.
The pH of developer solution is preferably 10.0～14.0.
Developing time is preferably 30～500 seconds, and, developing method can be puddle method (sheathed immersion method), spray process, Any one of infusion process etc..
Operation can also be rinsed after developing.In rinsing operation, after utilizing the washing developments such as pure water Substrate is removed accompanying developer solution and removes development residue.Purging method can use known method.For example, it is possible to lift Go out spray irrigation, immersion rinse etc..
In the operation (also referred to as post-bake process) of (5), by obtained eurymeric image being heated and by acid Decomposability group thermally decomposes, and generates carboxyl or phenolic hydroxyl group, cross-links with crosslinkable groups, cross-linking agent etc., it is possible to shape Become cured film.This heating is preferably used the heater such as heating plate or baking oven and advises at set point of temperature such as 180～400 DEG C The heat treated fixed time, if the most on hot plate, then heat treated 5～90 minutes, if baking oven, then heat treated 30～ 120 minutes.By so carrying out cross-linking reaction, it is possible to form the more excellent protecting film such as thermostability, hardness or layer insulation Film.Further, carry out under nitrogen atmosphere when carrying out heat treated, thus can also improve the transparency further.
Before rear baking, it is also possible to toast after carrying out after toasting at a lower temperature and (add middle Roaster Sequence).When carrying out middle baking, enter under high temperature more than 200 DEG C after preferably heating 1～60 minute at 90～180 DEG C Toast after row.And, it is also possible to toasted centre, rear baking is divided into the multistage in 3 stages more than to heat.By this Middle baking, the design of rear baking, it is possible to adjust the cone angle of pattern.These heating can use heating plate, baking oven, infrared ray to add The known heating means such as hot device.
It addition, before rear baking, it is possible to utilize active ray to formed figuratum substrate carry out whole face expose again (after Exposure) after carry out after toast, thus from the light acid producing agent being present in unexposed portion produce acid so that it is as promote hand over The catalyst function of connection operation such that it is able to promote the curing reaction of film.As preferably exposure when comprising post-exposure operation Light quantity, preferably 100～3,000mJ/cm2, particularly preferred 100～500mJ/cm2。
And then, the photosensitive polymer combination of the present invention cured film obtained is also used as dry-etching resist. When the cured film obtained carrying out heat cure by post-bake process is used as dry-etching resist, can carry out being ashed, The dry-etchings such as plasma etching, ozone etching process as etch processes.
[cured film]
The cured film of the present invention is that the photosensitive polymer combination of the invention described above is solidified the cured film obtained.
The cured film of the present invention can be suitable as interlayer dielectric.Further, the cured film of the present invention is preferably by above-mentioned The cured film that the forming method of the cured film of the present invention obtains.
By the photosensitive polymer combination of the present invention, also have relatively when available insulating properties excellence, at high temperature baking The interlayer dielectric of the high transparency.Use the interlayer dielectric of photosensitive polymer combination of the present invention due to sensitivity Good and solvent tolerance excellent, therefore various aobvious at liquid crystal indicator, organic EL display, touch panel display device etc. In the purposes of showing device etc. useful.
[liquid crystal indicator]
The liquid crystal indicator of the present invention has the cured film of the present invention.
As the liquid crystal indicator of the present invention, except having the photosensitive polymer combination and shape using the invention described above Beyond the planarization film become or interlayer dielectric, it is not particularly limited, the known liquid crystal using various structures can be enumerated Display device.
Such as, the TFT's (Thin-Film Transistor) possessed as the liquid crystal indicator of the present invention is concrete Example, can enumerate non-crystalline silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..The cured film of the present invention is special due to electricity Property excellent, therefore can preferably with these TFT combination and use.
Further, as the liquid crystal indicator adoptable liquid crystal drive mode of the present invention, TN (Twisted can be enumerated Nematic) mode, VA (Vertical Alignment) mode, IPS (In-Plane-Switching) mode, FFS (Fringe Field Switching) mode, OCB (Optical Compensated Bend) mode etc..
In panel is constituted, even if also may be used in the liquid crystal indicator of COA (Color Filter on Array) mode To use the cured film of the present invention, such as, can serve as organic insulating film (115) or the Japan of Japanese Unexamined Patent Publication 2005-284291 The organic insulating film (212) of JP 2005-346054.Further, the adoptable liquid crystal of liquid crystal indicator as the present invention takes Concrete aligned to film can enumerate friction orientation method, optical alignment method etc..And, it is also possible to pass through Japanese Unexamined Patent Publication PSA (Polymer Sustained described in 2003-149647 publication or Japanese Unexamined Patent Publication 2011-257734 publication Alignment) technology carries out polymer orientation support.
Further, the photosensitive polymer combination of the present invention and the cured film of the present invention are not limited to such use, permissible For various uses.Such as, in addition to planarization film or interlayer dielectric, it is also possible to be suitable for color filter protecting film, Or for the thickness of the liquid crystal layer in liquid crystal indicator being remained constant sept or arranging in solid-state imager Lenticule etc. on color filter.
Fig. 1 is the concept sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.This color liquid crystal shows Showing device 10 has the liquid crystal panel of back light unit 12 for the back side, and wherein, liquid crystal panel is configured with and is being pasted with the 2 of polarizing coating The element of the TFT16 that all pixels of configuration are corresponding between sheet glass substrate 14,15.At each element being formed on glass substrate In, connect up the ito transparent electrode 19 of tangible pixel electrode by the contact hole 18 that is formed in cured film 17.Saturating at ITO Prescribed electrode 19 is provided with the layer of liquid crystal 20 and is configured with the RGB color filter 22 of black matrix".
Light source as backlight is not particularly limited, it is possible to use known light source.For example, it is possible to enumerate White LED, Blue/red/greens etc. are multi-colored led, fluorescent lamp (cold-cathode tube), organic EL etc..
Further, liquid crystal indicator can also be set to the device of 3D (stereoscopic vision) type or be set to the dress of touch panel type Put.Alternatively, it is also possible to be set to pliability device, can serve as described in Japanese Unexamined Patent Publication 2011-145686 publication the 2nd layer Between interlayer dielectric (520) described in dielectric film (48) or Japanese Unexamined Patent Publication 2009-258758 publication, Japanese Unexamined Patent Publication Organic insulating film (PAS) described in Fig. 1 of 2007-328210 publication.
Use Fig. 2 that liquid crystal indicator described in Fig. 1 of Japanese Unexamined Patent Publication 2007-328210 publication is said Bright.
In Fig. 2, symbol SUB1 is glass substrate, has multiple scan signal line and intersects many with multiple scan signal lines Individual video signal cable.At each near intersections, there is TFT.
On glass substrate SUB1, it is sequentially formed with the semiconductor film PS of basement membrane UC, silicon etc., gate insulating film from below The gate electrode GT of GI, TFT, the 1st interlayer dielectric IN1.1st interlayer dielectric IN1 is formed the drain electrode of TFT The source electrode SD2 of SD1 and TFT.
Drain electrode SD1 is connected to TFT through the contact hole being formed from gate insulating film GI and the 1st interlayer dielectric IN1 Drain region.Source electrode SD2 is connected to through the contact hole being formed from gate insulating film GI and the 1st interlayer dielectric IN1 The source region of TFT.
Drain electrode SD1 and source electrode SD2 are formed with the 2nd interlayer dielectric IN2.At the 2nd interlayer dielectric IN2 On be formed with organic insulating film PAS.Organic insulating film PAS can use the photosensitive polymer combination of the present invention to be formed.
Organic insulating film PAS is formed opposite electrode CT and reflectance coating RAL.
Opposite electrode CT and reflectance coating RAL are formed with the 3rd interlayer dielectric IN3.On the 3rd interlayer dielectric IN3 It is formed with pixel electrode PX.Pixel electrode PX is through being formed from the 2nd interlayer dielectric IN2 and the contact of the 3rd interlayer dielectric IN3 Hole is connected with the source electrode SD2 of TFT.
When the photosensitive polymer combination using the present invention forms organic insulating film PAS, due to organic insulating film PAS's Excellent heat resistance, therefore, it is possible to improve the masking temperature of the 3rd interlayer dielectric IN3, it is possible to masking goes out finer and close film.
Further, since the photosensitive polymer combination of the present invention can form thermostability and the cured film of compactness excellence, Therefore UC, IN1, IN2, the IN3 generally formed by inorganic material also is able to use the photosensitive polymer combination of the present invention to carry out shape Become.
About the detailed content of the liquid crystal indicator shown in Fig. 2, it is referred to Japanese Unexamined Patent Publication 2007-328210 publication Record, its content is incorporated herein.
It addition, Fig. 2 shows the figure of top gate structure, but it is readily adaptable for use in the display of bottom gate configuration equally Device.
[organic EL display]
The organic EL display of the present invention has the cured film of the present invention.
As the organic EL display of the present invention, except having the photosensitive polymer combination shape using the invention described above Beyond the planarization film become or interlayer dielectric, it is not particularly limited, can enumerate and use the known various of various structures Organic EL display.
Such as, the tool of the TFT (Thin-Film Transistor) possessed as the organic EL display of the present invention Style, can enumerate non-crystalline silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..The cured film of the present invention is due to electricity Excellent, therefore preferably can combine with these TFT and use.
Fig. 3 is the composition concept map of an example of organic EL display.Represent the organic EL display of bottom emission type In the schematic cross sectional views of substrate, there is planarization film 4.
Glass substrate 6 is formed the TFT1 of bottom gate type, and is formed by Si to cover the state of this TFT13N4 The dielectric film 3 constituted.After being formed at this contact hole omitting diagram on the insulating film 3, via this contact hole, at dielectric film 3 Upper formation is connected to the distribution 2 (highly 1.0 μm) of TFT1.Distribution 2 is for connecting between TFT1 or being connected in operation thereafter The organic EL element formed and the parts of TFT1.
And then, in order to make the concavo-convex planarization caused by being formed of distribution 2, with landfill by distribution 2 cause concavo-convex State forms planarization film 4 on the insulating film 3.
Planarization film 4 is formed the organic EL element of bottom emission type.That is, the first electrode 5 being made up of ITO via Contact hole 7 is connected to distribution 2 and is formed on planarization film 4.Further, the first electrode 5 is equivalent to the anode of organic EL element.
It is formed with the dielectric film 8 of the shape covering the first electrode 5 periphery, by arranging this dielectric film 8, it is possible to prevent first The short circuit between the second electrode formed in electrode 5 and operation behind.
Although it addition, not shown in Fig. 3, but being deposited with successively across desired pattern mask and arrange hole transmission layer, have Machine luminescent layer, electron transfer layer, then, the second electrode that whole the formation in surface is made up of Al, use ultraviolet solid Change type epoxy resin seals with the laminating of glass for sealing plate, thus obtains being connected to it in each organic EL element The active matrix organic EL display device of the TFT1 being driven.
The photosensitive polymer combination of the present invention is owing to sensitivity is good and the cured film excellent such as solvent tolerance, therefore The Resist patterns that the photosensitive polymer combination using the present invention is formed is made next door and is used as the structural portion of MEMS Part, or the part as Mechanical Driven assembly assembled and used.As this MEMS device, the most permissible Enumerate SAW color filter, BAW color filter, gyro sensor (gyro sensor), the micro-shutter (micro of display Shutter), the group such as imageing sensor (image sensor), Electronic Paper, ink gun, biochip (biochip), sealant Part.More specifically example is illustrated in Japanese Unexamined Patent Application Publication 2007-522531, Japanese Unexamined Patent Publication 2008-250200, Japanese Unexamined Patent Publication 2009- In 263544 grades.
The photosensitive polymer combination of the present invention is excellent due to flatness and the transparency, the most such as, can be used for being formed Dike layer (bank layer) (16) described in Fig. 2 of Japanese Unexamined Patent Publication 2011-107476 publication and planarization film (57), day Next door (12) described in Fig. 4 (a) of this JP 2010-9793 publication and planarization film (102), Japanese Unexamined Patent Publication 2010- Dike floor (221) described in Figure 10 of No. 27591 publications and the 3rd interlayer dielectric (216b), Japanese Unexamined Patent Publication 2009-128577 The 2nd interlayer dielectric (125) described in Fig. 4 (a) of number publication and the 3rd interlayer dielectric (126), Japanese Unexamined Patent Publication 2010- Planarization film (12) described in Fig. 3 of No. 182638 publications and pixel separation dielectric film (14) etc..In addition, it is also possible to It is appropriately used in order to the thickness of the liquid crystal layer in liquid crystal indicator to be remained constant sept, facsimile machine, reprography The brilliant imaging optical system carrying color filter such as machine, solid-state imager or the lenticule of the joints of optical fibre.
Additionally, due to light resistance, thermostability and resistance to chemical reagents are excellent, therefore LED encapsulant, semiconductor element are protected Protect dielectric film, semiconductor element distribution dielectric film again, multilayer printed circuit board dielectric film, welding protection film, cover layer thin Film (cover layer film), baseplate-laminating film etc. are useful.
[touch panel display device]
The touch panel display device of the present invention has the cured film of the present invention.The touch panel display device of the present invention is excellent Select touch panel insulating barrier and or all or part of of protective layer be made up of the solidfied material of the present invention.Further, the present invention Touch panel display device preferably at least have transparency carrier, ITO electrode, IZO electrode, other transparency electrodes, metal electrode and Insulating barrier and or protective layer.
As transparency carrier spendable in the touch panel display device of the present invention, it may be preferred to enumerate glass substrate, Quartz base plate, transparent resin substrate etc..
The touch panel display device of the present invention such as can manufacture as follows.
I.e., it is possible to manufacture via following operation: operation 1, by various methods such as ink-jet application modes, with ITO The mode of electrode contact is coated with the photosensitive polymer combination of the present invention；Operation 2, photosensitive coat in above-mentioned ITO electrode Property resin combination on mounting there is the mask of patterns of openings of regulation shape, and carry out active energy beam and irradiate and expose Light；Operation 3, develops to the photosensitive polymer combination after exposure；And operation 4, add the photoresist group after heat development Compound.
In operation 1, when photosensitive resin coating compositions in the way of contacting with ITO electrode, be coated with this At least some of of bright photosensitive polymer combination contacts with ITO electrode.
Operation 2 can be carried out in the same manner as above-mentioned exposure process, and optimal way is the most identical.
Operation 3 can be carried out in the same manner as above-mentioned developing procedure, and optimal way is the most identical.
Operation 4 can be carried out in the same manner as above-mentioned post-bake process, and optimal way is the most identical.
The touch panel display device of the present invention can be to use electrostatic capacitance mode, resistive film mode, optical mode etc. each Known to kind, mode is as detection mode.Wherein, preferred electrostatic capacitance mode.
As the type of touch panel, so-called interior insert-type (in-cell) (such as, Japanese Unexamined Patent Application Publication 2012-can be enumerated Fig. 5, Fig. 6, Fig. 7, Fig. 8 of No. 517051 publications), so-called outer insert-type (on-cell) (such as, Japanese Unexamined Patent Publication 2013-168125 Figure 19, Fig. 1 and Fig. 5 of Japanese Unexamined Patent Publication 2012-89102), OGS (One Glass Solution) type, TOL (Touch on Lens) type (such as Fig. 2 of Japanese Unexamined Patent Publication 2013-54727, Fig. 2, Fig. 3, Fig. 4, Fig. 5 of Japanese Unexamined Patent Publication 2015-15042), other Structure (such as, Fig. 6 of Japanese Unexamined Patent Publication 2013-164871 publication), various outer hung type (out-cell) (so-called GG (glass On glass), so-called G1/G2, so-called GFF (Glass Film Film), so-called GF2, so-called GF1, so-called G1F etc.).
Touch panel and possess touch panel and can be suitable for " up-to-date touch as the touch panel display device of constitutive requirements Panel technology " (on July 6th, 2009 distribution Techno Times Co., Ltd.), male two chief editors of three paddy, " the technology of touch panel With exploitation ", CMC publishes (2004,12), FPDInternational 2009Forum T-11 and gives a lecture teaching material, Cypress Structure disclosed in Semiconductor Corporation Application Note AN2292 etc..
Embodiment
Hereinafter, enumerate embodiment and the present invention is carried out the brightest.Material shown in following example, use Amount, ratio, process content, process step etc. without departing from spirit of the invention, then can suitably change.Therefore, the present invention Scope be not limited to following.
The detailed content of the abbreviation of each compound used in expression embodiment and comparative example is as follows.
＜ (A) polysiloxanes ＞
(synthesis of A-1)
By 4-hydroxybenzyl trimethoxy silane 114.2g (0.5 mole), 3-glycidoxypropyltrime,hoxysilane 94.5g (0.4 mole), MTMS 6.8g (0.05 mole), phenyltrimethoxysila,e 9.9g (0.05 mole), DAA (DAA) 250g puts in there-necked flask, at room temperature stirring, dissolves while adding in water 54g through 30 minutes There is the phosphate aqueous solution of phosphoric acid 0.176g (being 0.1 mass % relative to the silane compound put into).Thereafter, by there-necked flask It is soaked in the oil bath of 40 DEG C, after stirring 30 minutes, through 30 minutes, oil bath is warming up to 115 DEG C.Heat up after starting 1 hour, The interior temperature of solution reaches 100 DEG C, begins to warm up 2 hours (interior temperature is 100～110 DEG C) of stirring from this temperature.
Methanol as by-product slips out in the reaction.The DAA solution of obtained polysiloxanes is injected into a large amount of water In, make polymer separate out, and carry out filtering, being dried and obtain A-1 precursor.
The 100g of obtained A-1 precursor is dissolved in oxolane 400mL, and add catalytic amount to toluene sulphur After acid, stir at 20 DEG C, drip on one side and ethyl vinyl ether 30g is dissolved in obtain in oxolane 30g molten Liquid.
After reacting 30 minutes, utilize strong aqua ammonia to be neutralized, in water 5L, drip the result of the reactant liquor of neutralization, obtain White solid.After being filtered, it is dissolved in acetone 300ml, and is added drop-wise in water 5L, be dried after filtration and obtain A- 1。
The weight average molecular weight of the polystyrene conversion that use GPC obtains is 5000.
Based on1In the analysis of H-NMR, A-1 confirms 70 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
The kind of the silane compound used in the synthesis of A-1 described below and mol ratio.
[table 1]
(synthesis of A-2)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-2.
Based on1In the analysis of H-NMR, A-2 confirms 70 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 2]
(synthesis of A-3)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-3.
Based on1In the analysis of H-NMR, A-3 confirms 70 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 3]
(synthesis of A-4)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-4.
Based on1In the analysis of H-NMR, A-4 confirms 70 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 4]
(synthesis of A-5)
By 3-silicochloroform base-1-cyclohexane carboxylic acid methyl ester 12.4g (0.045mol), glycidoxypropyl group trichlorine Silane 11.2g (0.045mol), methyl trichlorosilane 0.745g (0.005mol), phenyl trichlorosilane 1.06g (0.005mol) It is dissolved in toluene 150g, at room temperature stirs to drip and add in water 300g.After completion of dropwise addition, from reaction mixing Thing is isolated acidic aqueous phase, washes organic layer followed by water 1L, after water layer becomes neutrality, carry out 2 washings further. The solvent of organic layer is evaporated by vaporizer.This concentrated solution is heated 2 hours at 200 DEG C and is polymerized.
The solution carrying out dissolving by addition oxolane 800g in polymer and obtain is added drop-wise to 10% sodium hydroxide solution In 1,000g, heat 3 hours with 40 DEG C, make carbomethoxy hydrolyze.Utilize hydrochloric acid to become acidity and make polymer crystallize, go forward side by side Row filters, is dried and obtains A-5 precursor (polymer that the carboxyl of A-5 is not protected by tetrahydrofuran base).
In the way of identical with A-1, by high molecular weight reactive, A-5 precursor imported protection group, thus synthesize A-5.
Based on1In the analysis of H-NMR, in A-5, making dihydrofuran react with carboxyl, 78 moles of % are by tetrahydrochysene furan Mutter base.
The kind of the silane compound used in the synthesis of A-5 described below and mol ratio.
[table 5]
(synthesis of A-6)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-6.
Based on1In the analysis of H-NMR, A-6 confirms 78 moles of % of carboxyl by ethoxyethyl group.
[table 6]
(synthesis of A-7)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-7.
Based on1In the analysis of H-NMR, A-7 confirms 78 moles of % of carboxyl by ethoxyethyl group.
[table 7]
(synthesis of A-8)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-8.
Based on1In the analysis of H-NMR, A-8 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 8]
(synthesis of A-9)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-9.
Based on1In the analysis of H-NMR, A-9 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 9]
(synthesis of A-10)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-10.
Based on1In the analysis of H-NMR, A-10 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 10]
(synthesis of A-11)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-11.
Based on1In the analysis of H-NMR, A-11 confirms 75 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 11]
(synthesis of A-12)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-12.
Based on1In the analysis of H-NMR, A-12 confirms 75 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 12]
(synthesis of A-13)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-13.
Based on1In the analysis of H-NMR, A-13 confirms 70 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 13]
(synthesis of A-14)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-14.
Based on1In the analysis of H-NMR, A-14 confirms 92 moles of % of carboxyl by tetrahydrofuran base.
[table 14]
(synthesis of A-15)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-15.
Based on1In the analysis of H-NMR, A-15 confirms 88 moles of % of carboxyl by ethoxyethyl group.
[table 15]
(synthesis of A-16)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-16.
Based on1In the analysis of H-NMR, A-16 confirms 80 moles of % of carboxyl by tetrahydrofuran base.
[table 16]
(synthesis of A-17)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-17.
Based on1In the analysis of H-NMR, A-17 confirms 75 moles of % of hydrogen atom of phenolic hydroxyl group by ethyoxyl second Base.
[table 17]
(synthesis of A-18)
A-5 precursor is obtained in the way of the method described with the synthesis of A-5 is identical.
Make isobutene. carry out reacting by high molecular weight reactive and A-5 precursor is imported protection group and synthesizes A-18.
Based on1In the analysis of H-NMR, A-18 confirms 70 moles of % of carboxyl by the tert-butyl ester.
The kind of the silane compound used in the synthesis of A-18 described below and mol ratio.
[table 18]
(synthesis of A-101)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-101.
Based on1In the analysis of H-NMR, A-101 confirms 70 moles of % of carboxyl by ethoxyethyl group.
[table 19]
(synthesis of A-102)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-102.
Based on1In the analysis of H-NMR, A-102 confirms 70 moles of % of carboxyl by ethoxyethyl group.
[table 20]
(synthesis of A-103)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-103.
Based on1In the analysis of H-NMR, A-103 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 21]
(synthesis of A-104)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-104.
Based on1In the analysis of H-NMR, A-104 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 22]
(synthesis of A-105)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-105.
Based on1In the analysis of H-NMR, A-105 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 23]
(synthesis of A-201)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-201.
Based on1In the analysis of H-NMR, A-201 confirms 70 moles of % of carboxyl by ethoxyethyl group.
[table 24]
(synthesis of A-202)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-1, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-202.
Based on1In the analysis of H-NMR, A-202 confirms 70 moles of % of carboxyl by ethoxyethyl group.
[table 25]
(synthesis of A-203)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-203.
Based on1In the analysis of H-NMR, A-203 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 26]
(synthesis of A-204)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-204.
Based on1In the analysis of H-NMR, A-204 confirms 78 moles of % of carboxyl by tetrahydrofuran base.
[table 27]
(synthesis of A-205)
Use silane compound with compound shown below and mol ratio, and adjust kind and the amount of protection group, except this In addition, in the way of identical with A-5, mix following silane compound and make it react, importing protection group by high molecular weight reactive, Thus synthesize A-205.
Based on1In the analysis of H-NMR, A-205 confirms 80 moles of % of carboxyl by tetrahydrofuran base.
[table 28]
Silane compound, mol ratio
(synthesis of A '-1)
According to the record of 0117 paragraph of Japanese Unexamined Patent Publication 2013-92633 publication, synthesize A '-1 as polysiloxanes, This polysiloxanes contain there is the construction unit of the protected group of carboxylic acid and without having the construction unit of crosslinkable groups.
Add in the glass reaction vessel possess thermometer and agitating device the toluene 300g as solvent, 2,4,6, 8-tetramethyl-ring tetrasiloxane 240g (1 mole), acrylic acid-tert-butyl ester 64.1g (0.5 mole), 4-t-butoxystyrene 352g (2 moles) and the platinum-divinyl tetramethyl disiloxane complex (Karstedt catalyst) as catalyst 0.05g, stirs reaction at 60 DEG C and evaporates solvent in 10 hours, obtain polysiloxanes (A '-1) precursor.
The toluene 200g as solvent, poly-silica is added in the glass reaction vessel possess thermometer and agitating device The 656g (01 mole) of alkane (A '-1) precursor, trimethoxyvinyl silane 221g (0.15 mole) and as catalyst platinum- Divinyl tetramethyl disiloxane complex (Karstedt catalyst) 0.001g, stirs and reacts 10 at 60 DEG C Hour.
Then, adding phenyltrimethoxysila,e 45.6g (0.23 mole) in this reaction system, ice cooling stirs To 5～10 DEG C, dripped 5% oxalic acid aqueous solution 50g through 30 minutes, and then stir 15 hours at 10 DEG C.50 DEG C, decompression Under carry out reflux dewatering/dealcoholation treatment, 50 DEG C, the toluene solvant of solvent is converted to PGMEA (the mono-first of propylene glycol 1-under decompression Ether 2-acetas), after being set to the PGMEA solution of 30%, remove solid content by filtration, obtain polysiloxanes (A '-1) 30%PGMEA solution.The matter average molecular weight obtained by gpc analysis is 6300.
The synthesis of '-1 (A ')
According to the record of 0121 paragraph of Japanese Unexamined Patent Publication 2013-92633, synthesize A ' '-1 as polysiloxanes, this poly-silicon Oxygen alkane contains the construction unit with epoxy radicals without having the construction unit of the protected group of carboxylic acid.
Add in the glass reaction vessel possess thermometer and agitating device the toluene 200g as solvent, 2,4,6, 8-tetramethyl-ring tetrasiloxane 120g (0.5 mole), allyl glycidyl ether 228g (2 moles) and platinum-divinyl tetramethyl Base disiloxane complex (Karstedt catalyst) 9mg, stirs after reacting 15 hours at 50～60 DEG C, At 60 DEG C, decompression evaporates solvent, obtains A ' '-1.The assay value of epoxide equivalent is 174.
(synthesis of A '-3)
According to the record of 0056 paragraph of Japanese Unexamined Patent Publication 2009-263522, synthesize A '-3 as polysiloxanes, this poly-silicon Oxygen alkane contains the construction unit with the group that silanol group is protected by acetal and the construction unit with epoxy radicals.
Phenyltrimethoxysila,e 89.2g is put in the 1L there-necked flask possess thermometer, blender and cooler (0.45 mole), 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane 110.9g (0.45 mole), methanol 360g, Stirring ice cooling on one side is to less than 10 DEG C.Putting into the acetic acid aqueous solution 90g of 0.1M in Dropping funnel, ice cooling is while dripping The result added, with the condensation reaction that is hydrolyzed that generates heat.Interior temperature is risen to room temperature, after stirring ripening 2 hours, ester is set and connects Clutch, evaporates methanol under heating normal pressure.Persistently evaporate until interior temperature exceedes the boiling point of methanol, thus obtain the poly-of nebulousurine thickness Siloxane solution.Now, the quantity of methyl alcohol captured is 382g.In this polysiloxane solution, add ethyl acetate 300g, utilize Pure water washes 2 solution dissolved.Utilize rotary evaporator to concentrate this polysiloxane solution, thus obtain water white poly- Siloxane solution A 233g (solid component concentration 62.2 mass %).
The weight average molecular weight (GPC polystyrene standard) of this polysiloxanes is 4.2 × 103.Further, utilize alkaline lysis not Remaining methoxyl group can be detected.Utilize29Si-NMR obtains the existence ratio of T0～T3, calculates following average composition formula.
Ph0.5(EP)0.5Si(OH)0.72O1.14
EP:2-(3,4-expoxycyclohexyl) ethyl
Ph: phenyl
Obtained polysiloxanes 80.4g is substituted by tetrahydrofuran solution (solid constituent by ethyl acetate solution solvent Concentration 20 mass %) after, put in the 1L there-necked flask possessing thermometer, blender and cooler, and add methanesulfonic acid 1.0g (0.01 mole).
Then, below ice cooling to 10 DEG C, stir and remain the state of less than 10 DEG C in interior temperature and utilize dropping liquid Funnel dropping ethyl-1-propylene ether 19.4g (0.23 mole).After dropping, after at room temperature reacting 2 hours, add triethylamine 1.0g (0.01 mole), terminates reaction.Reactant liquor is moved on to 1L eggplant type flask, utilizes rotary evaporator to evaporate under room temperature reduces pressure Remove oxolane, add methylisobutylketone 300g and 0.01N acetic acid aqueous solution 250ml and water cleans reactant liquor.Repeat total After counting 3 these cleaning operations, isolate organic layer, utilize rotary evaporator to concentrate, obtain as water white A '-3 49.0g of acetalation polysiloxanes.
According to13The result of C-NMR, the acetal radical Replacement rate calculating this A '-3 is 32.5 moles of %.
＜ (B) light acid producing agent ＞
B-1:PAG-103 (trade name, following shown structure, BASF AG's system)
B-1 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 45]
B-2: the structure (synthesis example will be described later) shown in following
It addition, the Ts in formula represents tosyl (p-toluenesulfonyl).
B-2 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 46]
B-3: structure shown in following is (according to described in the paragraph 0108 of Japanese Unexamined Patent Application Publication 2002-528451 publication Method synthesizes.)
B-3 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 47]
B-4: (synthesis example will be described later the structure shown in following.)
B-4 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 48]
B-5:GSID-26-1, triaryl sulfonium salts (BASF AG's system)
B-5 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 49]
B-6:4,7-bis-n-butoxy-1-naphthyl Tetramethylene sulfide triflate
B-6 is the light acid producing agent producing the acid that pKa is less than 3.
B-7: the structure (synthesis example will be described later) shown in following
B-7 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 50]
B-8: the structure shown in following (synthesizes according to method described in 249 paragraphs of WO11/087011.)
B-8 is the light acid producing agent producing the acid that pKa is less than 3.
[chemical formula 51]
Structure shown in B '-1:(is following.Quinone di-azido compound)
B '-1 is the compound of the acid producing pKa more than 3.
[chemical formula 52]
The synthesis ＞ of ＜ B-2
1-amino-beta naphthal hydrochlorate (Tokyo Chemical Industry Co., Ltd. system) 4.0g is made to be suspended in N- In methyl pyrrolidone (Wako Pure Chemical Co., Ltd. system) 16g, add sodium bicarbonate (Wako Pure Chemical Co., Ltd. system) after 3.4g, drip 4,4-dimethyl-3-oxopentanoic (Wako Pure Chemical Co., Ltd.'s system) 4.9g, heats 2 hours under nitrogen atmosphere at 120 DEG C.After letting cool, in reaction mixture, add water, acetic acid Ethyl ester carries out separatory, utilizes magnesium sulfate to be dried organic facies, and carries out filtering, concentrating and obtain thick B-1-2A.By thick B-1-2A Carry out silica gel column chromatography purification and obtain intermediate B-1-2A 1.7g.
Mixing B-1-2A (1.7g) and xylol (6mL), add p-methyl benzenesulfonic acid monohydrate (Wako Pure Chemical Co., Ltd. system) 0.23g, and heat 2 hours at 140 DEG C.After letting cool, in reaction mixture, add water, second Acetoacetic ester carries out separatory, after utilizing magnesium sulfate to be dried organic facies, carries out filtering, concentrating and obtain thick B-1-2B.
Mixing THF (2mL) and thick B-1-2B total amount, dropping 2M hydrochloric acid/THF solution 6.0mL, then adds under ice-cooling Amyl nitrite (Wako Pure Chemical Co., Ltd. system) (0.84g), stirs 2 hours after being warming up to room temperature.To Add water in obtained reactant mixture, ethyl acetate carries out separatory, after utilizing water to clean organic layer, utilizes magnesium sulfate It is dried, and carries out filtering, concentrating and obtain the thick B-1-2C of intermediate.
Thick for intermediate B-1-2C total amount is mixed with acetone (10mL), adds triethylamine (Wako Pure under ice-cooling Chemical Co., Ltd. system) (1.2g), paratoluensulfonyl chloride (Tokyo Chemical Industry Co., Ltd. system) (1.4g), after, it is warming up to room temperature and stirs 1 hour.Add water in obtained reaction mixture, ethyl acetate is carried out Separatory, after utilizing magnesium sulfate to be dried organic facies, carries out filtering, concentrating and obtain thick B-1-2.Utilize cold methanol by thick B-1-2 After carrying out repulped (reslurry), carry out filtering, being dried and obtain B-1-2 (1.2g).
It addition, B-21H-NMR spectrum (300MHz, CDCl3) it is δ=8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).
The synthesis ＞ of ＜ B-4
To beta naphthal (10g), chlorobenzene (30mL) aaerosol solution in add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), mixed liquor is heated to 40 DEG C and makes it react 2 hours.Under ice-cooling, in reactant liquor, 4NHCl is dripped water-soluble Liquid (60mL), and add ethyl acetate (50mL) and carry out separatory.Potassium carbonate (19.2g) is added, at 40 DEG C in organic layer After reacting 1 hour, add 2NHCl aqueous solution (60mL) and carry out separatory, after concentration of organic layers, utilize diisopropyl ether (10mL) crystal is carried out repulped, and carry out filtering, being dried and obtain ketonic compound (6.5g).
Acetic acid (7.3g), 50 matter are added in the aaerosol solution of obtained ketonic compound (3.0g) and methanol (30mL) Amount % aqueous hydroxylamine solution (8.0g), and be heated to reflux.After letting cool, add water (50mL), the crystal separated out is filtered, After cold methanol cleans, it is dried and obtains oxime compound (2.4g).
Obtained oxime compound (1.8g) is dissolved in acetone (20mL), adds triethylamine under ice-cooling (1.5g), paratoluensulfonyl chloride (2.4g), be warming up to room temperature and make it react 1 hour.Water (50mL) is added in reactant liquor, right After the crystal separated out filters, utilize methanol (20mL) to carry out repulped, and carry out filtering, being dried and obtain B-1-1's Compound (said structure) (2.3g).
It addition, 1H-NMR spectrogram (300MHz, CDCl of B-43) it is δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
The synthesis ＞ of ＜ B-7
Put in the separate type flask be equipped with agitator and thermometer N-hydroxyl naphthalimide sodium salt 33.6g, 4-dimethylaminopyridine 0.72g and oxolane 300 milliliters, be stirred at room temperature 25 DEG C and make it dissolve.Then, add Enter (+) 10-sulphur acyl chloride of camphor 42g, after stirring 3 hours, add triethylamine 15g, thereafter, be stirred at room temperature 10 hours.Connect , distilled water 300 milliliters loads reaction solution, leaches separated out precipitation.Use acetone and hexane, this precipitation is repeated Carry out repeatedly reprecipitation to process, obtain N-Camphora sulfonyloxy-1,8-naphthalimide 12g.
(synthesis of B '-1)
Flow down at drying nitrogen, by TrisP-PA (trade name, Honshu Chemical Industry Co., Ltd. system) 21.23g (0.05 mole) and 5-naphthoquinone two nitrine sulfonic acid chloride 37.62g (0.14 mole) are dissolved in Isosorbide-5-Nitrae-dioxane 450g, and It is set to room temperature.The triethylamine mixed with 1,4-dioxane 50g is dripped wherein not becoming in system in the way of more than 35 DEG C 15.58g (0.154 mole).After dropping, stir 2 hours at 30 DEG C.Filter triethylamine salt, filtrate is put in water.Its After, collect separated out precipitation by filtration.Utilize vacuum drier to be dried this precipitation, obtain quinone two nitrine of said structure Compound.
＜ (C) solvent ＞
C-1:PGMEA (propylene glycol 1-monomethyl ether 2-acetas)
C-2:MEDG (Methylethyl diethylene glycol)
(alkali compounds)
TBA: tri-n-butylamine
(other additives)
DBA:9,10-dibutoxy anthracene
FA-630:Shin-Etsu Chemical Co., Ltd. system, silicone surfactant " FA-630 " (trade name)
MW-30HM:NIKALAC MW-30HM (following structure)
[chemical formula 53]
The preparation ＞ of ＜ photosensitive polymer combination
Coordinate each composition as described in following table and be stirred and make solvent solution, and utilizing bore 0.2 μ The politef filter of m filters, and obtains the photosensitive polymer combination of each embodiment and comparative example.It addition, close In crosslinkable groups equivalent, following assay method is utilized to obtain.
Mensuration ＞ of ＜ crosslinkable groups equivalent
Weigh the solid constituent of a certain amount of photosensitive polymer combination, measure bridging property base contained in this solid constituent Group's amount.It addition, when crosslinkable groups is epoxy radicals, utilize the mensuration of the epoxide equivalent of defined in JIS K7236:2001 Method is obtained.About other crosslinkable groups beyond epoxy radicals, change volumetric solution, obtain also by identical assay method.
A: less than 1000
B:1000 is less than 1500
More than C:1500
The evaluation ＞ of ＜ storage stability
Measure and just prepared viscosity N after photosensitive polymer combination0(unit: Pa s) and at 10 DEG C preserve 30 days Viscosity N afterwards1(unit: Pa s), and calculate the value of following formula.
|(N1-N0)|/N0
The value of above-mentioned numerical expression represents the rheological parameters' change with time of viscosity, and numerical value is the least, the most preferred.Be evaluated by following benchmark, 1 and 2 is realistic scale.
1: less than 0.04
2:0.04 is less than 0.08
More than 3:0.08
The evaluation ＞ of ＜ sensitivity
Under hexamethyldisiloxane (HMDS) steam, by glass substrate (EAGLE XG, 0.7mm thickness (Corning Incorporated Co., Ltd. system)) expose 30 seconds, after each photosensitive polymer combination of slot coated, on hot plate with Within 90 DEG C/120 seconds, carry out prebake conditions and make solvent volatilize, thus form the photosensitive polymer combination layer of thickness 3.0 μm.
Then, Canon Co., Ltd. MPA 5500CF (high voltage mercury lamp) is used, by obtained photoresist group Compound layer is exposed with the mask pattern of diameter 6 μm hole shape.Further, alkaline developer (the tetramethyl hydroxide of 0.5% is utilized Aqueous ammonium), after the photosensitive polymer combination layer after development exposure in 23 DEG C/60 seconds, utilize ultrapure water 20 seconds.Logical Crossing these operations, Optimum i x ray exposure x amount (Eopt) when obtaining the hole differentiating a diameter of 6 μm is used as sensitivity.By following Benchmark is evaluated, and 1,2 and 3 is realistic scale.
It addition, for embodiment 18, comparative example 1 and comparative example 2, after exposure, heat 3 minutes in heating plate at 90 DEG C (add PEB (Post exposure bake) operation) afterwards to develop.
1: less than 80mJ/cm2
2:80mJ/cm2Less than 100mJ/cm2
3:100mJ/cm2Less than 140mJ/cm2
4:140mJ/cm2Less than 180mJ/cm2
5:180mJ/cm2Above
The evaluation ＞ of ＜ developability
Under hexamethyldisiloxane (HMDS) steam, by glass substrate (EAGLE XG, 0.7mm thickness (Corning Incorporated Co., Ltd. system)) expose 30 seconds, after each photosensitive polymer combination of slot coated, with 90 DEG C/120 seconds Carry out prebake conditions on hot plate and make solvent volatilize, thus form the photosensitive polymer combination layer of thickness 3.0 μm.
Then, Canon Co., Ltd. MPA 5500CF (high voltage mercury lamp) is used, by obtained photoresist group The compound layer line with 5 μm and the mask pattern in space, be used in the optimum exposure obtained in sensitivity evaluation and be exposed.And And, utilize alkaline developer (tetramethylammonium hydroxide aqueous solution of 0.5%), by the photosensitive polymer combination layer after exposure with 23 DEG C/within 60 seconds, develop after, utilize ultrapure water 20 seconds.Utilize this pattern of observation by light microscope, and by following benchmark It is evaluated.1,2 is realistic scale.
1: the edge of pattern is clean and tidy
2: have at the edge of pattern somewhat loosen
3: the marginal existence at pattern loosens.Or it is unpatterned.
The evaluation ＞ of ＜ thermostability
Under hexamethyldisiloxane (HMDS) steam, by glass substrate (EAGLE XG, 0.7mm thickness (Corning Incorporated Co., Ltd. system)) expose 30 seconds, after each photosensitive polymer combination of slot coated, with 90 DEG C/120 seconds Carry out prebake conditions on hot plate and make solvent volatilize, thus form the photosensitive polymer combination layer of thickness 3.0 μm.
Then, Canon Co., Ltd. MPA 5500CF (high voltage mercury lamp) is used, with 300mJ/cm2Light exposure carry out Whole exposure, and heat 60 minutes at 230 DEG C in an oven, thus form cured film.Then, as heat resistant test, drying Case heats 60 minutes at 300 DEG C, obtains the cured film after heat resistant test.Measure the transmission of the cured film after this heat resistant test Rate.
Use spectrophotometer (U-3000:Hitachi, Ltd. system), under wavelength 400nm, measure absorbance.Unit Represent with %.Being evaluated by following benchmark, 1,2 and 3 is realistic scale.
More than 1:96%
2:92% is less than 96%
3:88% is less than 92%
4: less than 88%
The evaluation ＞ of ＜ solvent tolerance
Respectively feel in the upper slot coated of glass substrate (0.7mm thickness (Corning Incorporated Co., Ltd. system)) After photosensitive resin composition, with the condition of 90 DEG C/120 seconds, carry out on hot plate heating and removing solvent, thus form film The photosensitive polymer combination layer of thick 3.0 μm.
Utilize Canon Co., Ltd. PLA-501F exposure machine (ultrahigh pressure mercury lamp), will be formed with obtained photonasty The substrate of resin composition layer becomes 300mJ/cm with integrating irradiation dose2(illumination: 20mW/cm2, i ray) mode expose Light, thereafter, utilizes baking oven to be heated 60 minutes by this substrate at 220 DEG C and obtain cured film, and measures thickness (t0).
This cured film is impregnated 10 minutes in the NMP of 60 DEG C, measures the thickness (t1) carried out after pure water rinsing.Under by Formula obtains rate of change when being set to t0, the thickness after immersion rinse is set to t1 by the thickness before dipping.
(t1―t0)/t0×100
It addition, metewand is as follows.1,2 and 3 is practical no problem level.
1: rate of change is 0% less than 5%
2: rate of change is 5% less than 8%
3: rate of change is 8% less than 10%
4: rate of change is more than 10%
5: rate of change is negative (cured film is dissolved)
[table 29]
[table 30]
From the above results, the sensitivity of the photosensitive polymer combination of the present invention shown in embodiment 1～48 is excellent, The cured film that solvent tolerance is excellent can be formed.Further, the photosensitive polymer combination of the present invention shown in embodiment 1～48 Storage stability and developability are excellent.And then, it is possible to form the cured film of excellent heat resistance.
On the other hand, and with containing the construction unit with the protected group of carboxylic acid do not contain and there is crosslinkable groups The polysiloxanes (A '-1) of construction unit and without there is the construction unit of the protected group of carboxylic acid and containing having epoxy radicals The solvent tolerance of comparative example 1,2 of polysiloxanes (A ' '-1) of construction unit poor.
Further, use containing there is the construction unit of the group that silanol group is protected by acetal and there is the structure of epoxy radicals The solvent tolerance of the comparative example 3 of the polysiloxanes (A '-3) of unit is poor.And then, storage stability is poor.
Further, use the B '-1 as the compound producing the pKa acid more than 3 as the comparative example 4 of light acid producing agent Sensitivity is poor.
The making ＞ of ＜ organic EL display
(embodiment 101)
Following methods is utilized to make the organic EL display (with reference to Fig. 3) using thin film transistor (TFT) (TFT).
Glass substrate 6 is formed the TFT1 of bottom gate type, and is formed by Si to cover the state of this TFT13N4Constitute Dielectric film 3.Then, after this dielectric film 3 is formed at this contact hole omitting diagram, via this contact hole, in insulation The distribution 2 (highly 1.0 μm) being connected to TFT1 is formed on film 3.This distribution 2 is for connecting between TFT1 or being connected to thereafter Organic EL element formed in operation and the parts of TFT1.
And then, in order to make the concavo-convex planarization caused by being formed of distribution 2, with landfill by distribution 2 cause concavo-convex State forms planarization film 4 on the insulating film 3.When forming planarization film 4 on the insulating film 3, by the photonasty tree of embodiment 1 Oil/fat composition slot coated is on substrate, and after carrying out prebake conditions (90 DEG C × 2 minutes) on hot plate, uses high-pressure mercury Lamp, after irradiating i ray (365nm) with the optimum exposure obtained sensitivity evaluation, utilizes aqueous alkali molten above mask Liquid carries out developing and forming pattern, and carries out the heat treated of 60 minutes at 230 DEG C.
Coating during photosensitive resin coating compositions is good, expose, develop, burn till after obtained cured film On do not find the generation of wrinkle or crackle.It addition, the mean step difference of distribution 2 is 500nm, the film of made planarization film 4 Thickness is 2,000nm.
Then, obtained planarization film 4 is formed the organic EL element of bottom emission type.First, will be made up of ITO The first electrode 5 be connected to distribution 2 to be formed on planarization film 4 via contact hole 7.Thereafter, it is coated with commercially available resist also Carry out prebake conditions, and be exposed via the mask of desired pattern, develop.Using this Resist patterns as mask, logical Cross and use the Wet-type etching of ITO etchant to carry out pattern processing.Thereafter, anticorrosive additive stripping liquid controlling (Remover 100, AZ is used Electronic MaterialsCo., Ltd. system), at 50 DEG C, peel off described Resist patterns.So obtained first electrode 5 anodes being equivalent to organic EL element.
Then, the dielectric film 8 of the shape covering the first electrode 5 periphery is formed.Dielectric film 8 uses the photosensitive of embodiment 1 Property resin combination, utilizes method same as described above to form dielectric film 8.By arranging this dielectric film 8, it is possible to prevent first The short circuit between the second electrode formed in electrode 5 and operation behind.
It addition, in vacuum deposition apparatus, it is deposited with successively via desired pattern mask and hole transmission layer, organic is set Luminescent layer, electron transfer layer.Then, the second electrode being made up of Al in whole formation of surface.Take out from evaporator Obtained aforesaid substrate, uses ultraviolet hardening epoxy resin to seal with the laminating of glass for sealing plate.
More than by, obtain the active matrix being connected in each organic EL element the TFT1 that it is driven The organic EL display of type.Execute alive result via drive circuit, demonstrate good display characteristic, it is known that be reliable The organic EL display that property is higher.
(embodiment 102～148)
In embodiment 101 into, the photosensitive polymer combination of embodiment 1 is changed the photoresist of embodiment 2～48 Compositions, in addition, makes organic EL display in the same manner as embodiment 101.To obtained organic EL display Apply the result of driving voltage, demonstrate good display characteristic, it is known that be the organic EL display that reliability is higher.
The making ＞ of ＜ liquid crystal indicator
(embodiment 201)
In active array type LCD described in Fig. 1 of No. 3321003 publications of Japanese Patent No., pass through Cured film 17 formed below, as interlayer dielectric, obtains the liquid crystal indicator of embodiment 201.That is, the sense of embodiment 1 is used Photosensitive resin composition, utilizes identical with the forming method of the planarization film 4 of the organic EL display in above-described embodiment 101 Method form cured film 17 as interlayer dielectric.
Obtained liquid crystal indicator is applied the result of driving voltage, demonstrates good display characteristic, it is known that be The liquid crystal indicator that reliability is higher.
(embodiment 202～248)
In embodiment 201 into, the photosensitive polymer combination of embodiment 1 is changed the photoresist of embodiment 2～48 Compositions, in addition, makes liquid crystal indicator in the same manner as embodiment 201.Obtained liquid crystal indicator is applied The result of driving voltage, demonstrates good display characteristic, it is known that be the liquid crystal indicator that reliability is higher.
(embodiment 251)
In liquid crystal indicator described in Fig. 1 of Japanese Unexamined Patent Publication 2007-328210 publication, utilize following methods Form organic insulating film PAS and obtain liquid crystal indicator.
First, according to Japanese Unexamined Patent Publication 2007-328210 publication, the battle array formed to tightly front for organic insulating film PAS is produced Row substrate.
Then, under hexamethyldisiloxane steam, this substrate is exposed 30 seconds, thereafter, the sense of slot coated embodiment 1 After photosensitive resin composition, at 90 DEG C in heating plate prebake conditions 2 minutes and make solvent volatilize, thus form photonasty tree Oil/fat composition layer.Then, use Canon Co., Ltd. MPA7800CF, use high voltage mercury lamp, from the sectional hole patterns of diameter 7 μm Mask above obtained photosensitive polymer combination layer irradiated i with the optimum exposure obtained in sensitivity evaluation penetrate Line (365nm).Further, alkaline developer (tetramethylammonium hydroxide aqueous solution of 0.5%) is utilized, with development exposure in 23 DEG C/60 seconds After photosensitive polymer combination layer after, utilize ultrapure water 20 seconds.Then, use ultrahigh pressure mercury lamp, irradiate with integrating Amount becomes 300mJ/cm2(energy intensity: 20mW/cm2, by i radionetric survey) in the way of whole exposure, thereafter, utilize baking oven, At 300 DEG C, this substrate is heated 30 minutes and obtain organic insulating film PAS.
Later operation carries out according to Japanese Unexamined Patent Publication 2007-328210 publication and obtains liquid crystal indicator.
In the present embodiment, owing to using the higher material of thermostability in PAS, therefore by interlayer dielectric IN3 with layer Between dielectric film IN2 equal at a temperature of be filmed.Thereby, it is possible to IN3 to be made the film of densification.
Obtained liquid crystal indicator is applied the result of driving voltage, demonstrates the best display characteristic, can Know it is the higher liquid crystal indicator of reliability.
(embodiment 252～298)
In embodiment 251 into, the photosensitive polymer combination of embodiment 1 is changed the photoresist of embodiment 2～48 Compositions, in addition, makes liquid crystal indicator in the same manner as embodiment 251.
Obtained liquid crystal indicator is applied the result of driving voltage, demonstrates the best display characteristic, can Know it is the liquid crystal indicator that reliability is higher.
The making ＞ of ＜ touch panel display device
(embodiment 301)
Touch panel display device is made by methods as described below.
The formation ＞ of ＜ the first transparent electrode pattern
The formation ＞ ＞ of ＜ ＜ transparent electrode layer
The front panel being pre-formed with the intensive treatment glass (300mm × 400mm × 0.7mm) of mask layer is imported to very In plenum chamber, use SnO2Containing ratio is the ITO target (indium: stannum=95:5 (mol ratio)) of 10 mass %, by DC magnetron sputtering (condition: the temperature of base material 250 DEG C, argon pressure 0.13Pa, oxygen pressure 0.01Pa) forms the ito thin film of thickness 40nm, thus obtains shape Become to have the front panel of transparent electrode layer.The sheet resistance of ito thin film is 80 Ω/.
Then, commercially available etching resist is coated on ITO and be dried and form etching resist layer.Will exposure Distance between mask (having the quartzy exposed mask of transparent electrode pattern) face and etching resist layer is set as 100 μm, with Light exposure 50mJ/cm2After (i ray) carries out pattern exposure, utilize developer solution to develop, and then carry out 130 DEG C, 30 minutes Rear baking process, thus obtain being formed with transparent electrode layer and the front panel of etching light photoresist layer pattern.
Will be formed with the front panel of transparent electrode layer and etching light photoresist layer pattern to impregnated in and add ITO erosion Carve agent (hydrochloric acid, potassium chloride solution.Liquid temperature 30 DEG C) etching groove in, process within 100 seconds, dissolve removal be not etched resist The transparent electrode layer of the exposed area that layer covers, thus obtain the transparency electrode layer pattern with band etching resist layer pattern Front panel.
Then, the front panel of transparency electrode layer pattern with band etching resist layer pattern be impregnated in special against corrosion Agent stripper removes etching light photo-sensitive resin, thus obtains being formed with mask layer and the first transparent electrode pattern Front panel.
The formation ＞ ＞ of ＜ ＜ insulating barrier
The photosensitive resin composition of coating Examples 1 on the front panel being formed with mask layer and the first transparent electrode pattern Thing is also dried (thickness 1 μm, 90 DEG C, 120 seconds) and obtains photosensitive polymer combination layer.Exposed mask (had insulation The quartzy exposed mask of layer pattern) distance between face and photosensitive polymer combination layer is set as 30 μm, with in sensitivity The optimum exposure obtained in evaluation carries out pattern exposure.
Then, utilize the tetramethylammonium hydroxide aqueous solution of 2.38 mass %, at 23 DEG C, pass through puddle Faxian shadow 15 seconds, And then utilize ultrapure water 10 seconds.Then, carry out 220 DEG C, the rear baking of 45 minutes process obtain being formed mask layer, the One transparent electrode pattern, the front panel of insulating layer pattern.
The formation ＞ of ＜ the second transparent electrode pattern
The formation ＞ ＞ of ＜ ＜ transparent electrode layer
In the way of identical with the formation of above-mentioned first transparent electrode pattern, the front panel formed to insulating layer pattern is entered Row DC magnetron sputtering processes (condition: the temperature 50 C of base material, argon pressure 0.13Pa, oxygen pressure 0.01Pa) and forms thickness 80nm's Ito thin film, thus obtain being formed with the front panel of transparent electrode layer.The sheet resistance of ito thin film is 110 Ω/.
In the way of identical with the formation of the first transparent electrode pattern, use commercially available etching resist, be formed Insulating layer pattern, transparent electrode layer and the erosion that first transparent electrode pattern, the photosensitive polymer combination of use embodiment 1 are formed Carve front panel (the rear baking process of Resist patterns；130 DEG C, 30 minutes).
And then, it is etched removing etching resist layer in the way of identical with the formation of the first transparent electrode pattern, Thus obtain being formed with the insulation of the photosensitive polymer combination formation of mask layer, the first transparent electrode pattern, use embodiment 1 Layer pattern and the front panel of the second transparent electrode pattern.
The formation ＞ of electric conductivity important documents different from first and second transparent electrode pattern for ＜
In the way of identical with the formation of first and second transparent electrode pattern above-mentioned, to being formed with the first transparency electrode figure The front panel of case, the insulating layer pattern that the photosensitive polymer combination of use embodiment 1 is formed and the second transparent electrode pattern enters Row DC magnetron sputtering processes, thus obtains being formed with the front panel of aluminum (Al) thin film of thickness 200nm.
In the way of identical with the formation of first and second transparent electrode pattern above-mentioned, commercially available etching resist is used to obtain To being formed with the first transparent electrode pattern, the insulating layer pattern using the photosensitive polymer combination of embodiment 1 to be formed, second saturating (rear baking processes the front panel of prescribed electrode pattern and etching Resist patterns；130 DEG C, 30 minutes).
And then, in the way of identical with the formation of the first transparent electrode pattern, it be etched (30 DEG C, 50 seconds) remove erosion Carve resist layer (45 DEG C, 200 seconds), thus obtain being formed with mask layer, the first transparent electrode pattern, the sense of use embodiment 1 Insulating layer pattern that photosensitive resin composition is formed, the second transparent electrode pattern and different from first and second transparent electrode pattern The front panel of electric conductivity important document.
The formation ＞ of ＜ protective clear layer
In the way of identical with the formation of insulating barrier, formed to different from first and second transparent electrode pattern above-mentioned On the front panel of electric conductivity important document the photosensitive polymer combination of coating Examples 1 and be dried (thickness 1 μm, 90 DEG C, 120 Second), thus obtain photosensitive polymer combination film.And then, it is exposed, develops, post-exposure (1,000mJ/cm2), toast afterwards Processing and obtain being laminated with the front panel of insulating barrier (protective clear layer), this insulating barrier is with coverage mask layer, the first transparent electrical Pole pattern, the insulating layer pattern of photosensitive polymer combination formation of use embodiment 1, the second transparent electrode pattern and first And second the whole mode of the different electric conductivity important document of transparent electrode pattern use the photosensitive polymer combination of embodiment 1 to carry out shape Become.
The making ＞ of ＜ touch panel display device
Fit on the liquid crystal display cells that method described in utilizing Japanese Unexamined Patent Publication 2009-47936 publication manufactures Previously fabricated front panel, and utilize known method to produce to possess capacitive input device touching as constitutive requirements Touch display apparatus.
The evaluation ＞ of ＜ front panel and touch panel display device
In the first transparent electrode pattern, the second transparent electrode pattern and the electric conductivity important document respective conduction different from them Property aspect no problem, on the other hand, there is between the first transparent electrode pattern and the second transparent electrode pattern insulating properties, make Good display characteristic has been obtained for touch panel.And then, first and second transparent electrode pattern is difficult to be gone out by visuognosis, Arrive the touch panel display device that display characteristic is excellent.
(embodiment 302～348)
In embodiment 301 into, the photosensitive polymer combination of embodiment 1 is changed the photoresist group of embodiment 2～48 Compound, in addition, makes touch panel display device in the same manner as embodiment 301.Obtained touch panel display device Do not have in terms of the first transparent electrode pattern, the second transparent electrode pattern and the respective electric conductivity of electric conductivity important document different from them Problematic, on the other hand, between the first transparent electrode pattern and the second transparent electrode pattern, there is insulating properties, as touch surface Plate has obtained good display characteristic.And then, first and second transparent electrode pattern is not easy to be gone out by visuognosis, has obtained excellent Different display characteristic.
Symbol description
1-TFT (thin film transistor (TFT)), 2-distribution, 3-dielectric film, 4-planarization film, 5-the first electrode, 6-glass substrate, 7- Contact hole, 8-dielectric film, 10-liquid crystal indicator, 12-back light unit, 14,15-glass substrate, 16-TFT, 17-cured film, 18-contact hole, 19-ITO transparency electrode, 20-liquid crystal, 22-color filter.

Claims (16)

1. a photosensitive polymer combination, it contains:
Polysiloxanes A, has construction unit a1 and construction unit a2, described construction unit a1 and has selected from carboxyl by acid decomposability Group and the phenolic hydroxyl group of radical protection are had by least one in the group of acid decomposability radical protection, described construction unit a2 Crosslinking property group；
Light acid producing agent B, producing pKa is the acid of less than 3；And
Solvent C.
Photosensitive polymer combination the most according to claim 1, wherein,
Described acid decomposability group is acetal radical.
Photosensitive polymer combination the most according to claim 1 and 2, wherein,
Described construction unit a1 is selected from the knot represented by the construction unit represented by following formula a1-1 and following formula a1-2 At least one in structure unit；
[chemical formula 1]
In formula a1-1, a1-2, a represents 0 or 1, R1And R2Separately represent hydrogen atom, alkyl or aryl, R1And R2In At least one represents alkyl or aryl, R3Represent alkyl or aryl, R1Or R2With R3Can connect and form cyclic ether, R4Represent alkane Base, aryl or aralkyl, L11Represent singly-bound or divalent linking group, L2Represent singly-bound or divalent linking group, RxRepresent alkyl or Halogen atom, m1 represents the integer of 0～4.
Photosensitive polymer combination the most according to any one of claim 1 to 3, wherein,
The crosslinkable groups that described construction unit a2 is had be selected from cyclic ether and there is ethylenic unsaturated bond group in At least one.
Photosensitive polymer combination the most according to any one of claim 1 to 4, wherein,
Described construction unit a2 is selected from the knot represented by the construction unit represented by following formula a2-1 and following formula a2-2 At least one in structure unit；
[chemical formula 2]
In formula a2-1, a2-2, a represents 0 or 1, R5Represent alkyl, aryl or aralkyl, RYRepresent alkyl or halogen atom, L3Table Showing singly-bound or divalent linking group, n represents 0 or 1, about m2, represent the integer of 0～2 when n is 0, represent 0～3 when n is 1 Integer, m3 represents the integer of 0～6.
Photosensitive polymer combination the most according to any one of claim 1 to 5, wherein,
Polysiloxanes A is possibly together with the construction unit a3 with acidic group.
Photosensitive polymer combination the most according to claim 6, wherein,
Described construction unit a3 contains at least one in carboxyl and phenolic hydroxyl group as acidic group.
8. according to the photosensitive polymer combination described in claim 6 or 7, wherein,
In polysiloxanes A total amount contained in photosensitive polymer combination, the molal quantity of construction unit a1 and construction unit a3 The total of molal quantity be 10:90～90:10 with the ratio of the molal quantity of construction unit a2.
Photosensitive polymer combination the most according to any one of claim 1 to 8, wherein,
Crosslinkable groups equivalent in the solid constituent of photosensitive polymer combination is less than 1500.
Photosensitive polymer combination the most according to any one of claim 1 to 9, wherein,
Described smooth acid producing agent B be in salt compound, oxime sulfonate compounds and acid imide sulfonate compound extremely Few one.
The manufacture method of 11. 1 kinds of cured film, it comprises:
Photosensitive polymer combination according to any one of claim 1 to 10 is coated the operation on substrate；
The operation of solvent is removed from the photosensitive polymer combination coated described substrate；
The operation that the photosensitive polymer combination removing solvent is exposed；
The operation that exposed photosensitive polymer combination is developed；And
Operation by developed photosensitive polymer combination heat cure.
12. 1 kinds of cured film, it obtains for being solidified by the photosensitive polymer combination according to any one of claim 1 to 10 Cured film or the cured film that formed for the manufacture method by the cured film described in claim 11.
13. cured film according to claim 12, it is interlayer dielectric.
14. 1 kinds of liquid crystal indicators, it has the cured film described in claim 12 or 13.
15. 1 kinds of organic EL displays, it has the cured film described in claim 12 or 13.
16. 1 kinds of touch panel display devices, it has the cured film described in claim 12 or 13.
CN201580008378.9A 2014-02-13 2015-01-30 Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device Pending CN105980931A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014-025343 2014-02-13
JP2014025343 2014-02-13
PCT/JP2015/052636 WO2015122293A1 (en) 2014-02-13 2015-01-30 Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device

Publications (1)

Publication Number Publication Date
CN105980931A true CN105980931A (en) 2016-09-28

Family

ID=53800041

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580008378.9A Pending CN105980931A (en) 2014-02-13 2015-01-30 Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device

Country Status (4)

Country Link
JP (1) JPWO2015122293A1 (en)
KR (1) KR20160102538A (en)
CN (1) CN105980931A (en)
WO (1) WO2015122293A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113166548A (en) * 2018-10-30 2021-07-23 中央硝子株式会社 Resin composition, photosensitive resin composition, cured film, method for producing cured film, patterned cured film, and method for producing patterned cured film
CN113318945A (en) * 2021-07-01 2021-08-31 漳州建晟家具有限公司 Children's furniture panel surface UV colored paint photocuring equipment

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6826361B2 (en) * 2015-05-13 2021-02-03 東京応化工業株式会社 Photosensitive composition for forming an insulating film and a method for forming an insulating film pattern
CN108055851B (en) * 2015-09-09 2021-03-30 日产化学工业株式会社 Coating agent for planarizing pattern reverse containing silicon
JP6607109B2 (en) * 2016-03-22 2019-11-20 Ｊｓｒ株式会社 Cured film, display element, cured film forming material, and cured film forming method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10324748A (en) * 1997-01-31 1998-12-08 Shin Etsu Chem Co Ltd Macromolecular silicone, chemically amplifiable positive type resist material and pattern-formation process
JP2001100417A (en) * 1999-09-28 2001-04-13 Fuji Photo Film Co Ltd Positive type photoresist composition
JP2001147538A (en) * 1999-11-22 2001-05-29 Fuji Photo Film Co Ltd Positive type resist laminated body
JP2002006494A (en) * 2000-06-22 2002-01-09 Fuji Photo Film Co Ltd Positive resist laminate
TW546542B (en) * 1997-08-06 2003-08-11 Shinetsu Chemical Co High molecular weight silicone compounds, resist compositions, and patterning method

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3533951B2 (en) * 1997-08-06 2004-06-07 信越化学工業株式会社 Polymeric silicone compound, resist material and pattern forming method
JP4235344B2 (en) * 2000-05-22 2009-03-11 富士フイルム株式会社 Positive silicon-containing resist composition for two-layer resist and pattern forming method
JP4373082B2 (en) 2001-12-28 2009-11-25 富士通株式会社 Alkali-soluble siloxane polymer, positive resist composition, resist pattern and method for producing the same, and electronic circuit device and method for producing the same
JP4262516B2 (en) * 2003-05-12 2009-05-13 富士フイルム株式会社 Positive resist composition
JP5136777B2 (en) 2008-04-25 2013-02-06 信越化学工業株式会社 Polyorganosiloxane compound, resin composition containing the same, and pattern forming method thereof
JP2013092633A (en) 2011-10-25 2013-05-16 Adeka Corp Positive photosensitive composition
JP6064570B2 (en) * 2012-12-10 2017-01-25 Jsr株式会社 Radiation sensitive resin composition for display element, cured film, method for producing cured film, semiconductor element and display element

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10324748A (en) * 1997-01-31 1998-12-08 Shin Etsu Chem Co Ltd Macromolecular silicone, chemically amplifiable positive type resist material and pattern-formation process
TW546542B (en) * 1997-08-06 2003-08-11 Shinetsu Chemical Co High molecular weight silicone compounds, resist compositions, and patterning method
JP2001100417A (en) * 1999-09-28 2001-04-13 Fuji Photo Film Co Ltd Positive type photoresist composition
JP2001147538A (en) * 1999-11-22 2001-05-29 Fuji Photo Film Co Ltd Positive type resist laminated body
JP2002006494A (en) * 2000-06-22 2002-01-09 Fuji Photo Film Co Ltd Positive resist laminate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113166548A (en) * 2018-10-30 2021-07-23 中央硝子株式会社 Resin composition, photosensitive resin composition, cured film, method for producing cured film, patterned cured film, and method for producing patterned cured film
CN113318945A (en) * 2021-07-01 2021-08-31 漳州建晟家具有限公司 Children's furniture panel surface UV colored paint photocuring equipment

Also Published As

Publication number Publication date
KR20160102538A (en) 2016-08-30
JPWO2015122293A1 (en) 2017-03-30
WO2015122293A1 (en) 2015-08-20

Similar Documents

Publication Publication Date Title
CN105683838B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN105814488B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN105531627B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN105579908B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN106716252A (en) Photosensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device, organic electroluminescence display device, and touch panel
CN104685416B (en) Photosensitive polymer combination, using its cured film preparation method, cured film, liquid crystal display device and organic EL display device
CN104541202B (en) Resin combination, cured film, object and its preparation method and display device with pattern
CN105980931A (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device
CN104981736A (en) Photosensitive resin composition for inkjet application, heat-treated substance, manufacturing method therefor, resin-pattern manufacturing method, liquid-crystal display, organic electroluminescent display, touch panel, manufacturing method therefor, and touch-panel display
CN105190437A (en) Photosensitive resin composition, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device
CN104662476B (en) Photosensitive polymer combination, the manufacturing method of pattern, the manufacturing method of cured film, organic EL display device and liquid crystal display device
CN104395826B (en) Photosensitive polymer combination, cured film and its manufacturing method, organic EL display device, liquid crystal display device and composition
CN105467748A (en) Manufacturing method for metal pattern substrate, touch sensor, touch screen, liquid display device, and organic EL display device
KR20160085303A (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device
CN105911818A (en) Photoresist composition, hardening film making method, hardening film and application thereof
CN104977813A (en) Pattern forming method, hardening substances, manufacturing method of touch screen or display screen, and display device
CN105324718A (en) Photosensitive resin composition, cured-film manufacturing method, cured film, liquid-crystal display, and organic el display
CN105911819A (en) Photoresist composition, hardening film making method, hardening film and application thereof
CN104756010B (en) Photosensitive polymer combination, hardening thing and its manufacturing method, resin pattern manufacturing method, cured film and its application
WO2016052389A1 (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescent display device, and touch panel
CN105917274B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN106200263A (en) Photosensitive polymer combination, cured film and its manufacture method, liquid crystal indicator, organic electroluminescence display device and method of manufacturing same and touch screen
WO2016052390A1 (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescent display device, and touch panel
CN104662474B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, organic EL display device and liquid crystal display device
CN105051608A (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160928