CN104685416B - Photosensitive polymer combination, using its cured film preparation method, cured film, liquid crystal display device and organic EL display device - Google Patents

Photosensitive polymer combination, using its cured film preparation method, cured film, liquid crystal display device and organic EL display device Download PDF

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Publication number
CN104685416B
CN104685416B CN201380049705.6A CN201380049705A CN104685416B CN 104685416 B CN104685416 B CN 104685416B CN 201380049705 A CN201380049705 A CN 201380049705A CN 104685416 B CN104685416 B CN 104685416B
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group
structural unit
photosensitive polymer
compound
acid
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CN104685416A (en
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霜山达也
疋田政宪
佐竹亮
柏木大助
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/039—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
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements
    • 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
    • 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
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The present invention provide a kind of photosensitive polymer combination, using its cured film preparation method, cured film, liquid crystal display device and organic EL display device.The photosensitive polymer combination contains: (A) includes the component of polymer for meeting polymer of at least one in following (1) and (2): (1) including the polymer of the structural unit of structural unit and (a2) with bridging property base for the group that (a1) there is acidic group to be protected by sour decomposability base；(2) include the group that (a1) there is acidic group to be protected by sour decomposability base structural unit polymer and the structural unit including (a2) with bridging property base polymer；(B) photoacid generator；(C) molecular weight is 1000 or less, includes the aromatic heterocyclic compounds of at least two coordination atom in aromatic rings comprising at least one nitrogen-atoms and in aromatic rings；And (D) solvent.Photosensitive polymer combination of the invention not only maintains high sensitivity and good chemical resistance.

Description

Photosensitive polymer combination, using its cured film preparation method, cured film, liquid crystal Showing device and organic EL display device
Technical field
The present invention relates to a kind of positive type photosensitive organic compound, the forming method of cured film, cured film, liquid crystal display dresses It sets and organic electroluminescent (electroluminescence, EL) display device.More specifically, it is related to one kind to be suitable for Form the planarization of the electronic components such as liquid crystal display device, organic EL display device, integrated circuit component, solid photographic element The forming method of film, the positive type photosensitive organic compound of protective film or interlayer dielectric and the cured film using it.
Background technique
Thin film transistor (TFT) (Thin Film Transistor, hereinafter referred to as " TFT ") type liquid crystal display element or magnetic head member In the electronic components such as part, integrated circuit component, solid photographic element, insulated between the wiring of stratiform generally for making to be configured to and It is provided with interlayer dielectric.The material for forming interlayer dielectric is preferably used for the number of steps of pattern form necessary to obtaining It is few, and with sufficient flatness, therefore photosensitive polymer combination is widely used.Such photosensitive polymer combination example Patent document 1 can such as be enumerated.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2011-209681 bulletin
Summary of the invention
Subject to be solved by the invention
When the manufacture of the electronic components such as above-mentioned display device, multi-chemical liquid is used, it is necessary to have to these chemicals The patience of liquid.Furthermore, it desired to the high panel reliability under the conditions of high-temperature, high humility, high pressure, as display in recent years fills The High precision set, it is required that being gradually increased.
In addition, in the photosensitive polymer combination used to form the interlayer dielectric in electronic component, sometimes Aromatic heterocyclic compounds are added as sensitizer or light-initiated auxiliary agent.But the result that present inventor is studied can To know, the chemical-resistant after the film hardening of these photosensitive polymer combinations is low, if using these photosensitive polymer combinations, There is a situation where to be easy to produce Display panel unevenness in panel reliability test.
It is an object of the present invention to solve the above subject, purpose is to provide a kind of photosensitive polymer combination, and sensitivity is high, firmly Change the good chemical resistance of film, and inhibits the generation of Display panel unevenness in panel reliability test.In turn, purpose is to mention For forming method, cured film, organic EL display device and the liquid of a kind of cured film using such photosensitive polymer combination Crystal device.
Technical means to solve problem
Based on the above situation, present inventor is actively studied, research as a result, it has been found that, by using have regulation Molecular weight, in aromatic rings comprising at least one nitrogen-atoms and in aromatic rings include at least two coordination atom aromatic series Heterocyclic compound not only maintains high sensitivity, but also good chemical resistance.The mechanism is not known simultaneously, it is believed that low molecular weight Aromatic heterocyclic compounds are easily transferred to substrate-side, the coordination atom in aromatic heterocyclic compounds and basal substrate phase interaction With, and inhibit the decomposition product intrusion from the photosensitive polymer combination generated under the conditions of high-temperature, high humility, high pressure In basal substrate, panel reliability is helped to improve.In addition it estimates, aromatic heterocyclic compounds promote the crosslinking of cured film, have Help improve chemical-resistant.
Means to solve the above problems are the means of following<1>, the means of preferably following<2>to<16>.
<1>a kind of photosensitive polymer combination, it includes:
(A) include the component of polymer for meeting the polymer of at least one in following (1) and (2):
(1) structural unit and (a2) for including the residue that (a1) there is acidic group protect by sour decomposability base are with being crosslinked The polymer of the structural unit of property base,
(2) include the residue that (a1) there is acidic group to be protected by sour decomposability base structural unit polymer and including (a2) polymer of the structural unit with bridging property base；
(B) photoacid generator；
(C) aromatic heterocyclic compounds；And
(D) solvent；And
The molecular weight of above-mentioned (C) aromatic heterocyclic compounds is 1000 hereinafter, and above-mentioned (C) aromatic heterocyclic compounds Include at least one nitrogen-atoms in aromatic rings, and includes at least two coordination atom in aromatic rings.
<2>photosensitive polymer combination according to<1>, wherein the aromatic heterocyclic compounds of above-mentioned (C) are 5 yuan Cyclic aromatic heterocycle compound, includes 5 yuan of cyclic aromatic heterocycle structures and 6 member rings fragrance at 6 member ring aromatic heterocyclic compounds Either one or two of polycycle aromatic heterocyclic compounds of at least one in race's heterocycle structure.
<3>photosensitive polymer combination according to<1>or<2>, wherein above-mentioned coordination atom is nitrogen-atoms, sulphur original Either one or two of son, oxygen atom.
<4>photosensitive polymer combination according to any one of<1>to<3>, wherein in the polymer of above-mentioned (A), (a2) bridging property base contained in the structural unit with bridging property base is selected from epoxy group, oxetanylmethoxy and-NH- CH2It is at least one kind of in group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1~20).
<5>photosensitive polymer combination according to any one of<1>to<4>, wherein above-mentioned acid decomposability base is tool There is the group for the structure being protected in the form of acetal.
<6>photosensitive polymer combination according to any one of<1>to<5>, wherein the component of polymer of above-mentioned (A) Either one or two of for so that the polymer containing acidic group.
<7>photosensitive polymer combination according to any one of<1>to<6>, wherein the photoacid generator of above-mentioned (B) For oxime sulfonate compounds.
<8>photosensitive polymer combination according to any one of<1>to<7>, wherein the heteroaromatic of above-mentioned (C) Compound includes 2~3 coordination atoms in aromatic rings.
<9>photosensitive polymer combination according to any one of<1>to<8>, wherein the heteroaromatic of above-mentioned (C) Compound includes at least two nitrogen-atoms in aromatic rings.
<10>photosensitive polymer combination according to any one of<1>to<9>, wherein above-mentioned (C) heteroaromatic Ring possessed by compound is the condensed ring of monocycle, and/or 2 or 3 rings.
<11>photosensitive polymer combination according to any one of<1>to<10>, without amino as above-mentioned (C) Substituent group possessed by aromatic rings in aromatic heterocyclic compounds.
<12>a kind of forming method of cured film comprising:
(1) photosensitive polymer combination according to any one of<1>to<11>is coated on the step of the coating on substrate Suddenly；
(2) solvent removal step of solvent is removed from the photosensitive polymer combination being coated with；
(3) step of exposure that the photosensitive polymer combination for eliminating solvent is exposed using actinic ray；
(4) development step developed using aqueous developer to exposed photosensitive polymer combination；And
(5) the rear baking procedure of thermmohardening is carried out to developed photosensitive polymer combination.
<13>forming method of the cured film according to<12>, wherein after above-mentioned development step, above-mentioned rear baking step Include the steps that carrying out blanket exposure to developed photosensitive polymer combination before rapid.
<14>a kind of cured film is formed using the method according to<12>or<13>.
<15>cured film according to<14>, is interlayer dielectric.
<16>a kind of organic EL display device or liquid crystal display device comprising according to hardening described in<14>or<15> Film.
The effect of invention
According to the present invention, it is possible to provide a kind of photoresist group for not only maintaining high sensitivity but also good chemical resistance Close object, the manufacturing method of pattern, organic EL display device, the manufacturing method of liquid crystal display device and cured film.
Detailed description of the invention
Fig. 1 shows the composition concept maps of an example of liquid crystal display device.Indicate the active matrix base in liquid crystal display device The schematic cross sectional view of plate, including the cured film 17 as interlayer dielectric.
Fig. 2 indicates the composition concept map of an example of organic EL display device.Indicate that organic EL of bottom emission type shows dress The schematic cross sectional view of substrate in setting, including planarization film 4.
The explanation of symbol
1,16:TFT
2: wiring
3,8: insulating film
4: planarization film
5: first electrode
6: glass substrate
7,18: contact hole
10: liquid crystal display device
12: back light unit
14,15: glass substrate
17: cured film
19:ITO transparent electrode
20: liquid crystal
22: colored filter
Specific embodiment
Hereinafter, the contents of the present invention are described in detail.The explanation for the constitutive requirements recorded below is sometimes based upon this hair Bright representative embodiments carry out, but the present invention is not limited to such embodiment.In addition, institute in present specification Call "~", be using comprising its front and back documented by numerical value as lower limit value and upper limit value meaning come using.
In addition, not recording the statement for being substituted and being unsubstituted in the statement of the group (atomic group) in this specification It not only comprising without substituent group, but also include with substituent group.Such as so-called " alkyl ", not only taken comprising not having The alkyl (alkyl being unsubstituted) of Dai Ji, and include the alkyl (alkyl being substituted) with substituent group.
In turn, so-called (methyl) acrylic acid, refers to acrylic acid and/or methacrylic acid.
Photosensitive polymer combination (hereinafter sometimes referred to " composition of the invention ") of the invention includes:
(A) include the component of polymer for meeting the polymer of at least one in following (1) and (2):
(1) structural unit and (a2) for including the residue that (a1) there is acidic group protect by sour decomposability base are with being crosslinked The polymer of the structural unit of property base；
(2) include the residue that (a1) there is acidic group to be protected by sour decomposability base structural unit polymer and including (a2) polymer of the structural unit with bridging property base；
(B) photoacid generator；
(C) aromatic heterocyclic compounds；And
(D) solvent；And
The molecular weight of above-mentioned (C) aromatic heterocyclic compounds is 1000 hereinafter, former comprising at least one nitrogen in aromatic rings Son, and include at least two coordination atom in aromatic rings.In addition, photosensitive polymer combination of the invention is preferably that chemistry increases Width positive type photosensitive organic compound.
Hereinafter, composition of the invention is described in detail.
<(A) component of polymer>
Composition of the invention include following polymer at least one as component of polymer: (1) include (a1) have The structural unit and (a2) for the group that acidic group is protected by sour decomposability base have bridging property base structural unit polymer, with And (2) include the polymer of the structural unit for the group that (a1) there is acidic group to be protected by sour decomposability base and have including (a2) The polymer of the structural unit of bridging property base.In turn, it also may include other than these polymer polymer.As long as not saying especially It is bright, then (A) component of polymer (hereinafter sometimes referred to " (A) ingredient ") in the present invention refer in addition to comprising above-mentioned (1) and/or It (2) also include the other polymers optionally added other than.
<<structural unit (a1)>>
Ingredient A includes at least the structural unit for the group that (a1) there is acidic group to be protected by sour decomposability base.Pass through (A) ingredient Including structural unit (a1), the high photosensitive polymer combination of sensitivity can be made into.
" group that acidic group is protected by sour decomposability base " in the present invention can be used as acidic group and sour decomposability base and Well known group, is not particularly limited.Specific acidic group preferably enumerates carboxyl and phenolic hydroxyl group.In addition, sour decomposability base It can be used the group for being easier to decompose because of acid (for example, ester structure, the THP trtrahydropyranyl of group represented by aftermentioned formula (A1) The acetals such as ester group or tetrahydrofuran base ester group system functional group) or compare the group for being difficult to decompose because of acid (for example, the tert-butyl ester The three-levels alkylcarbonic acid such as the three-levels such as base alkyl, tert-butyl carbonate base ester group).
(a1) structural unit for the group protected with acidic group by sour decomposability base preferably has is protected by sour decomposability base The structural unit or structural unit with the protection phenolic hydroxyl group protected by sour decomposability base of the protection carboxyl of shield.
Hereinafter, successively to the structural unit (a1-1) with the protection carboxyl protected by sour decomposability base and having by acid The structural unit (a1-2) of the protection phenolic hydroxyl group of decomposability base protection is illustrated respectively.
<<<structural unit that (a1-1) has the protection carboxyl protected by sour decomposability base>>>
The above-mentioned structural unit (a1-1) with the protection carboxyl protected by sour decomposability base is the structure list with carboxyl The structural unit with protection carboxyl that the carboxyl of member is protected by sour decomposability base explained in detail below.
It is workable in the above-mentioned structural unit (a1-1) with the protection carboxyl protected by sour decomposability base above-mentioned to have There is no particular restriction for the structural unit of carboxyl, and well known structural unit can be used.Such as can enumerate: be originated from unsaturated monocarboxylic, Structural unit (the a1- of unsaturated carboxylic acid in the molecules such as unsaturated dicarboxylic, unsaturated tricarboxylic acids at least one carboxyl etc. 1-1)；Or there is the structural unit (a1-1-2) of ethylene unsaturated group and the structure from acid anhydrides simultaneously.
Hereinafter, successively to as the above-mentioned structural unit with carboxyl come using (a1-1-1) be originated from molecule in have extremely The structural unit and (a1-1-2) of the unsaturated carboxylic acid of few 1 carboxyl etc. have ethylene unsaturated group simultaneously and are originated from acid The structural unit of the structure of acid anhydride is illustrated respectively.
<<<<structural unit that (a1-1-1) is originated from unsaturated carboxylic acid in molecule at least one carboxyl etc.>>>>
Structural unit (a1-1-1) as the above-mentioned unsaturated carboxylic acid from molecule at least one carboxyl etc. can make With following cited unsaturated carboxylic acid used in the present invention.That is, unsaturated monocarboxylic can for example be enumerated: acrylic acid, Methacrylic acid, butenoic acid, α-chloroacrylic acid, cinnamic acid, 2- (methyl) acryloyl-oxyethyl-succinic acid, 2- (methyl) third Alkene trimethylammonium hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl-phthalic acid etc..In addition, unsaturation two Carboxylic acid can for example be enumerated: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc..In addition, for being had The unsaturated polybasic carboxylic acid of the structural unit of carboxyl can also be its acid anhydrides.It can specifically enumerate: maleic anhydride, itaconic acid Acid anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid can be list (2- methacryloxyalkyl) ester of polybasic carboxylic acid, example It can such as enumerate: succinic acid list (2- acryloyl-oxyethyl) ester, succinic acid list (2- methacryloxyethyl) ester, adjacent benzene two Formic acid list (2- acryloyl-oxyethyl) ester, phthalic acid list (2- methacryloxyethyl) ester etc..In turn, unsaturated Polybasic carboxylic acid can be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, such as can enumerate: ω-carboxy-polycaprolactone Mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc..In addition, unsaturated carboxylic acid also can be used: acrylic acid -2- Carboxyethyl, methacrylic acid -2- carboxyethyl, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4- carboxyl benzene Ethylene etc..
Wherein, above-mentioned from the unsaturation in molecule at least one carboxyl in order to be formed for the viewpoint of developability The structural unit (a1-1-1) of carboxylic acid etc., it is preferable to use acrylic acid, methacrylic acid, 2- (methyl) acryloyl-oxyethyl- Succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl-O-phthalic The acid anhydrides etc. of acid or unsaturated polybasic carboxylic acid, more preferably uses acrylic acid, methacrylic acid, 2- (methyl) acryloyl-oxy Base ethyl hexahydrophthalic acid.
The structural unit (a1-1-1) of the above-mentioned unsaturated carboxylic acid from molecule at least one carboxyl etc. can be wrapped individually It also may include two or more containing a kind.
<<<<structural unit that (a1-1-2) has ethylene unsaturated group and the structure from acid anhydrides simultaneously>>>>
Simultaneously there is ethylene unsaturated group and the structural unit (a1-1-2) of the structure from acid anhydrides to be preferably derived from makes Hydroxyl in the presence of structural unit with ethylene unsaturated group is reacted with acid anhydrides and the unit of monomer that obtains.
Well known acid anhydrides can be used in above-mentioned acid anhydrides, can specifically enumerate: maleic anhydride, succinic anhydride, itaconic acid Acid anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride (chlorendic The dibasic acid anhydrides such as anhydride)；Trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride Equal acid anhydrides.In these acid anhydrides, for the viewpoint of developability, preferably phthalic anhydride, tetrabydrophthalic anhydride or Succinic anhydride.
For the viewpoint of developability, above-mentioned acid anhydrides is preferably 10 moles of %~100 mole % to the reactivity of hydroxyl, more Preferably 30 moles of %~100 mole %.
<<<<workable acid decomposability base in structural unit (a1-1)>>>>
Workable above-mentioned acid point in the above-mentioned structural unit (a1-1) with the protection carboxyl protected by sour decomposability base Above-mentioned sour decomposability base can be used in Xie Xingji.
With regard to the formative, photosensitive of the basic physical properties of photosensitive polymer combination, especially sensitivity or pattern form, contact hole Property resin combination storage stability viewpoint for, in these sour decomposability bases, preferably carboxyl is in the form of acetal The protection carboxyl protected.And then for the viewpoint of sensitivity, in sour decomposability base, more preferably carboxyl is by the following general formula (a1-10) the protection carboxyl that the form of the acetal represented by is protected.In addition, in carboxyl for by the following general formula (a1-10) institute table In the case where the protection carboxyl that the form of the acetal shown is protected, that protects carboxyl is integrally formed-(C=O)-O-CR101R102 (OR103) structure.
General formula (a1-10)
[changing 1]
(in formula (a1-10), R101And R102Respectively indicate hydrogen atom or alkyl, wherein R101With R102It is hydrogen atom Except situation.R103Indicate alkyl.R101Or R102With R103It can link and form cyclic ether.)
In above-mentioned general formula (a1-10), R101~R103Respectively indicate hydrogen atom or alkyl, abovementioned alkyl can for straight-chain, It is branch's chain state, cricoid any.Herein, R is not present101And R102Both expressions hydrogen atom the case where, R101And R102's At least one indicates alkyl.
In above-mentioned general formula (a1-10), in R101、R102And R103Indicate alkyl in the case where, abovementioned alkyl can for straight-chain, Branch's chain state is cricoid any.
The alkyl of above-mentioned straight-chain or branch's chain state is preferably carbon number 1~12, more preferably carbon number 1~6, and then preferred For carbon number 1~4.It can specifically enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the second butyl, tertiary fourth Base, n-pentyl, neopentyl, n-hexyl, 2,3- dimethyl -2- butyl (thexyl), n-heptyl, n-octyl, 2- ethylhexyl, just Nonyl, positive decyl etc..
Above-mentioned cyclic alkyl is preferably carbon number 3~12, more preferably carbon number 4~8, and then preferably carbon number 4~6.It is above-mentioned Cyclic alkyl can for example be enumerated: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, isoborneol Base etc..
Abovementioned alkyl can have substituent group, and substituent group can illustrate: halogen atom, aryl, alkoxy.With halogen atom In the case where substituent group, R101、R102、R103As halogenated alkyl, with aryl as substituent group, R101、 R102、R103As aralkyl.
Above-mentioned halogen atom can illustrate: fluorine atom, chlorine atom, bromine atom, iodine atom, be preferably fluorine in these halogen atoms Atom or chlorine atom.
In addition, above-mentioned aryl is preferably the aryl of carbon number 6~20, more preferably carbon number 6~12, specifically, can illustrate Phenyl, Alpha-Methyl phenyl, naphthalene etc., the alkyl replaced through aryl are integrally that aralkyl can illustrate benzyl, α-methylbenzyl, benzene second Base, naphthyl methyl etc..
Above-mentioned alkoxy is preferably the alkoxy of carbon number 1~6, more preferably carbon number 1~4, and then more preferably methoxyl group Or ethyoxyl.
In addition, abovementioned alkyl be naphthenic base in the case where, above-mentioned naphthenic base can have carbon number 1~10 straight-chain or The alkyl of branch's chain state can have carbon number 3 in the case where alkyl is the alkyl of straight-chain or branch's chain state as substituent group ~12 naphthenic base is as substituent group.
These substituent groups can be further substituted with through above-mentioned substituent group.
In above-mentioned general formula (a1-10), in R101、R102And R103In the case where indicating aryl, above-mentioned aryl is preferably carbon number 6 ~12, more preferably carbon number 6~10.Above-mentioned aryl can have substituent group, and above-mentioned substituent group can preferably illustrate carbon number 1~6 Alkyl.Aryl can for example illustrate: phenyl, tolyl, cumenyl, 1- naphthalene etc..
In addition, R101、R102And R103The carbon atom that can be mutually bonded and be bonded with them is formed together ring.R101With R102、 R101With R103Or R102With R103Ring structure in the case where bond can for example be enumerated: cyclobutyl, cyclopenta, cyclohexyl, suberyl, Tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc..
In addition, in above-mentioned general formula (a1-10), preferably R101And R102Either one or two of be hydrogen atom or methyl.
It is used to form the free-radical polymerised list with the structural unit for protecting carboxyl represented by above-mentioned general formula (a1-10) Body can be used commercially available, it is possible to use with known method synthesis.Such as using Japanese Patent Laid-Open 2011-221494 public affairs Synthetic method recorded in 0037~numbered paragraphs of numbered paragraphs 0040 of report etc. synthesizes.
Under first preferred configuration of the above-mentioned structural unit (a1-1) with the protection carboxyl protected by sour decomposability base is State structural unit represented by general formula (A2 ').
[changing 2]
General formula (A2 ')
(in formula, R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of be alkyl or virtue Base, R3Indicate alkyl or aryl, R1Or R2With R3It can link and form cyclic ether, R4Indicate that hydrogen atom or methyl, X indicate Singly-bound or arlydene.)
In R1And R2In the case where for alkyl, preferably carbon number be 1~10 alkyl.In R1And R2In the case where for aryl, Preferably phenyl.R1And R2It is respectively preferably the alkyl of hydrogen atom or carbon number 1~4.
R3Indicate alkyl or aryl, the preferably alkyl of carbon number 1~10, the more preferably alkyl of carbon number 1~6.
X indicates singly-bound or arlydene, preferably singly-bound.
Under second preferred configuration of the above-mentioned structural unit (al-1) with the protection carboxyl protected by sour decomposability base is State the structural unit of general formula.
[changing 3]
(in formula, R121Indicate the alkyl of hydrogen atom or carbon number 1~4, L1Indicate carbonyl or phenylene, R122~R128Point Not Biao Shi hydrogen atom or carbon number 1~4 alkyl.)
R121Preferably hydrogen atom or methyl.
L1Preferably carbonyl.
R122~R128Preferably hydrogen atom.
The preferred concrete example of the above-mentioned structural unit (a1-1) with the protection carboxyl protected by sour decomposability base can illustrate Following structural units.In addition, R indicates hydrogen atom or methyl.
[changing 4]
<<<structural unit that (a1-2) has the protection phenolic hydroxyl group protected by sour decomposability base>>>
The above-mentioned structural unit (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base is with phenolic hydroxyl group Structural unit by sour decomposability base explained in detail below protected have protection phenolic hydroxyl group structural unit.
<<<<structural unit that (a1-2-1) has phenolic hydroxyl group>>>>
The above-mentioned structural unit with phenolic hydroxyl group can enumerate hydroxy styrenes architecture unit or novolaks system resin In structural unit, in these structural units, for the viewpoint of sensitivity, be preferably derived from hydroxy styrenes or Alpha-Methyl The structural unit of hydroxy styrenes.In addition, the structural unit with phenolic hydroxyl group is preferably also following for the viewpoint of sensitivity Structural unit represented by general formula (a1-20).
General formula (a1-20)
[changing 5]
(in general formula (a1-20), R220Indicate hydrogen atom or methyl, R221Indicate singly-bound or bivalence linking base, R222Table Show the straight chain of halogen atom or carbon number 1~5 or the alkyl of branch's chain state, a indicates 1~5 integer, b indicate 0~4 it is whole Number, a+b are 5 or less.In addition, in R222There are in the case where 2 or more, these R222It can be mutually different also identical.)
In above-mentioned general formula (a1-20), R220Indicate hydrogen atom or methyl, preferably methyl.
In addition, R221Indicate singly-bound or bivalence linking base.In the case where singly-bound, sensitivity can be improved, and then can be improved hard Change the transparency of film, therefore preferably.R221Bivalence linking base can illustrate alkylidene, R221It can be enumerated for the concrete example of alkylidene: Methylene, ethylidene, propylidene, isopropylidene, sub- normal-butyl, isobutylidene, sub- tert-butyl, pentylidene, isoamylidene, Asia are new Amyl, hexylidene etc..Wherein, R221Preferably singly-bound, methylene, ethylidene.In addition, above-mentioned bivalence linking base can have substitution Base, substituent group can enumerate halogen atom, hydroxyl, alkoxy etc..In addition, a indicates 1~5 integer, but with regard to effect of the invention For in terms of viewpoint or manufacture readily, preferably a is 1 or 2, and more preferably a is 1.
In addition, when with R221On the basis of the carbon atom of bond when (1), the binding site of the hydroxyl in phenyl ring is preferably It is bonded to 4.
R222For the alkyl of the straight chain or branch's chain state of halogen atom or carbon number 1~5.Can specifically enumerate: fluorine is former Son, chlorine atom, bromine atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, isopentyl, new penta Base etc..Wherein for manufacturing readily aspect, preferably chlorine atom, bromine atom, methyl or ethyl.
In addition, b indicates 0 or 1~4 integer.
<<<<workable acid decomposability base in structural unit (a1-2)>>>>
It is workable above-mentioned in the above-mentioned structural unit (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base Sour decomposability base can with it is above-mentioned have by sour decomposability base protect protection carboxyl structural unit (a1-1) in workable on It states sour decomposability base and is used in the same manner well known, be not particularly limited.With regard to the basic physical properties of photosensitive polymer combination, especially For the viewpoint of sensitivity or the formative of pattern form, the storage stability of photosensitive polymer combination, contact hole, sour decomposability Structural unit in base preferably with the protection phenolic hydroxyl group protected by acetal.In turn, for the viewpoint of sensitivity, acid is decomposed Property base in more preferably phenolic hydroxyl group acetal represented by above-mentioned general formula (a1-10) form come the protection phenol hydroxyl protected Base.In addition, the protection phenolic hydroxyl group being protected in the form of being the acetal represented by above-mentioned general formula (a1-10) in phenolic hydroxyl group In the case where, that protects phenolic hydroxyl group is integrally formed-Ar-O-CR101R102(OR103) structure.In addition, Ar indicates arlydene.
The preference of the acetal ester structure of phenolic hydroxyl group can illustrate: R101=R102=R103=methyl or R101=R102=first Base and R103The combination of=benzyl.
In addition, be used to form the structural unit for the protection phenolic hydroxyl group protected with phenolic hydroxyl group by the form of acetal Free radical polymerization monomer can for example be enumerated: record in the numbered paragraphs 0042 of Japanese Patent Laid-Open 2011-215590 bulletin Monomer etc..
In these monomers, for the viewpoint of the transparency, the preferably 1- alkoxy alkane of methacrylic acid 4- hydroxylphenyl ester The THP trtrahydropyranyl protective of base protective, methacrylic acid 4- hydroxylphenyl ester.
The concrete example of the acetal protecting group of phenolic hydroxyl group can enumerate 1- alkoxyalkyl, such as can enumerate: 1- ethyoxyl second Base, 1- methoxy ethyl, 1- n-butoxyethyl, 1- isobutoxyethy, 1- (2- chloroethoxy) ethyl, 1- (2- ethyl hexyl Oxygroup) ethyl, 1- positive propoxy ethyl, 1- cyclohexyloxy ethyl, 1- (2- cyclohexylethoxy radical) ethyl, 1- Benzyloxyethyl Deng these groups can be used alone or two or more is applied in combination.
It is used to form the freedom of the structural unit (a1-2) of the above-mentioned protection phenolic hydroxyl group for having and being protected by sour decomposability base Base polymerizable monomer can be used commercially available, it is possible to use synthesize in a known manner.For example, can be by making with phenolic hydroxyl group Compound reacted and synthesized with vinyl ethers in the presence of acid catalyst.Above-mentioned synthesis can make have phenolic hydroxyl group Monomer and the preparatory combined polymerization of other monomers, are then reacted with vinyl ethers in the presence of acid catalyst.
The preferred concrete example of the above-mentioned structural unit (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base can Following structural units are illustrated, but the present invention is not limited to these structural units.
[changing 6]
[changing 7]
[changing 8]
<<<preferred configuration of structural unit (a1)>>>
In the case where the polymer containing above structure unit (a1) is substantially free of structural unit (a2), contain the knot In the polymer of structure unit (a1), structural unit (a1) is preferably 20 moles of %~100 mole %, and more preferably 30 moles of %~ 90 moles of %.
In the case where the polymer containing above structure unit (a1) contains following structural units (a2), contain the structure In the polymer of unit (a1) and structural unit (a2), for the viewpoint of sensitivity, this composition unit (a1) is preferably 3 moles of % ~70 moles of %, more preferably 10 moles of %~60 mole %.In addition, on workable especially in above structure unit (a1) In the case where stating the structural unit that sour decomposability base is the protection carboxyl protected with carboxyl by the form of acetal, preferably 20 Mole %~50 mole %.
With it is above-mentioned with the structural unit (a1-2) for the protection phenolic hydroxyl group protected by sour decomposability base compared with, it is above-mentioned to have There is quick feature of developing by the structural unit (a1-1) of the protection carboxyl of sour decomposability base protection.Therefore, it is being intended to quickly show In the case where shadow, it is however preferred to have by the structural unit (a1-1) of the protection carboxyl of sour decomposability base protection.On the contrary, being intended to slow down In the case where development, it is preferable to use there is the structural unit (a1-2) for the protection phenolic hydroxyl group protected by sour decomposability base.
<<structural unit that (a2) has bridging property base>>
(A) ingredient includes the structural unit (a2) with bridging property base.As long as above-mentioned bridging property base passes through heat treatment And generate the group of sclerous reaction, then it is not particularly limited.The form of structural unit with preferred bridging property base can enumerate packet Containing selected from by epoxy group, oxetanylmethoxy ,-NH-CH2Group and ethylene represented by-O-R (alkyl that R is carbon number 1~20) At least one kind of structural unit in property the formed group of unsaturated group, be preferably selected from epoxy group, oxetanylmethoxy and- NH-CH2It is at least one kind of in group represented by-O-R (alkyl that R is carbon number 1~20).Wherein, photoresist of the invention Preferably above-mentioned (A) ingredient of composition includes comprising structural unit at least one kind of in epoxy group and oxetanylmethoxy.In more detail For, following structural unit can be enumerated.
<<<structural unit that (a2-1) has epoxy group and/or oxetanylmethoxy>>>
Above-mentioned (A) polymer preferably contains the structural unit (structural unit with epoxy group and/or oxetanylmethoxy (a2-1)).The cyclic ether group of above-mentioned 3 member ring is also referred to as epoxy group, and the cyclic ether group of 4 member rings is also referred to as oxetanylmethoxy.
The above-mentioned structural unit (a2-1) with epoxy group and/or oxetanylmethoxy in 1 structural unit as long as have At least one epoxy group or oxetanylmethoxy can also have 1 or more epoxy group and 1 or more oxa- ring fourth The oxetanylmethoxy of base, 2 or more epoxy groups or 2 or more, is not particularly limited, it is however preferred to have add up to 1~ 3 epoxy groups and/or oxetanylmethoxies more preferably have epoxy group and/or the oxetanylmethoxy for adding up to 1 or 2, And then preferably there is 1 epoxy group or oxetanylmethoxy.
The concrete example for being used to form the free radical polymerization monomer of the structural unit with epoxy group can for example be enumerated: propylene Acid glycidyl ester, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-propyl acrylic acid shrink sweet Grease, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid -3,4- epoxy group butyl ester, methacrylic acid -3,4- epoxy group fourth Ester, acrylic acid -3,4- epoxycyclohexanecarboxylate, methacrylic acid -3,4- epoxycyclohexanecarboxylate, α-ethylacrylate -3,4- Epoxycyclohexanecarboxylate, vinylbenzyl glycidyl ether, shrinks to vinyl benzyl at adjacent vinylbenzyl glycidyl ether Glycerin ether, No. 4168443 bulletins of Japanese Patent No. 0031~numbered paragraphs of numbered paragraphs 0035 in record contain ester ring type The compound etc. of epoxy skeleton, these contents are incorporated herein in specification.
The concrete example for being used to form the free radical polymerization monomer of the structural unit with oxetanylmethoxy can for example be enumerated: That records in 0011~numbered paragraphs of numbered paragraphs 0016 of Japanese Patent Laid-Open 2001-330953 bulletin has oxa- ring fourth (methyl) acrylate of base etc., these contents are incorporated herein in specification.
It is used to form the free-radical polymerised list of the above-mentioned structural unit (a2-1) with epoxy group and/or oxetanylmethoxy The concrete example of body is preferably the monomer containing metacrylic acid ester structure, the monomer containing acrylate structural.
In these monomers preferably are as follows: glycidyl methacrylate, acrylic acid 3,4- epoxycyclohexanecarboxylate, methyl-prop Olefin(e) acid 3,4- epoxycyclohexanecarboxylate, acrylic acid (3- Ethyloxetane -3- base) methyl esters and methacrylic acid (3- second Base oxetanes -3- base) methyl esters.These structural units, which can be used alone, or two or more to be applied in combination by a kind.
The preferred concrete example of the above-mentioned structural unit (a2-1) with epoxy group and/or oxetanylmethoxy can illustrate following knots Structure unit.In addition, R indicates hydrogen atom or methyl.
[changing 9]
<<<structural unit that (a2-2) has ethylene unsaturated group>>>
1 kind of the above-mentioned structural unit (a2) with bridging property base can enumerate the structural unit with ethylene unsaturated group (a2-2) (hereinafter also referred to " structural unit (a2-2) ").The above-mentioned structural unit (a2-2) with ethylene unsaturated group is preferred , with the structural unit of ethylene unsaturated group, with ethylene unsaturated group and more preferably to there is carbon in end on side chain The structural unit of the side chain of number 3~16, and then the structural unit preferably with side chain represented by the following general formula (a2-2-1).
General formula (a2-2-1)
[changing 10]
(in general formula (a2-2-1), R301Indicate the bivalence linking base of carbon number 1~13, R302Indicate hydrogen atom or methyl, * Indicate the position with the connection of the main chain of the structural unit (a2) with bridging property base.)
R301For the bivalence linking base of carbon number 1~13, comprising alkenyl, cycloalkenyl, arlydene or by these moiety combinations and The group obtained, also may include the keys such as ester bond, ehter bond, amido bond, urethane bond.In addition, bivalence linking base can be arbitrary Position has the substituent groups such as hydroxyl, carboxyl.R301Concrete example can enumerate following bivalence linking bases.
[changing 11]
It include above-mentioned R in side chain represented by above-mentioned general formula (a2-2-1)301Represented divalent concatenating group, preferably rouge The side chain of fat race.
In addition to this, (a2-2) there is the structural unit of ethylene unsaturated group can refer to Japanese Patent Laid-Open 2011- The record of 0072~numbered paragraphs of numbered paragraphs 0090 of No. 215580 bulletins, these contents are incorporated herein in specification.
< < < (a2-3) has-NH-CH2- structural unit of group represented by O-R (alkyl that R is carbon number 1~20) > > >
Polymer used in the present invention, which preferably also contains, has-NH-CH2- O-R the alkyl of carbon number 1~20 (R for) institute The structural unit (a2-3) of the group of expression.By containing structural unit (a2-3), can be caused by slowly heating hard Change reaction, can get the excellent cured film of various characteristics.Herein, R is preferably the alkyl of carbon number 1~9, more preferably carbon number 1~4 Alkyl.In addition, alkyl can be straight chain, branch perhaps any preferably straight chain of cricoid alkyl or the alkyl of branch. Structural unit (a2) is more preferably the structural unit with group represented by the following general formula (a2-30).
General formula (a2-30)
[changing 12]
(in general formula (a2-30), R1Indicate hydrogen atom or methyl, R2Indicate the alkyl of carbon number 1~20.)
R2The preferably alkyl of carbon number 1~9, and then the alkyl of preferably carbon number 1~4.In addition, alkyl can be straight chain, divide Prop up perhaps any preferably straight chain of cricoid alkyl or the alkyl of branch.
R2Concrete example can enumerate methyl, ethyl, normal-butyl, isobutyl group, cyclohexyl and n-hexyl.Wherein it is preferably Isobutyl group, normal-butyl, methyl.
<<<preferred configuration of structural unit (a2)>>>
In the case where the polymer containing above structure unit (a2) is substantially free of structural unit (a1), contain the knot In the polymer of structure unit (a2), structural unit (a2) is preferably 5 moles of %~90 mole %, more preferably 20 moles of %~80 Mole %.
In the case where the polymer containing above structure unit (a2) contains above structure unit (a1), contain the structure In the polymer of unit (a1) and structural unit (a2), for the viewpoint of chemical-resistant, this composition unit (a2) is preferably 3 Mole %~70 mole %, more preferably 10 moles of %~60 mole %.
In the present invention, in turn, no matter any form, in all structural units of (A) ingredient, preferably rub containing 3 The structural unit (a2) of your %~70 mole % more preferably contains 10 moles of %~60 mole %.
If in above-mentioned numberical range, then transparent and resistance toization of the cured film obtained by photosensitive polymer combination Learning moral character becomes good.
<<(a3) other structures unit>>
In the present invention, (A) ingredient can also wrap other than including above structure unit (a1) and/or structural unit (a2) Containing the other structures unit (a3) other than these structural units.These structural units also may include above-mentioned component of polymer (1) and/ Or component of polymer (2).In addition, also may include substantially not in addition to above-mentioned component of polymer (1) or component of polymer (2) Component of polymer containing structural unit (a1) and structural unit (a2) but including other structures unit (a3).Removing above-mentioned polymerization Other than object ingredient (1) or component of polymer (2), also comprising being substantially free of structural unit (a1) and structural unit (a2) but wrapping In the case where the component of polymer for including other structures unit (a3), in all component of polymer, the blending amount of the component of polymer Preferably 60 mass % hereinafter, more preferably 40 mass % hereinafter, in turn be preferably 20 mass % or less.
As the monomer of other structures unit (a3), there is no particular restriction, such as can enumerate: phenylethylene, (methyl) propylene Acid alkyl ester, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, bicyclic insatiable hunger With compounds, maleimide compounds class, unsaturated aromatic compound, conjugated diene based compound, unsaturation Monocarboxylic acid, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.In addition, as described later, may also include tool There is the structural unit of acidic group.Monomer as other structures unit (a3) can be used alone or two or more is applied in combination.
Hereinafter, enumerating the preferred implementation form of component of polymer of the invention, but the present invention is not limited to these implementations Form.
(the 1st implementation form)
Component of polymer (1) further includes the form of a kind or other structures unit of more than two kinds (a3).
(the 2nd implementation form)
Component of polymer (2) include the group that (a1) there is acidic group to be protected by sour decomposability base structural unit polymerization Object further includes the form of a kind or other structures unit of more than two kinds (a3).
(the 3rd implementation form)
The polymer of structural unit including (a2) with bridging property base of component of polymer (2) further includes a kind or 2 kinds The form of above other structures unit (a3).
(the 4th implementation form)
In either one or two of above-mentioned 1st implementation form~the 3rd implementation form, the structural unit conduct including including at least acidic group The form of other structures unit (a3).
(the 5th implementation form)
It in addition to above-mentioned component of polymer (1) or component of polymer (2), and then include to be substantially free of structural unit (a1) And the form of structural unit (a2) but the polymer including other structures unit (a3).
(the 6th implementation form)
Combined form of more than two kinds comprising above-mentioned 1st implementation form~the 5th implementation form.
(the 7th implementation form)
Including at least the form of component of polymer (2).Especially in above-mentioned 1st implementation form~the 6th implementation form, at least Form comprising component of polymer (2).
Specifically, structural unit (a3) can enumerate the structural unit from following compound: styrene, tert-butoxy benzene Ethylene, methyl styrene, hydroxy styrenes, α-methylstyrene, acetoxy-styrene, methoxy styrene, ethoxybenzene Ethylene, chlorostyrene, vinylbenzoate, vinyl benzoic acid ethyl ester, 4-HBA (3- methacryloxy Propyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (first Base) isopropyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid benzyl Ester, (methyl) isobornyl acrylate, acrylonitrile, ethylene glycol single acetyl acetic acid esters list (methyl) acrylate etc..In addition to this, The chemical combination recorded in 0021~numbered paragraphs of numbered paragraphs 0024 of Japanese Patent Laid-Open 2004-264623 bulletin can be enumerated Object.
In addition, other structures unit (a3) is preferably phenylethylene, has alicyclic skeleton for the viewpoint of electrical characteristics Group.It can specifically enumerate: styrene, t-butoxystyrene, methyl styrene, hydroxy styrenes, Alpha-Methyl benzene second Alkene, (methyl) dicyclopentanyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid Benzyl ester etc..
In addition, other structures unit (a3) is preferably (methyl) alkyl acrylate for the viewpoint of adhesion.Specifically For can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid are just Butyl ester etc., more preferably (methyl) methyl acrylate.In the structural unit for constituting polymer (A), above structure unit (a3) Containing ratio is preferably 60 moles of % hereinafter, more preferably 50 moles of % hereinafter, be preferably 40 moles of % or less in turn.Lower limit value can For 0 mole of %, but it can be for example set as 1 mole of % or more, and then 5 moles of % or more can be set as.If in above-mentioned numberical range, The various characteristics of the cured film then obtained by photosensitive polymer combination become good.
Other structures unit (a3) preferably includes acidic group.By the inclusion of acidic group, and becomes easy and be dissolved in the aobvious of alkalinity In shadow liquid, more effective fruit effect of the invention is played.So-called acidic group in the present invention refers to proton dissociation of the pKa less than 7 Base.The monomer that can form acidic group is usually used as the structural unit comprising acidic group, and acidic group is set into polymer.It is logical It crosses in the polymer containing such structural unit comprising acidic group, and exists to become easy and be dissolved in inclining in alkaline-based developer To.
Acidic group used in the present invention can illustrate: from carboxylic acid group, from sulfoamido, from phosphonic acid base, source From sulfonic, from phenolic hydroxyl group, sulfoamido, sulfimide base etc., it is preferably derived from carboxylic acid group's and/or is originated from phenol Property hydroxyl.
Structural unit used in the present invention comprising acidic group is more preferably the structural unit for being originated from styrene or is originated from second The structural unit of alkenyl compound is originated from (methyl) acrylic acid and/or the structural unit of its ester.
In the present invention, especially for the viewpoint of sensitivity, preferably containing the structural unit with carboxyl or with phenol The structural unit of property hydroxyl.
Structural unit comprising acidic group is preferably 1 mole of %~80 mole % of the structural unit of all component of polymer, More preferably 1 mole of %~50 mole %, and then preferably 5 moles of %~40 mole %, particularly preferably 5 moles of %~30 rub You are %, especially preferably 5 moles of %~20 mole %.
It also may include being substantially free of knot in addition to above-mentioned component of polymer (1) or component of polymer (2) in the present invention Structure unit (a1) and structural unit (a2) but the polymer including other structures unit (a3).
Such polymer is preferably the resin on side chain with carboxyl.Such as it can enumerate: such as Japanese Patent Laid-Open No. Sho 59- No. 44615, Japan Patent examined patent publication 54-34327, Japan Patent examined patent publication 58-12577, Japan Patent examined patent publication 54- No. 25957, Japanese Patent Laid-Open No. Sho 59-53836, Japanese Patent Laid-Open No. Sho 59-71048 each bulletin in documented first Base acrylic copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymers, acid/maleic acid copolymers, part ester Change acid cellulose derivative on acid/maleic acid copolymers etc. and side chain with carboxyl, in the polymer with hydroxyl Made of middle addition acid anhydrides etc., and then the high molecular polymer on side chain with (methyl) acryloyl group can be also enumerated as preferred 's.
Such as it can enumerate: (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2- hydroxyl second It is recorded in ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer, Japanese Patent Laid-Open 7-140654 bulletin (methyl) acrylic acid 2- hydroxy propyl ester/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer, third Olefin(e) acid 2- hydroxyl -3- phenoxy-propyl/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer Object, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc..
In addition to this, it also can be used: Japanese Patent Laid-Open 7-207211 bulletin, Japanese Patent Laid-Open 8-259876 Number bulletin, Japanese Patent Laid-Open 10-300922 bulletin, Japanese Patent Laid-Open 11-140144 bulletin, Japan Patent are special Open flat 11-174224 bulletin, Japanese Patent Laid-Open 2000-56118 bulletin, Japanese Patent Laid-Open 2003-233179 public affairs The well known high-molecular compound recorded in report, Japanese Patent Laid-Open 2009-52020 bulletin etc., these contents are incorporated to this Shen It please be in specification.
These polymer can only include a kind, also may include two or more.
These polymer can also be used commercially available: SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (being manufactured above by Sartomer (Sartomer) company), A Lufeng (ARUFON) UC- 3000, A Lufeng (ARUFON) UC-3510, A Lufeng (ARUFON) UC-3900, A Lufeng (ARUFON) UC-3910, A Lufeng (ARUFON) UC-3920, A Lufeng (ARUFON) UC-3080 ((stock) manufacture is synthesized by East Asia above), Zhuan Chen (Joncryl) 690, Zhuan Chen (Joncryl 678, Zhuan Chen (Joncryl) 67, Zhuan Chen (Joncryl) 586 (being manufactured above by BASF (BASF)) Deng.
<<molecular weight of (A) polymer>>
(A) molecular weight of polymer is with polystyrene converted weight average molecular weight, and preferably 1,000~200,000, More preferably 2,000~50,000 range.If in above-mentioned numberical range, then various characteristics are good.Quantity mean molecule The ratio (dispersion degree) of amount and weight average molecular weight is preferably 1.0~5.0, and more preferably 1.5~3.5.
<<manufacturing method of (A) polymer>>
In addition, the synthetic method of (A) ingredient is it is also known that a variety of methods can be by using free radical polymerization if enumerating an example Initiator will include at least the free-radical polymerised list for being used to form structural unit represented by above-mentioned (a1) and above-mentioned (a3) The free radical polymerization monomer mixture of body, is polymerize in organic solvent to synthesize.In addition, so-called high score can also be passed through Son reaction is to synthesize.
Relative to 100 mass parts of all solids ingredient, photosensitive polymer combination of the invention is preferably with 50 mass parts The ratio of~99.9 mass parts includes (A) ingredient, includes more preferably (A) ingredient with 70 mass parts~98 mass parts ratio.
<(B) photoacid generator>
Photosensitive polymer combination of the invention contains (B) photoacid generator.Photoacid generator used in the present invention ( Referred to as " (B) ingredient ") be preferably 300nm or more to wavelength, the preferably actinic ray of wavelength 300nm~450nm is felt The compound of acid is answered and generates, but there is no restriction to its chemical structure.In addition, about being that the photochemical of 300nm or more is penetrated to wavelength The photoacid generator that line does not incude directly, as long as being that the photochemical of 300nm or more is penetrated to wavelength and being used in combination with sensitizer Line is incuded to generate the compound of acid, then can also be combined with sensitizer to be preferably used.The acid of light used in the present invention Producing agent is preferably to generate the photoacid generator that pKa is 4 acid below, and more preferably generation pKa is that the light acid of 3 acid below produces The photoacid generator that raw agent, most preferably generation pKa are 2 acid below.
The example of photoacid generator can be enumerated: trichloromethyl-s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazonium first Hydride compounds, acid imide sulfonate compound and oxime sulfonate compounds etc..In these compounds, with regard to the viewpoint of insulating properties For, it is preferable to use oxime sulfonate compounds.These photoacid generators can be used alone and a kind or make two or more combination With.Trichloromethyl-s-triazine, two virtue base Iodonium salts, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative Concrete example can illustrate and recorded in 0083~numbered paragraphs of numbered paragraphs 0088 of Japanese Patent Laid-Open 2011-221494 bulletin Compound.
Oxime sulfonate compounds are that there is the compound of oxime sulfonates structure can preferably illustrate containing the following general formula (B1) The compound of represented oxime sulfonates structure.
General formula (B1)
[changing 13]
(in general formula (B1), R21Indicate alkyl or aryl.Wavy line indicates the key with other groups.)
Any group can be substituted, R21In alkyl can be straight-chain, can be branch-like, can also for ring-type.It is right below The substituent group allowed is illustrated.
R21Alkyl be preferably carbon number 1~10 straight-chain or branch-like alkyl.R21Alkyl can be through carbon number 6~11 Aryl, carbon number 1~10 alkoxy or naphthenic base (include the endocyclics alicyclic ring such as 7,7- dimethyl -2- oxo norborny Base, preferably bicyclic alkyl etc.) it is replaced.
R21Aryl be preferably carbon number 6~11 aryl, more preferably phenyl or naphthalene.R21Aryl can be through rudimentary Replaced alkyl, alkoxy or halogen atom.
Above compound containing oxime sulfonates structure represented by above-mentioned general formula (B1) is preferably also the following general formula (B2) Represented oxime sulfonate compounds.
[changing 14]
(in formula (B2), R42Indicate that alkyl or aryl, X indicate that alkyl, alkoxy or halogen atom, m4 indicate 0~3 Integer, when m4 be 2 or 3 when, multiple X may be the same or different.)
Alkyl as X is preferably the straight-chain or branch-like alkyl of carbon number 1~4.
Alkoxy as X is preferably the straight-chain or branch-like alkoxy of carbon number 1~4.
Halogen atom as X is preferably chlorine atom or fluorine atom.M4 is preferably 0 or 1.It is special in above-mentioned general formula (B2) Not You Xuanwei m4 be 1, X be methyl, the position of substitution of X is ortho position, R42Straight-chain alkyl, 7,7- dimethyl-for carbon number 1~10 2- oxo norbornylmethyl or compound to toluyl groups.
Compound containing oxime sulfonates structure represented by above-mentioned general formula (B1) is preferably also the following general formula (B3) institute table The oxime sulfonate compounds shown.
[changing 15]
(in formula (B3), R43With the R in formula (B2)42Meaning is identical, X1Indicate the alkane of halogen atom, hydroxyl, carbon number 1~4 Base, the alkoxy of carbon number 1~4, cyano or nitro, n4 indicate 0~5 integer.)
R in above-mentioned general formula (B3)43It is preferred that are as follows: methyl, ethyl, n-propyl, normal-butyl, n-octyl, trifluoromethyl, five fluorine Ethyl, perfluor-n-propyl, perfluor-normal-butyl, p-methylphenyl, 4- chlorphenyl or pentafluorophenyl group, particularly preferably n-octyl.
X1The preferably alkoxy of carbon number 1~5, more preferably methoxyl group.
N4 is preferably 0~2, and particularly preferably 0~1.
The concrete example of compound represented by above-mentioned general formula (B3) can be enumerated: α-(methylsulfonyloxyimino) benzene second Nitrile, α-(ethylsulfonyloxy imino group) benzene acetonitrile, α-(n-propyl sulfonyloxyimino) benzene acetonitrile, α-(normal-butyl sulphonyl Oxygroup imino group) benzene acetonitrile, α-(4- tosyloxy imino group) benzene acetonitrile, α-[(methylsulfonyloxyimino) -4- first Phenyl] acetonitrile, α-[(ethylsulfonyloxy imino group) -4- methoxyphenyl] acetonitrile, [(the n-propyl sulfonyloxy Asia α - Amino) -4- methoxyphenyl] acetonitrile, α-[(normal-butyl sulfonyloxyimino) -4- methoxyphenyl] acetonitrile, α-[(4- first Phenylsulfonyloxy imino group) -4- methoxyphenyl] acetonitrile.
The concrete example of preferred oxime sulfonate compounds can enumerate following compounds (i)~compound (viii) etc., can be single It solely uses a kind or be two kinds or more.Compound (i)~compound (viii) can be used as commercially available product to obtain.In addition, It can be applied in combination with other kinds of (B) photoacid generator.
[changing 16]
Compound containing oxime sulfonates structure represented by above-mentioned general formula (B1) is preferably also the following general formula (OS-1) institute The compound of expression.
[changing 17]
In above-mentioned general formula (OS-1), R101Indicate hydrogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl, acyl group, ammonia first Acyl group, sulfamoyl, sulfo group, cyano, aryl or heteroaryl.R102Indicate alkyl or aryl.
X101Expression-O- ,-S- ,-NH- ,-NR105-、-CH2-、-CR106H- or-CR105R107, R105~R107Indicate alkane Base or aryl.
R121~R124Separately indicate hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxy carbonyl Base, alkyl-carbonyl, aryl carbonyl, amide groups, sulfo group, cyano or aryl.R121~R124In 2 can mutually be bonded respectively And form ring.
R121~R124Preferably hydrogen atom, halogen atom and alkyl, in addition, also preferably enumerating R121~R124In At least two be mutually bonded and formed the form of aryl.Wherein, for the viewpoint of sensitivity, preferably R121~R124It is hydrogen The form of atom.
Already described functional group can have substituent group in turn.
Compound represented by above-mentioned general formula (OS-1) is more preferably compound represented by the following general formula (OS-2).
[changing 18]
In above-mentioned general formula (OS-2), R101、R102、R121~R124It is identical as meaning in formula (OS-1) respectively, and preference Also identical.
R in these preferences, in more preferably above-mentioned general formula (OS-1) and above-mentioned general formula (OS-2)101For cyano or The form of person's aryl, most preferably by represented by above-mentioned general formula (OS-2) and R101For the form of cyano, phenyl or naphthalene.
In addition, the stereochemical structure (E, Z etc.) of oxime or benzothiazole ring can be respectively any in above-mentioned oxime sulfonate compounds It is a, it can also be mixture.
Can be suitable in the present invention compound represented by the above-mentioned general formula (OS-1) that uses concrete example can enumerate it is Japanese specially Compound (the exemplary compounds recorded in 0128~numbered paragraphs of numbered paragraphs 0132 of sharp special open 2011-221494 bulletin B-1~exemplary compounds b-34), but the present invention is not limited to this.
In the present invention, the compound containing oxime sulfonates structure represented by above-mentioned general formula (B1) is preferably the following general formula (OS-3), oxime sulfonate compounds represented by the following general formula (OS-4) or the following general formula (OS-5).
[changing 19]
(in general formula (OS-3)~general formula (OS-5), R22、R25And R28Separately indicate alkyl, aryl or heteroaryl Base, R23、R26And R29Separately indicate hydrogen atom, alkyl, aryl or halogen atom, R24、R27And R30Separately Indicate halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X1~X3Independently earth's surface Show oxygen atom or sulphur atom, n1~n3Separately indicate 1 or 2, m1~m3Separately indicate 0~6 integer.)
In above-mentioned general formula (OS-3)~general formula (OS-5), R22、R25And R28In alkyl, aryl or heteroaryl can have Substituent group.
In above-mentioned formula (OS-3)~formula (OS-5), R22、R25And R28In alkyl be preferably can have total carbon number of substituent group 1~30 alkyl.
In addition, in above-mentioned general formula (OS-3)~general formula (OS-5), R22、R25And R28In aryl preferably can have a substitution The aryl of total carbon number 6~30 of base.
In addition, in above-mentioned general formula (OS-3)~general formula (OS-5), R1In heteroaryl preferably can have the total of substituent group The heteroaryl of carbon number 4~30.
In above-mentioned general formula (OS-3)~general formula (OS-5), R22、R25And R28As long as heteroaryl at least one ring in is heteroaryl Fragrant ring, such as miscellaneous aromatic rings and phenyl ring can also contracting rings.
In above-mentioned general formula (OS-3)~general formula (OS-5), R23、R26And R29Preferably hydrogen atom, alkyl or aryl, it is more excellent It is selected as hydrogen atom or alkyl.
In above-mentioned general formula (OS-3)~general formula (OS-5), there are 2 or more R in compound23、R26And R29In, preferably 1 or 2 be alkyl, aryl perhaps halogen atom more preferably 1 be alkyl, aryl or halogen atom, particularly preferably It is alkyl for 1, and remaining is hydrogen atom.
R23、R26And R29In alkyl be preferably can have substituent group total carbon number 1~12 alkyl, can more preferably have The alkyl of total carbon number 1~6 of substituted base.
R23、R26And R29In aryl be preferably can have substituent group total carbon number 6~30 aryl.
In above-mentioned general formula (OS-3)~general formula (OS-5), X1~X3Separately indicate O or S, preferably O.
It include X in above-mentioned general formula (OS-3)~general formula (OS-5)1~X3Ring as ring element is 5 member rings or 6 member rings.
In above-mentioned general formula (OS-3)~general formula (OS-5), n1~n31 or 2 is separately indicated, in X1~X3For the feelings of O Under condition, n1~n3It is separately preferably 1, in addition, in X1~X3In the case where S, n1~n3It is separately preferably 2.
In above-mentioned general formula (OS-3)~general formula (OS-5), R24、R27And R30Separately indicate halogen atom, alkyl, alkane Oxygroup, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.Wherein, R24、R27And R30Separately be preferably alkyl or Person's alkoxy.
R24、R27And R30In alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl can have substitution Base.
In above-mentioned general formula (OS-3)~general formula (OS-5), R24、R27And R30In alkyl preferably can have the total of substituent group The alkyl of carbon number 1~30.
In above-mentioned general formula (OS-3)~general formula (OS-5), R24、R27And R30In alkoxy preferably can have a substituent group The alkoxy of total carbon number 1~30.
In addition, in above-mentioned general formula (OS-3)~general formula (OS-5), m1~m3Separately indicate 0~6 integer, preferably For 0~2 integer, more preferably 0 or 1, particularly preferably 0.
In addition, the respective substituent group about above-mentioned (OS-3)~(OS-5), Japanese Patent Laid-Open 2011-221494 public affairs The preferred scope of (OS-3) recorded in 0092~numbered paragraphs of numbered paragraphs 0109 of report~(OS-5) substituent group is also the same Ground is preferred.
In addition, the compound containing oxime sulfonates structure represented by above-mentioned general formula (B1) is particularly preferably the following general formula (OS-6) oxime sulfonate compounds represented by either one or two of~general formula (OS-11).
[changing 20]
(in formula (OS-6)~formula (OS-11), R301~R306Indicate alkyl, aryl or heteroaryl, R307Indicate hydrogen atom Or bromine atom, R308~R310、R313、R316And R318Separately indicate hydrogen atom, the alkyl of carbon number 1~8, halogen atom, Chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, R311And R314Separately indicate hydrogen atom, Halogen atom, methyl or methoxyl group, R312、R315、R317And R319Separately indicate hydrogen atom or methyl.)
Preferred scope and Japanese Patent Laid-Open 2011-221494 public affairs in above-mentioned general formula (OS-6)~general formula (OS-11) (OS-6) recorded in 0110~numbered paragraphs of numbered paragraphs 0112 of report~(OS-11) preferred scope is identical.
The concrete example of oxime sulfonate compounds represented by above-mentioned general formula (OS-3)~above-mentioned general formula (OS-5) can be enumerated day The compound recorded in 0114~numbered paragraphs of numbered paragraphs 0120 of this patent special open 2011-221494 bulletin, but this hair It is bright to be not limited to these compounds.
It is (excellent relative to all resin components in photosensitive polymer combination in photosensitive polymer combination of the invention It is selected as solid component, more preferably copolymer is total) 100 mass parts, (B) photoacid generator is preferably to use 0.1 mass parts ~10 mass parts more preferably use 0.5 mass parts~10 mass parts.Also two or more may be used.
<(C) aromatic heterocyclic compounds>
Composition of the invention contains (C) aromatic heterocyclic compounds.(C) molecular weight of aromatic heterocyclic compounds is 1000 hereinafter, and (C) aromatic heterocyclic compounds include at least one nitrogen-atoms in aromatic rings, and include in aromatic rings At least two coordination atom.By containing aromatic heterocyclic compounds, sensitivity can be not only maintained, but also chemical-resistant can be improved. In addition, the panel that can improve display device is aobvious if being used for display device for cured film is formed by by composition of the invention Show unevenness.
(C) molecular weight of aromatic heterocyclic compounds is for 1000 hereinafter, preferably 750 hereinafter, more preferably 500 or less. By the way that molecular weight is set as low molecule, molecule is easy mobile to substrate-side.Lower limit value is preferably 1 or more, and more preferably 50 or more.
The so-called coordination atom for constituting heteroaromatic, refers to the atom with coordinate bonding capability, such as can illustrate: nitrogen Atom, oxygen atom, sulphur atom, phosphorus atoms etc., more preferably nitrogen-atoms, oxygen atom, sulphur atom.(C) aromatic heterocyclic compounds Comprising at least two coordination atom, wherein at least 1 is nitrogen-atoms.Coordination atom is preferably in (C) aromatic heterocyclic compounds 1 It include 2~3 in the aromatic rings of molecule.In coordination atom, at least one is nitrogen-atoms, and preferably at least 2 are nitrogen-atoms. In addition, can also be the form that bond has hydrogen atom in coordination atom.In addition, (C) aromatic heterocyclic compounds are preferably free of Basic group, and then be preferably free of amino.
(C) aromatic heterocyclic compounds can have substituent group T on aromatic rings.Substituent group T can for example be enumerated: carbon number 1~ 10 alkyl, the alkoxy of carbon number 1~10, the thio alkoxy of carbon number 1~10, hydroxyl, carboxyl, acetyl group, cyano, halogen are former Sub (fluorine atom, chlorine atom, bromine atom, iodine atom) etc..These substituent groups can further have substituent group.However, in the present invention (C) aromatic heterocyclic compounds used are preferably unsubstituted or through methyl substituted compound.
In addition, being preferably free of substituent group of the amino as aromatic rings for may refrain from the viewpoint that sensitivity reduces.
(C) it as long as aromatic heterocyclic compounds are aromatic ring, is not particularly limited, preferably 5 yuan of cyclic aromatic series are miscellaneous Cycle compound, 6 cyclic aromatic heterocycle compounds include in 5 yuan of cyclic aromatic heterocycle structures and 6 yuan of cyclic aromatic heterocycle structures The polycycle aromatic heterocyclic compounds of at least one.
So-called polycycle aromatic heterocyclic compounds refer to 2 or more independent aromatic rings each other by associative key And the aliphatic ring and/or fragrance of the aromatic rings of the compound (such as bipyridyl etc.) being bonded or 1 or more and 1 or more The compound (such as phenanthroline etc.) of race's cyclic condensation.In the present invention, if constituting at least one of polycycle aromatic heterocyclic compounds Ring is 5 yuan of cyclic aromatic heterocycle structures or 6 yuan of cyclic aromatic heterocycle structures, then other rings can be any ring, other rings are excellent It is selected as in phenyl ring, 5 yuan of cyclic aromatic heterocycles and 6 yuan of cyclic aromatic heterocycles, is more preferably selected from phenyl ring and 6 yuan of cyclophanes In fragrant race's heterocycle.The quantity for forming the ring of polycycle aromatic heterocyclic compounds is preferably to have 2 or 3 in 1 molecule, more preferably It is 2.
5 member ring aromatic heterocyclic compounds are preferred are as follows: imidazole compound, pyrazoles based compound, oxazole based compound, different Oxazole based compound, thiazole compound, isothiazole based compound, three azole compounds, oxadiazoles based compound, thiadiazoles system Compound etc..
Imidazole compound is preferred are as follows: imidazoles, 1- methylimidazole, 1- ethyl imidazol(e), 1- n-propyl imidazoles, 1- isopropyl miaow Azoles, 1- butyl imidazole, 1- decyl -2-methylimidazole, 1,2- methylimidazole, 2-ethyl-4-methylimidazole, 2- heptadecyl miaow Azoles, 1- (seven fluorine bytyries) imidazoles, 2-methylimidazole, 4-methylimidazole, 2- phenylimidazole, 4- phenylimidazole, 1- benzyl imidazole, 4- methyl -2- phenylimidazole, 1- acetyl imidazole, 1- imidazoleacetic acid, 4- imidazolyl carboxylic acid, 4,5- imidazole-2-carboxylic acid etc..
Pyrazoles based compound is preferably: pyrazoles, 1- methylpyrazole, 3- methylpyrazole, 4-methylpyrazole, 1- ethylpyrazol, 3- ethylpyrazol, 4- ethylpyrazol, 1- Phenylpyrazole, 3- Phenylpyrazole, 4- Phenylpyrazole, 3,5- diisopropyl pyrazoles, 3- (three Methyl fluoride) pyrazoles, 4- bromine pyrazoles, 4- chlorine pyrazoles, 3,5- dimethyl pyrazole, 1,3,5- trimethylpyrazols, 3,5- dimethyl -1- benzene Base pyrazoles, 3- (4- tolyl) pyrazoles, 3- (4- methoxyphenyl) pyrazoles, 3- (4- bromophenyl) pyrazoles, 3- methyl-1-phenyl pyrazoline The bromo- 3- methylpyrazole of azoles, 4-, 3- (4- bromophenyl) pyrazoles, 3- (4- fluorophenyl) pyrazoles, bromo- 3, the 5- dimethyl pyrazole of 4-, 4- Bromo- 1- Phenylpyrazole, 3- (4- chlorphenyl) pyrazoles, 3,5- dimethyl -1- hydroxymethylpyrazolcompound, pyrazoles -3- carboxylic acid, pyrazoles -4- Carboxylic acid etc..
Oxazole based compound is preferred are as follows: oxazole, 2,4- dimethyl oxazoline, 4- oxazolyl phenyl, 5- oxazolyl phenyl, 2,4- hexichol Base oxazole, 2,5- diphenyloxazole, 2,4,5- trimethyl oxazoles, 5- [3- (trifluoromethyl) phenyl] oxazole, 2- methyl -4,5- bis- Oxazolyl phenyl, 5- ethyoxyl -4- methyl oxazole, 4- oxazole carboxylic acid, 4- oxazole carboxylic acid, ethyl ester etc..
Isoxazole based compound is preferred are as follows: bromo- 3, the 5- bis- of isoxazole, 5- methylisoxazole, 3,5- dimethyl isoxazole, 4- Methylisoxazole, 3- chloromethyl -5- methylisoxazole, 4- (chloromethyl) -3,5- dimethyl isoxazole, iodo- 3, the 5- dimethyl of 4- Isoxazole, 3-hydroxy-5-methylisoxazole, 5- methyl -3- isoxazole carboxylic acid, -4 carboxylic acid of 5- methylisoxazole etc..
Thiazole compound is preferred are as follows: thiazole, 2- methylthiazol, 2- ethyl thiazole, 2- n-propyl thiazole, 2- isopropyl thiophene Azoles, 2- normal-butyl thiazole, 2- isobutyl thiazole, 2- phenyl thiazole, 4- methylthiazol, 5- methylthiazol, 2,4- dimethylthiazole, 4,5- dimethylthiazoles, 2- ethyl -4- methylthiazol, 2- ethyl -4,5- dimethylthiazole, 2- isopropyl-4-methyl thiazole, 2- Isobutyl group -4- methylthiazol, 4- methyl -2- phenyl thiazole, 4- methyl -5- vinylthiazole, 2- isobutyl group -4,5- dimethyl thiophene Azoles, 2- methyl -4,5- diphenylthiazol, 2,4,5- trimethylthiazoles, 2- (trimethylsilyl) thiazole, 2- bromo thiazole, 4- bromine The bromo- 4- methylthiazol of thiazole, 5- bromo thiazole, 2-, 4- tert-butyl -2- methylthiazol, the second butyl of 2- thiazole, 2,4- dibromo thiophene Azoles, 2,5-, bis- bromo thiazole, 2,4- dichloro thiazole, 4,5- dimethyl -2- ethyl thiazole, 4,5- dimethyl-2-isopropyl thiazole, 2- Acetylthiazole, 2- acetyl group -4,5- dimethylthiazole etc., 2- ethoxythiazole, 5- hydroxymethyl thiazole, 2- hydroxyl -4- benzene Base thiazole, 2- methoxy thiazole.
Isothiazole based compound is preferably isothiazole.
Three azole compounds are preferably: 1,2,3-triazoles, 1,2,4- triazoles, 3- methyl-1 H-1,2,4- triazoles etc..
Oxadiazoles based compound is preferred are as follows: 1,2,3-oxadiazoles, 1,2,4- oxadiazoles, 1,3,4- oxadiazoles, 1,2,5- dislike Diazole, 2- chloromethyl -5- (4- aminomethyl phenyl) -1,3,4- oxadiazoles, 3- (chloromethyl) -1,2,4- oxadiazoles, 3- (chloromethyl) - 5- phenyl -1,2,4- oxadiazoles, 2,5- diphenyl -1,3,4- oxadiazoles, 5- methyl -3- phenyl -1,2,4- oxadiazoles, 2- (2- Methoxyphenyl) -5- phenyl -1,3,4- oxadiazoles, ethyl -1,2,4- oxadiazoles -3- carboxylic acid etc..
Thiadiazoles system compound is preferred are as follows: 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,3,4- thiadiazoles, 1,2,5- thiophenes Diazole, 2,5- dimethyl -1,3,4- thiadiazoles, 4- phenyl -1,2,3- thiadiazoles, 4,5- diphenyl -1,2,3- thiadiazoles, 3- Bromo- 5- chloro- 1, the bromo- 5- phenyl -1,3 of 2,4- thiadiazoles, 2-, 4- thiadiazoles, 2- chloromethyl -5- cyclopropyl -1,3,4- thiadiazoles, 3,4- bis- chloro- 1,2,5- thiadiazoles, 3,5- bis- chloro- 1,2,4- thiadiazoles etc..
6 member ring aromatic heterocyclic compounds are preferred are as follows: pyrimidine compound, pyridazine compound, pyrazine based compound, three Piperazine based compound etc..
Pyrimidine compound is preferred are as follows: pyrimidine, 2- chlorine pyrimidine, 2- Bromopyrimidine, 5- Bromopyrimidine, the bromo- 2- chlorine pyrimidine of 5-, 2- The chloro- 5- ethyl-pyrimidine of chloro- 4- methylpyrimidine, 2-, bromo- 2, the 4- dichloro pyrimidine of 5-, bromo- 4, the 6- dichloro pyrimidine of 5-, the chloro- 5- of the 2- positive last of the ten Heavenly stems Chloro- 4, the 6- dimethyl pyrimidine of yl pyrimidines, 2-, chloro- 2, the 6- dimethyl pyrimidine of 4-, pyrimidine -5-carboxylic acid, the bromo- 2- hydroxy pyrimidine of 5-, 5- Bromo- 2- methoxy pyrimidine, 4,6- dihydroxy-pyrimidine, 4,6- dimethoxypyridin, 4- hydroxy pyrimidine, 2,4,5- trihydroxy-pyrimidines Deng.
Pyridazine compound is preferred are as follows: 3- methyl pyridazine, 4- methyl pyridazine, 3,6- dichloro-pyridazine, the chloro- 4- methyl of 3,6- bis- Pyridazine, 3,4,6- trichlorine pyridazines, pyridazine -4- carboxylic acid, pyridazine -4,5- dicarboxylic acids, 3,6- dihydroxy -4- methyl pyridazine, 3- methoxy Radical pyridazine etc..
Pyrazine based compound is preferred are as follows: pyrazine, 2- methylpyrazine, 2- ethyl pyrazine, 2- n-propyl pyrazine, 2- isopropyl pyrrole Piperazine, 2- isobutyl pyrazine, 2- tert-butyl-pyrazin, 2- vinylpyrazine, 2- chloropyrazine, 2,3- dimethyl pyrazine, 2,5- dimethyl Pyrazine, 2,6- dimethyl pyrazine, 2,3- diethyl pyrazine, 2,3- diphenyl pyrazine, 2- methyl -3- n-propyl pyrazine, 2- ethyl - 3- methylpyrazine, 2- isobutyl group -3- methylpyrazine, 5- isobutyl group -2,3- dimethyl pyrazine, 2,3- diethyl -5- methylpyrazine, 3,5- dimethyl -2- ethyl pyrazines, 2,3,5- trimethylpyrazines, Tetramethylpyradine, 2,3- dimethyl -5- isopropyl Pyrazine, 2,3- dichloropyrazine, 2,6- dichloropyrazine, 2- acetyl group -3- methylpyrazine, 2- methoxypyrazine, 2- ethyoxyl pyrazine, 2- ethyoxyl -3- methylpyrazine, 2- ethyl -3- methoxypyrazine, 2- isopropyl -3- methoxypyrazine, 2- isobutyl group -3- methoxy Base pyrazine, 2- acetyl group pyrazine, 2- acetyl group -3- ethyl pyrazine, pyrazine carboxylic acid, pyrazine -2- carboxylate methyl ester etc..
Triazine based compound is preferred are as follows: 1,2,3- triazine, 1,2,4- triazines, 1,3,5-triazines, 2, and 4,6- tri- chloro- 1,3,5- Triazine, 2,4,6- triphenyls -1,3,5-triazines, 2,4,6- tri- (trifluoromethyl) -1,3,5-triazines etc., dimethoxy -1 2,4-, 3,5- triazines.
Polycycle aromatic heterocyclic compounds are preferred are as follows: benzimidazole based compound, benzopyrazoles based compound, benzo are disliked Azole compounds, benzo isoxazole based compound, benzothiazole based compound, benzotriazole based compound, benzoxadiazole system Compound, diazosulfide based compound, quinazoline based compound, phthalazines based compound, phenanthroline based compound, bipyridyl system Compound.
The concrete example of benzimidazole based compound is preferred are as follows: benzimidazole, 4- tolimidazole, 5- methyl benzo miaow Azoles, 6- tolimidazole, 7- tolimidazole, 4- ethyl benzo imidazole, 5- ethyl benzo imidazole, 6- ethyl benzo miaow Azoles, 7- ethyl benzo imidazole, 4- n-propyl benzimidazole, 5- n-propyl benzimidazole, 6- n-propyl benzimidazole, 7- n-propyl Benzimidazole, 4- isopropyl benzimidazole, 5- isopropyl benzimidazole, 6- isopropyl benzimidazole, 7- isopropyl benzimidazole, 1- butyl benzimidazole, 2- acetyl group benzimidazole, 2-Chlorobenzimidazole, 2- (chloromethyl) benzimidazole, 2,5- dimethyl benzene And imidazoles, 5- benzimidazole carboxylic acid, 2- hydroxybenzimidazole, 2- (hydroxymethyl) benzimidazole, 2- (3- hydroxypropyl) benzo Imidazoles, 2- (1- hydroxyethyl) benzimidazole, 5- benzimidazole carboxylic acid, 2- hydroxybenzimidazole etc..
The concrete example of benzopyrazoles based compound is preferred are as follows: chloro- 1H- benzopyrazoles of 1,2- benzopyrazoles, 3- etc..
The concrete example of benzoxazoles based compound is preferred are as follows: benzoxazoles, 2- methylbenzoxazole, 5- methyl benzo are disliked Azoles, 2,6- dichloro benzoxazoles, 2,5- dimethylbiphenyl oxazole, 5- fluoro-2-methylbenzene and oxazole, 2,5,6- trimethyl benzos are disliked Azoles, 2- chlorobenzene diozaiole, 2- methyl -5- phenyl benzoxazoles, 2- (2- hydroxy phenyl) benzoxazoles etc..
The concrete example of benzo isoxazole based compound is preferred are as follows: 1,2- benzo isoxazole, 1,2- benzo isoxazole -3- acetic acid Deng.
The concrete example of benzothiazole based compound is preferred are as follows: benzothiazole, 2- methylbenzothiazole, 2- ethyl benzo thiophene Azoles, 2- n-propyl benzothiazole, 2- isopropyl benzothiazole, 2- normal-butyl benzothiazole, 2- phenylbenzothiazol, 2,5- diformazan Base benzothiazole, 2,6- dimethyl-benzothiazole, 2, the chloro- 5- chloromethyl of 5,6- trimethyl benzothiazoles, 2- chloro benzothiazole, 2- The bromo- 2- chloro benzothiazole of thiazole, 6-, the bromo- 2- methylbenzothiazole of 5-, 2,6- dichlorobenzothiazole, 2- fluoro benzothiazole, 5- Chloro-2-methyl benzothiazole, 5- fluoro-2-methylbenzene and thiazole, 2- (4- bromophenyl) benzothiazole, 2- acetyl group benzothiazole, 2- hydroxybenzothiazole, 5- methoxyl group -2- methylbenzothiazole, 2- (2- hydroxy phenyl) benzothiazole, benzothiazole -6- carboxylic acid Deng.
Benzotriazole based compound is preferably: 1,2,3- benzotriazole, 4- methylbenzotrazole, 1- chlorobenzotriazole, 5- Chlorobenzotriazole, 1- methyl-1 H- benzotriazole, 2- methyl -2H- benzotriazole, 5- methyl-1 H- benzotriazole, 1- (chloromethane Base) -1H- benzotriazole, 4- hydroxybenzotriazole, 1- (methoxy)-IH- benzotriazole, 2- (2- hydroxy-5-methyl base benzene Base) benzotriazole, 1H- benzotriazole -1- methanol, 1,2,3- benzotriazole -5- carboxylate methyl esters, 1,2,4- benzotriazole -3- carboxylics Sour methyl esters, 4- methyl -2- phenyl -1,2,3-triazoles -5- carboxylic acid, 1- isopropyl benzotriazole -5- carboxylic acid, 1- amino benzotriazole Deng.
Benzoxadiazole based compound is preferred are as follows: 2,1,3- benzoxadiazoles, 4- fluoro- 2,1,3- benzoxadiazole, 4- are chloro- 2,1,3- benzoxadiazoles etc..
Diazosulfide based compound is preferred are as follows: 2,1,3- diazosulfides, 4,7- bis- bromo- 2,1,3- diazosulfide, 5,6- bis- bromo- 2,1,3- diazosulfide, 2,1,3- diazosulfide -5- carboxylic acid, 2-mercaptobenzothiazole, 6- amino -2- mercapto Base benzothiazole etc..
Quinazoline based compound is preferred are as follows: quinazoline, 4- chloro-quinazoline, 2,4- dichloroquinazoline, 4- hydroxyquinazoline, 5- Fluoro- 4- hydroxyquinazoline etc..
Phthalazines based compound is preferred are as follows: phthalazines, 6- methyl phthalazines, 1- chlorine phthalazines, Isosorbide-5-Nitrae-dichloro phthalazines etc..
Phenanthroline based compound is preferred are as follows: 1,10- phenanthroline, 5- methyl-1, chloro- 1, the 10- phenanthroline of 10- phenanthroline, 2-, Chloro- 1, the 10- phenanthroline of 5-, 3,8- dimethyl -1,10- phenanthroline, 4,7- dimethyl -1,10- phenanthroline, dimethyl -1 5,6-, 10- phenanthroline, 2,9- dibutyl -1,10- phenanthroline, 4,7- diphenyl -1,10- phenanthroline, chloro- 1, the 10- phenanthroline of 4,7- bis-, Bromo- 1, the 10- phenanthroline of 3-, 3,4,7,8- tetramethyl -1,10- phenanthroline, 4,7- dihydroxy -1,10- phenanthroline, 1,10- phenanthrene are coughed up Quinoline -2,9- dicarboxylic acids etc..
Bipyridyl based compound is preferred are as follows: 2,2 '-bipyridyls, 2,4 '-bipyridyls, 4,4 '-bipyridyls, phenyl -2 5-, 2 ' - Bipyridyl, phenyl -2 5-, 3 '-bipyridyls, phenyl -2 5-, 4 '-bipyridyls, 4,4 '-dimethyl -2,2 '-bipyridyls, 5,5 '-two 2,2 '-bipyridyl of methyl -, 6,6 '-dimethyl -2,2 '-bipyridyls, 4,4 '-dinonyl -2,2 '-bipyridyls, 4,4 '-two bromo- 2, 2 '-bipyridyls, 6,6 '-two bromo- 2,2 '-bipyridyls, 4,4 '-bis- (chloromethyl) -2,2 '-bipyridyls, 5,5 '-two chloro- 2,2 '-connection Pyridine, 5- bromo- 2,2 '-bipyridyls, 5- bromo- 2,3 '-bipyridyls, 5- bromo- 2,4 '-bipyridyls, 6- bromo- 2,2 '-bipyridyls, 4, 4 '-bis- (hydroxymethyl) -2,2 '-bipyridyls, 2,2 '-bipyridyl -3,3 '-dicarboxylic acids, 2,2 '-bipyridyl -4,4 '-dicarboxylic acids, 2,2 '-bipyridyl -5,5 '-dicarboxylic acids etc..
In these compounds, aromatic heterocyclic compounds are preferred are as follows: oxazole, 2,4,5- trimethyl oxazoles, isoxazole, 5- first Base isoxazole, thiazole, 5- methylthiazol, isothiazole, 1,2,3-triazoles, 1,2,4- triazoles, 1,2,3-oxadiazoles, 1,2,4- dislike two Azoles, 1,3,4- oxadiazoles, 1,2,5- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,3,4- thiadiazoles, 1,2,5- thiophenes Diazole, pyrimidine, 1,2,3- triazines, 1,2,4- triazines, 1,3,5-triazines, 1,2- benzopyrazoles, benzoxazoles, 5- methyl benzo are disliked Azoles, 1,2- benzo isoxazole, benzothiazole, 2,6- dimethyl-benzothiazole, 2,1,3- benzoxadiazole, 2,1,3- benzo thiophene two Azoles, 1,2,3- benzotriazole, quinazoline, phthalazines, 1,10- phenanthroline, 5- methyl-1,10- phenanthroline, 2,2 '-bipyridyls, 4, 4 '-bipyridyls, 5,5 '-dimethyl -2,2 '-bipyridyls, 2-mercaptobenzothiazole, 1- amino benzotriazole, 6- amino-2-mercapto phenyl formic Benzothiazole, more preferably: 1,2,3-triazoles, 1,2,4- triazoles, 1,2,3-oxadiazoles, 1,2,4- oxadiazoles, 1,3,4- dislike two Azoles, 1,2,5- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,3,4- thiadiazoles, 1,2,5- thiadiazoles, pyrimidine, 1,2, 3- triazine, 1,2,4- triazines, 1,3,5-triazines, 1,2- benzopyrazoles, 2,1,3- benzoxadiazole, 2,1,3- diazosulfide, 1,2,3- benzotriazole, quinazoline, phthalazines, 1,10- phenanthroline, 5- methyl-1,10- phenanthroline, 2,2 '-bipyridyls, 4,4 '-connection Pyridine, 5,5 '-dimethyl -2,2 '-bipyridyls.
Relative to 100 mass parts of all solids ingredient of photosensitive polymer combination, photosensitive resin composition of the invention The additive amount of aromatic heterocyclic compounds in object is preferably 0.01 mass parts~10 mass parts, and more preferably 0.01 mass parts~ 8 mass parts, and then preferably 0.01 mass parts~5 mass parts.
<(D) solvent>
Photosensitive polymer combination of the invention contains (D) solvent.Photosensitive polymer combination of the invention is preferably made It is standby to be dissolved in solution made of in (D) solvent at by essential component of the invention, in turn with aftermentioned any ingredient.
Well known solvent can be used in (D) solvent used in photosensitive polymer combination of the invention, can illustrate: ethylene glycol Monoalkyl ethers, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol two Alkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, Dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone, amide Class, lactone etc..In addition, the concrete example of (D) solvent used in photosensitive polymer combination of the invention can also enumerate Japan The solvent recorded in 0174~numbered paragraphs of numbered paragraphs 0178 of open patent 2011-221494 bulletin, these contents are simultaneously Enter in present specification.
In addition, optionally can also and then be added into these solvents: benzyl ether, two hexyl ethers, ethyleneglycol monophenylether acetic acid Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, benzylalcohol, benzene first Ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate etc. Solvent.These solvents, which can be used alone, or to be used in mixed way two or more by a kind.Workable solvent is preferably single in the present invention Solely using a kind or 2 kinds being used in combination, more preferably 2 kinds are used in combination, so preferably by propylene-glycol monoalky lether acetate esters or Person's dialkyl ether, oxalic acid esters and diethylene glycol dialkyl ether class or esters and butanediol alkylether acetates class are simultaneously With.
In addition, it be 130 DEG C of solvent, boiling points more than and less than 160 DEG C is 160 DEG C or more molten that ingredient D, which is preferably boiling point, The mixture of agent or these solvents.
Boiling point is that 130 DEG C of solvents more than and less than 160 DEG C can illustrate: propylene glycol methyl ether acetate (boiling point 146 DEG C), propylene glycol monoethyl ether acetate (boiling point is 158 DEG C), propylene glycol methyl-n-butyl ether (boiling point is 155 DEG C), propylene glycol first Base-positive propyl ether (boiling point is 131 DEG C).
Boiling point is that 160 DEG C or more of solvent can illustrate: 3- ethoxyl ethyl propionate (boiling point is 170 DEG C), diethylene glycol first (boiling point is for base ether (boiling point is 176 DEG C), propylene glycol monomethyl ether propionate (boiling point is 160 DEG C), dipropylene glycol methyl ether acetic acid esters 213 DEG C), 3- methoxyl group butyl ether acetic acid esters (boiling point is 171 DEG C), diethylene glycol diethyl ether (boiling point is 189 DEG C), diethylene glycol two Methyl ether (boiling point is 162 DEG C), propylene-glycol diacetate (boiling point is 190 DEG C), diethylene glycol monoethyl ether acetic acid esters (boiling point 220 DEG C), dimethyl ether (boiling point is 175 DEG C), 1,3-BDO diacetate esters (boiling point is 232 DEG C).
Relative to 100 mass parts of all resin components in photosensitive polymer combination, photoresist group of the invention The content for closing (D) solvent in object is preferably 50 mass parts~95 mass parts, and then preferably 60 mass parts~90 mass parts.
<other compositions>
In photosensitive polymer combination of the invention in addition to the above ingredients, (E) alcoxyl is optionally preferably added Base silane compound, (F) crosslinking agent, (G) sensitizer, (H) alkali compounds, (I) surfactant, (J) antioxidant.Into And can be added in photosensitive polymer combination of the invention acid proliferation generator, development accelerant, plasticiser, hot radical producing agent, Additive well known to thermal acid generator, ultraviolet absorbing agent, tackifier and organic or inorganic suspending agent etc..
(E) alkoxysilane compound containing trialkylsilyl group in molecular structure
Photosensitive polymer combination of the invention contains (E) alkoxysilane compound containing trialkylsilyl group in molecular structure (also referred to as " (E) ingredient ").If making With alkoxysilane compound containing trialkylsilyl group in molecular structure, then the adhesion of the film and substrate that are formed by photosensitive polymer combination of the invention can be improved, Or the property of the adjustable film formed by photosensitive polymer combination of the invention.Alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably dialkoxy Base silane compound or trialkoxy silane compound, more preferably trialkoxy silane compound.Alkoxy silane chemical combination The carbon number of alkoxy possessed by object is preferably 1~5.
Workable (E) alkoxysilane compound containing trialkylsilyl group in molecular structure, which preferably improves, in photosensitive polymer combination of the invention becomes base The inorganic matter of material, such as: the silicon compounds such as silicon, silica, silicon nitride, the contiguity of the metals such as gold, copper, molybdenum, titanium, aluminium and insulating film The compound of property.Specifically, well known silane coupling agent etc. is also effective.
Silane coupling agent can for example be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-methyl-prop Alkene propyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, three alkane of γ-chloropropyl Oxysilane, γ-mercaptopropyi trialkoxy silane, β-(3,4- epoxycyclohexyl) ethyltrialkoxysilanes, vinyl three Alkoxy silane.In these compounds, more preferably γ-glycidyloxypropyl silane or γ-metering system Propyl trialkoxy silane, and then preferably γ-glycidyloxypropyl silane, are especially more preferably 3- glycidoxypropyltrimewasxysilane.These compounds, which can be used alone, or two or more to be applied in combination by a kind.
In addition, also preferably using following compounds.
[changing 21]
[changing 22]
Among the above, Ph is phenyl.
(E) alkoxysilane compound containing trialkylsilyl group in molecular structure in photosensitive polymer combination of the invention is not particularly limited to these chemical combination Well known compound can be used in object.
Relative to 100 mass parts of all solids ingredient in photosensitive composite, photosensitive polymer combination of the invention In the content of (E) alkoxysilane compound containing trialkylsilyl group in molecular structure be preferably 0.1 mass parts~30 mass parts, more preferably 0.5 mass parts~20 Mass parts.
(F) crosslinking agent
Photosensitive polymer combination of the invention preferably optionally contains crosslinking agent.By add crosslinking agent, can make by The cured film that photosensitive polymer combination of the invention obtains forms stronger film.
As long as crosslinking agent Yin Re and generate cross-linking reaction, then without limitation.(except A ingredient).Such as it can add: following The intramolecular have the compound of 2 or more epoxy groups or oxetanylmethoxy, the crosslinking agent containing alkoxy methyl or Compound, block isocyanate compound at least one ethylene unsaturated double-bond etc..
Relative to 100 mass parts of all solids ingredient of photosensitive polymer combination, photosensitive resin composition of the invention The additive amount of crosslinking agent in object is preferably 0.01 mass parts~50 mass parts, more preferably 0.1 mass parts~30 mass parts, into And preferably 0.5 mass parts~20 mass parts.By with range addition, and obtain mechanical strength and excellent solvent resistance Cured film.Crosslinking agent can also be used together by more than one, and in this case all add up to crosslinking agent to calculate content.
<compound that intramolecular has 2 or more epoxy groups or oxetanylmethoxy>
There is intramolecular the concrete example of the compound of 2 or more epoxy groups can enumerate: bisphenol A type epoxy resin, bisphenol-f type Epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc..
These compounds can be used as commercially available product and obtain.Such as it can enumerate: JER157S70, JER157S65 (Mitsubishi Chemical Holding (Mitsubishi Chemical Holdings) (stock) manufacture) etc. Japanese Patent Laid-Open 2011-221494 bulletin The commercially available product etc. recorded in numbered paragraphs 0189.
In addition to this, it can enumerate: Ai Dike resin (ADEKA RESIN) EP-4000S, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike resin (ADEKA RESIN) EP-4010S, Ai Dike resin (ADEKA RESIN) EP- 4011S (above by Ai Dike (ADEKA) (stock) manufacture), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (is manufactured by Ai Dike (stock)) above, Dai Nake (Denacol) EX-611, Dai Nake (Denacol) EX-612, generation That section (Denacol) EX-614, Dai Nake (Denacol) EX-614B, Dai Nake (Denacol) EX-622, Dai Nake (Denacol) EX-512, Dai Nake (Denacol) EX-521, Dai Nake (Denacol) EX-411, Dai Nake (Denacol) EX-421, Dai Nake (Denacol) EX-313, Dai Nake (Denacol) EX-314, Dai Nake (Denacol) EX-321, for that Section (Denacol) EX-211, Dai Nake (Denacol) EX-212, Dai Nake (Denacol) EX-810, Dai Nake (Denacol) EX-811, Dai Nake (Denacol) EX-850, Dai Nake (Denacol) EX-851, Dai Nake (Denacol) EX-821, for that Section (Denacol) EX-830, Dai Nake (Denacol) EX-832, Dai Nake (Denacol) EX-841, Dai Nake (Denacol) EX-911, Dai Nake (Denacol) EX-941, Dai Nake (Denacol) EX-920, Dai Nake (Denacol) EX-931, for that Section (Denacol) EX-212L, Dai Nake (Denacol) EX-214L, Dai Nake (Denacol) EX-216L, Dai Nake (Denacol) EX-321L, Dai Nake (Denacol) EX-850L, Dai Nake (Denacol) DLC-201, Dai Nake (Denacol) DLC-203, Dai Nake (Denacol) DLC-204, Dai Nake (Denacol) DLC-205, Dai Nake (Denacol) DLC-206, Dai Nake (Denacol) DLC-301, Dai Nake (Denacol) DLC-402 is (above by the rapids chemical conversion of length (Nagase ChemteX) manufacture), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 are (above by Nippon Steel Chemistry manufacture), (Celloxide) 2021P, Sai Luo West Germany, Sai Luo West Germany (Celloxide) 2081, Sai Luo West Germany (Celloxide) 3000, Sai Luo West Germany (Celloxide) EHPE3150, Ai Boli obtains (Epolead) GT400, match fine jade ratio receives this (Celvenus) B0134, match fine jade ratio receive this (Celvenus) B0177 (Daicel (Daicel) (stock)) etc..
These commercially available products, which can be used alone, or two or more to be applied in combination by a kind.
In these compounds, more preferably enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolac are clear Paint shaped epoxy resin and aliphatic epoxy resin, particularly preferably enumerate bisphenol A type epoxy resin.
There is intramolecular the concrete example of the compound of 2 or more oxetanylmethoxies can be used: sub- dragon oxetanes (Aron Oxetane) OXT-121, sub- dragon oxetanes (Aron Oxetane) OXT-221, sub- imperial oxetanes (Aron Oxetane) OX-SQ, sub- dragon oxetanes (Aron Oxetane) PNOX ((stock) manufacture is synthesized by East Asia above).
In addition, the compound comprising oxetanylmethoxy is preferably used alone or mixes with the compound comprising epoxy group It uses.
In addition, other crosslinking agents it may also be preferred to use the numbered paragraphs of Japanese Patent Laid-Open 2012-8223 bulletin The crosslinking agent containing alkoxy methyl recorded in 0107~numbered paragraphs 0108 and have at least one ethylene unsaturated double The compound etc. of key, these contents are incorporated herein in specification.Crosslinking agent containing alkoxy methyl is preferably alkoxy methyl Change glycoluril.
<block isocyanate compound>
In photosensitive polymer combination of the invention, it also may be preferable for ground is using blocked isocyanate based compound as crosslinking Agent.As long as block isocyanate compound has the compound of blocked isocyanate ester group, then it is not particularly limited, it is just indurative For viewpoint, preferably 1 intramolecular has the compound of 2 or more blocked isocyanate ester groups.
In addition, the so-called blocked isocyanate ester group in the present invention, refers to the group that can generate isocyanate group because of heat, example Such as, the group for reacting block agent with isocyanate group to protect isocyanate group can preferably be illustrated.In addition, above-mentioned block is different Cyanic acid ester group is preferably the group that isocyanate group can be generated because of 90 DEG C~250 DEG C of heat.
In addition, block isocyanate compound is not particularly limited its skeleton, as long as having 2 isocyanides in 1 molecule Perester radical, then can be arbitrary, preferably aliphatic, alicyclic or aromatic polyisocyanate, such as can be suitable for using: 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI), isophorone diisocyanate, 1,6- hexa-methylene diisocyanate Ester, 1,3- trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4- tri-methyl hexamethylene diisocyanates Ester, 2,4,4- trimethyl hexamethylene diisocyanates, 1,9-, nine methylene diisocyanate, 1,10- decamethylene, two isocyanide Acid esters, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-diethyl ether diisocyanate, 4,4 '-diisocyanate of diphenyl methane-, neighbour Xylene diisocyanate, m xylene diisocyanate, paraxylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanic acid Ester), hexamethylene -1,3- dimethylene diisocyanate, hexamethylene-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5- naphthalene, two isocyanide Acid esters, paraphenylene diisocyanate, 3,3 '-xylene -4,4 '-diisocyanate, 4,4 '-diphenyl ether diisocyanates, Tetrachloro phenylene vulcabond, norbornene alkyl diisocyanate, hydrogenation 1,3- eylylene diisocyanate, hydrogenation Isosorbide-5-Nitrae- The chemical combination of the isocyanate compounds such as eylylene diisocyanate and the prepolymer type skeleton as derived from these compounds Object.In these compounds, particularly preferably toluene di-isocyanate(TDI) (tolylene diisocyanate, TDI) or diphenylmethyl Alkane diisocyanate (diphenylmethane diisocyanate, MDI), hexamethylene diisocyanate (hexamethylene diisocyanate, HDI), isophorone diisocyanate (isophorone diisocyanate, IPDI)。
The parent structure of block isocyanate compound in photosensitive polymer combination of the invention can be enumerated: biuret (biuret) type, isocyanuric acid ester (isocyanurate) type, adduct (adduct) type, 2 functional prepolymer types etc..
The block agent for forming the block structure of above-mentioned block isocyanate compound can be enumerated: oxime compound, lactamization Close object, phenolic compounds, alcoholic compound, amine compounds, activity methene compound, pyrazole compound, mercaptan compound, imidazoles system Compound, imide series compound etc..In these compounds, it is particularly preferably selected from oxime compound, lactam compound, phenolate Close object, alcoholic compound, amine compounds, activity methene compound, the block agent in pyrazole compound.
Above-mentioned oxime compound can enumerate oxime and ketoxime, can specifically illustrate: acetoxime (acetoxime), formaldoxime (formaldoxime), hexamethylene oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diphenyl-ketoxime etc..
Above-mentioned lactam compound can illustrate: epsilon-caprolactams, butyrolactam etc..
Above-mentioned phenolic compounds can illustrate: phenol, naphthols, cresols, xylenol, the phenol replaced through halogen etc..
Above-mentioned alcoholic compound can illustrate: methanol, ethyl alcohol, propyl alcohol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol list Alkyl ether, lactic acid alkyl ester etc..
As above-mentioned amine compounds, 1 grade of amine and 2 grades of amine can be enumerated, can also be aromatic amine, aliphatic amine, alicyclic Amine it is any, can illustrate: aniline, diphenylamine, aziridine, polyethyleneimine etc..
Above-mentioned activity methene compound can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, second Methyl acetoacetate etc..
Above-mentioned pyrazole compound can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc..
Above-mentioned mercaptan compound can illustrate: alkyl hydrosulfide, aryl mercaptan etc..
Workable block isocyanate compound can be used as commercially available product and obtain in photosensitive polymer combination of the invention It takes, such as preferably can be used: the Crow AP of resistance to moral Si Tebu (Coronate AP Stable) M, the resistance to moral in Crow (Coronate) 2503, the resistance to moral in Crow (Coronate) 2515, the resistance to moral in Crow (Coronate) 2507, the resistance to moral in Crow (Coronate) 2513, gram Luo Naide (Coronate) 2555, the resistance to moral of rice Leo (Millionate) MS-50 are (above by Japanese polyurethanes industry (Nippon Polyurethane Industry) (stock) manufacture), the resistance to moral of Plutarch (Takenate) B-830, the resistance to moral of Plutarch (Takenate) the resistance to moral of B-815N, Plutarch (Takenate) B-820NSU, the resistance to moral of Plutarch (Takenate) B-842N, the resistance to moral of Plutarch (Takenate) the resistance to moral of B-846N, Plutarch (Takenate) B-870N, the resistance to moral of Plutarch (Takenate) B-874N, the resistance to moral of Plutarch (Takenate) B-882N (being manufactured above by Mitsui Chemicals (stock)), Duo Naide (Duranate) 17B-60PX, Duo Naide (Duranate) 17B-60P, Duo Naide (Duranate) TPA-B80X, Duo Naide (Duranate) TPA-B80E, Duo Naide (Duranate) MF-B60X, Duo Naide (Duranate) MF-B60B, Duo Naide (Duranate) MF-K60X, Duo Naide (Duranate) MF-K60B, Duo Naide (Duranate) E402-B80B, Duo Naide (Duranate) SBN-70D, Duo Naide (Duranate) SBB-70P, Duo Naide (Duranate) K6000 (above by Asahi Chemical Industry chemical (stock) manufacture), De Shimo be (Desmodur) BL1100, De Shimo all (Desmodur) BL1265MPA/X, De Shimo all (Desmodur) BL3575/1, moral Scholar's mould all (Desmodur) BL3272MPA, De Shimo all (Desmodur) BL3370MPA, De Shimo all (Desmodur) BL3475BA/SN, De Shimo (Desmodur) BL5375MPA, De Shimo (Desmodur) VPLS2078/2, De Shimo are (Desmodur) BL4265SN, De Shimo all (Desmodur) PL340, De Shimo all (Desmodur) PL350, Su meter Dou (Sumidur) BL3175 (above by living to change Bayer carbamate (Sumika Bayer Urethane) (stock) manufacture) etc..
(G) sensitizer
Photosensitive polymer combination of the invention is in the combination with (B) photoacid generator, in order to promote its decomposition, preferably To contain sensitizer.Sensitizer absorbs actinic ray or radioactive ray and becomes electron excitation state.As electron excitation state Sensitizer contacted with photoacid generator and generate electronics transfer, energy transfer, fever the effects of.Photoacid generator produces as a result, Biochemical variation and decomposes, generate sour.The example of preferred sensitizer, which can be enumerated, belongs to following compounds, and 350nm extremely With the compound of absorbing wavelength under any wavelength of the wavelength region of 450nm.
The polynuclear aromatic same clan (such as: pyrene (pyrene), (perylene), triphenylene, anthracene, 9,10- dibutoxy anthracene, 9,10- diethoxy anthracenes, 3,7- dimethoxy anthracene, 9,10- dipropoxy anthracene), xanthene (xanthene) class (such as: fluorescence Element (fluorescein), eosin (eosin), erythrosine (erythrosine), rhodamine B (rhodamine B), Bangladesh's rose Rare red (rose bengal)), xanthone (xanthone) class (such as: xanthone, thioxanthone (thioxanthone), Dimethyl thioxanthone, diethyl thioxanthone), cyanine (cyanine) class (such as: thia-carbonyl cyanine (thiacarbocyanine), oxa- carbocyanine (oxacarbocyanine)), merocyanine (merocyanine) class (such as: portion Cyanine, carbonyl merocyanine (carbomerocyanine)) if, red cyanines (rhodacyanine) class, oxonols (oxonol) class, thiazine (thiazine) class (such as: thiophene gives repeated exhortations (thionine), methylenum careuleum (methylene blue), toluidine blue (toluidine Blue)), acridine (acridine) class (such as: acridine orange (acridine orange), chloroflavin (chloroflavin), a word used for translation Pyridine flavine (acriflavine)), acridone (acridone) class (such as: acridone, 10- butyl -2- chloro-acridine ketone, 10- fourth Base acridone), anthraquinone (anthraquinone) class (such as: anthraquinone), salt in side's acid (such as: side's acid inner salt), benzene second Alkenyl class, basicity styrene base class (such as: 2- [2- [4- (dimethylamino) phenyl] vinyl] benzoxazoles), cumarin (coumarin) class (such as: 7- lignocaine 4- methylcoumarin, 7- hydroxyl 4- methylcoumarin, 2,3,6,7- tetrahydro -9- first Base -1H, 5H, 11H [1] chromene simultaneously [6,7,8-ij] quinolizine -11- ketone).
In these sensitizers, preferably the 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.It is most preferably anthracene derivant in the polynuclear aromatic same clan.
Relative to 100 mass parts of photoacid generator of photosensitive polymer combination, photosensitive polymer combination of the invention In the additive amount of sensitizer be preferably 0 mass parts~1000 mass parts, more preferably 10 mass parts~500 mass parts, in turn Preferably 50 mass parts~200 mass parts.
Also two or more may be used.
(H) alkali compounds
Photosensitive polymer combination of the invention can contain (H) alkali compounds.(H) alkali compounds can be from chemical amplification Arbitrarily selection is in used in resist to use.Such as it can enumerate: aliphatic amine, aromatic amine, hetero ring type amine, level Four ammonium hydrogen Oxide, quarternary ammonium salt of carboxylic acid etc..The concrete example of these compounds can enumerate Japanese Patent Laid-Open 2011-221494 bulletin 0204~numbered paragraphs of numbered paragraphs 0207 in the compound recorded, these contents are incorporated herein in specification.In addition, The Thioureas such as N- cyclohexyl-N '-[2- (4- morpholinyl) ethyl] thiocarbamide can be used.
Workable alkali compounds can be used alone a kind in the present invention, and also two or more may be used.
Comprising other alkali compounds, relative to all solids ingredient in photosensitive polymer combination The content of 100 mass parts, (H) other alkali compounds in photosensitive polymer combination of the invention is preferably 0.001 mass Part~3 mass parts, more preferably 0.005 mass parts~1 mass parts.
(I) surfactant
Photosensitive polymer combination of the invention can contain (I) surfactant.(I) anion can be used in surfactant Any one of system, cationic system, nonionic system or both sexes, preferred surfactant are nonionic surfactant.
The example of nonionic surfactants can be enumerated: polyoxyethylene higher alkyl ether, polyoxyethylene higher alkyl Higher aliphatic acid diesters class, the silicone-based, fluorine system surfactant of phenyl ethers, polyoxyethylene glycol.In addition, can enumerate following Trade name: KP (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Po Lifuluo (Polyflow) (common prosperity society chemistry (stock) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials electronics is melted into the manufacture of (JEMCO) company), Mei Jiafa (Megafac) (DIC (DIC) (stock) system Make), Fu Lade (Fluorad) (Sumitomo 3M (stock) manufacture), A Sajia (Asahi Guard), Sha Fulong (Surflon) (rising sun nitre Sub (stock) manufacture), Pohle Floex (PoIyFox) (manufacture of Ou Nuofa (OMNOVA) company), SH-8400 (eastern beautiful DOW CORNING silicone (Toray Dow Corning Silicone)) etc. each series.
In addition, surfactant can be listed below copolymer as preference, which includes the following general formula (I-1) institute The structural unit A and structural unit B of expression, and utilize tetrahydrofuran (tetrahydrofuran, THF) as solvent In the case of gel permeation chromatography be measured obtained by polystyrene convert weight average molecular weight (Mw) be 1,000 with Above, 10,000 or less.
General formula (I-1)
[changing 23]
(in formula (I-1), R401And R403Respectively indicate hydrogen atom or methyl, R402Indicate that carbon number 1 or more, 4 is below straight Chain alkylidene, R404Indicate that hydrogen atom or 1 or more carbon number, 4 alkyl below, L indicate 3 or more carbon number, 6 alkylidenes below, P and q is the quality percentage for indicating polymerization ratio, and p indicates that 10 mass % or more, 80 mass % numerical value below, q indicate 20 matter % or more, 90 mass % numerical value below are measured, r indicates that 1 or more, 18 integers below, s indicate 1 or more, 10 integers below.)
Above-mentioned L is preferably branched alkylene groups represented by the following general formula (I-2).R in general formula (I-2)405Indicate carbon number 1 Above, 4 alkyl below, with regard to compatibility and for the aspect of the wetability in the face that is applied, preferably carbon number 1 or more, 3 or less Alkyl, the more preferably alkyl of carbon number 2 or 3.The sum of p and q (p+q) are preferably p+q=100, i.e. 100 mass %.
General formula (I-2)
[changing 24]
The weight average molecular weight (Mw) of above-mentioned copolymer is more preferably 1,500 or more, 5,000 or less.
These surfactants, which can be used alone, or to be used in mixed way two or more by a kind.
Relative to 100 mass parts of all solids ingredient in photosensitive polymer combination, photoresist group of the invention The additive amount for closing (I) surfactant in object is preferably 10 below the mass more preferably 0.001 mass parts~10 mass Part, and then preferably 0.01 mass parts~3 mass parts.
(J) antioxidant
Photosensitive polymer combination of the invention can contain antioxidant.As antioxidant, well known antioxygen can be contained Agent.The coloring that can prevent cured film is had the advantage that by addition antioxidant, or can be reduced as caused by decomposing Film thickness is reduced, in addition, heat resistant transparent is excellent.
Such antioxidant can for example be enumerated: phosphorous antioxidant, amides, hydrazides, amine antioxidant of being obstructed, sulphur Be antioxidant, phenolic antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, Hydroxy amine derivatives etc..In these compounds, with regard to the coloring of cured film, film thickness reduction viewpoint for, particularly preferably phenol system Antioxidant, acyl amine antioxidant, hydrazides system antioxidant, sulfur antioxidant.These compounds can be used alone a kind, Two or more can also be mixed.
The commercially available product of phenolic antioxidant can for example be enumerated: Ai Di Coase tower wave (Adekastab) AO-15, Ai Di Coase Tower wave (Adekastab) AO-18, Ai Di Coase tower wave (Adekastab) AO-20, Ai Di Coase tower wave (Adekastab) AO- 23, Ai Di Coase tower wave (Adekastab) AO-30, Ai Di Coase tower wave (Adekastab) AO-37, Ai Di Coase tower wave (Adekastab) AO-40, Ai Di Coase tower wave (Adekastab) AO-50, Ai Di Coase tower wave (Adekastab) AO-51, Chinese mugwort Enlightening Coase tower wave (Adekastab) AO-60, Ai Di Coase tower wave (Adekastab) AO-70, Ai Di Coase tower wave (Adekastab) AO-80, Ai Di Coase tower wave (Adekastab) AO-330, Ai Di Coase tower wave (Adekastab) AO- 412S, Ai Di Coase tower wave (Adekastab) AO-503, Ai Di Coase tower wave (Adekastab) A-611, Ai Di Coase tower wave (Adekastab) A-612, Ai Di Coase tower wave (Adekastab) A-613, Ai Di Coase tower wave (Adekastab) PEP-4C, Ai Di Coase tower wave (Adekastab) PEP-8, Ai Di Coase tower wave (Adekastab) PEP-8W, Ai Di Coase tower wave (Adekastab) PEP-24G, Ai Di Coase tower wave (Adekastab) PEP-36, Ai Di Coase tower wave (Adekastab) PEP- 36Z, Ai Di Coase tower wave (Adekastab) HP-10, Ai Di Coase tower wave (Adekastab) 2112, Ai Di Coase tower wave (Adekastab 260, Ai Di Coase tower wave (Adekastab) 522A, Ai Di Coase tower wave (Adekastab) 1178, Ai Dike Si Tabo (Adekastab) 1500, Ai Di Coase tower wave (Adekastab) C, Ai Di Coase tower wave (Adekastab) 135A, Chinese mugwort Enlightening Coase tower wave (Adekastab) 3010, Ai Di Coase tower wave (Adekastab) TPP, Ai Di Coase tower wave (Adekastab) CDA-1, Ai Di Coase tower wave (Adekastab) CDA-6, Ai Di Coase tower wave (Adekastab) ZS-27, Ai Di Coase tower wave (Adekastab) ZS-90, Ai Di Coase tower wave (Adekastab) ZS-91 (being manufactured above by Ai Dike (stock)), Yi Jialesi (Irganox) 245FF, Yi Jialesi (Irganox) 1010FF, Yi Jialesi (Irganox) 1010, Yi Jialesi (Irganox) MD1024, Yi Jialesi (Irganox) 1035FF, Yi Jialesi (Irganox) 1035, Yi Jialesi (Irganox) 1098, Yi Jialesi (Irganox) 1330, Yi Jialesi (Irganox) 1520L, Yi Jialesi (Irganox) 3114, Yi Jialesi (Irganox) 1726, easily plus Floex (Irgafos) 168,295 (BASF of Yi Jiamode (Irgamod) (stock) manufacture) etc..It wherein, can be suitable for using Ai Di Coase tower wave (Adekastab) AO-60, Ai Di Coase tower wave (Adekastab) AO-80, Yi Jialesi (IIrganox) 1726, Yi Jialesi (IIrganox) 1035, Yi Jialesi (IIrganox)1098。
Relative to all solids ingredient of photosensitive polymer combination, the content of antioxidant be preferably 0.1 mass %~ 10 mass %, the more preferably 0.2 mass % of mass %~5, particularly preferably 0.5 mass of mass %~4 %.By being set as the model It encloses, and obtains the substantially transparent property for being formed by film, and sensitivity when pattern formation also becomes good.
In addition, as the additive other than antioxidant, it can also be by " (daily magazine industry is new for the new expansion of polymeric additive Hear society (stock)) " in the various ultraviolet absorbing agents recorded or matal deactivator etc. make an addition to photosensitive resin composition of the invention In object.
[acid proliferation generator]
Photosensitive polymer combination of the invention can use acid proliferation generator for the purpose for improving sensitivity.
Workable acid proliferation generator is can to react further to generate acid by acid catalyst in the present invention, makes reaction system The compound that interior acid concentration rises is the compound being stabilized in the state of there is no acid.Such compound is due to logical It crosses 1 secondary response and increases by 1 or more acid, so accelerate to react with the progress of reaction, but due to generated acid Itself cause self to decompose, so the intensity of acid generated here, in terms of acid ionization constant, pKa, preferably 3 hereinafter, especially Preferably 2 or less.
The concrete example of acid proliferation generator can be enumerated: 0203~section of numbered paragraphs of Japanese Patent Laid-Open 10-1508 bulletin Fall number 0223,0016~numbered paragraphs of numbered paragraphs 0055 of Japanese Patent Laid-Open 10-282642 bulletin and Japan The compound recorded in patent special table level 9-512498 bulletin the 2nd row of the 12nd row~47th page of page 39, these contents are incorporated to In present specification.
Workable acid proliferation generator can be enumerated in the present invention decomposes using by acid that photoacid generator generates, generation dichloro The pKa such as acetic acid, trichloroacetic acid, methanesulfonic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid are the compound of 3 acid below.
It can specifically enumerate:
[changing 25]
Deng.
For the viewpoint of exposure portion and the dissolution contrast in unexposed portion, relative to 100 mass parts of photoacid generator, acid Content of the multiplication agent in photosensitive composite is preferably set as 10 mass parts~1,000 mass parts, and then is preferably set as 20 Mass parts~500 mass parts.
[development accelerant]
Photosensitive polymer combination of the invention can contain development accelerant.
Development accelerant can refer to 0171~numbered paragraphs of numbered paragraphs of Japanese Patent Laid-Open 2012-042837 bulletin 0172 record, the content are incorporated herein in specification.
Development accelerant can be used alone a kind, and also two or more may be used.
For sensitivity and the viewpoint of residual film ratio, relative to 100 mass parts of all solids ingredient of photosensitive composite, originally The additive amount of development accelerant in the photosensitive polymer combination of invention is preferably 0 mass parts~30 mass parts, more preferably 0.1 mass parts~20 mass parts, most preferably 0.5 mass parts~10 mass parts.
In addition, 0120~section of numbered paragraphs of Japanese Patent Laid-Open 2012-8223 bulletin also can be used in other additives The hot radical producing agent recorded in number 0121, the nitrogenous compound recorded in WO2011/136074A1 and hot acid is fallen to produce Raw agent, these contents are incorporated herein in specification.
<preparation method of photosensitive polymer combination>
Each ingredient is mixed with defined ratio and using any means, stirring and dissolving and prepare photosensitive resin composition Object.Such as ingredient can also be dissolved in solvent and after solution is made in advance respectively, these solution are mixed with defined ratio And prepare resin combination.The composition solution prepared in the above described manner can also be used the filter etc. that aperture is 0.2 μm to carry out After filtering, for using.
[manufacturing method of cured film]
Then, the manufacturing method of cured film of the invention is illustrated.
The manufacturing method of cured film of the invention preferably comprises the step of (1) below~(5).
(1) step being coated on photosensitive polymer combination of the invention on substrate；
(2) the step of solvent is removed from the photosensitive polymer combination being coated with；
(3) the step of photosensitive polymer combination for eliminating solvent being exposed using actinic ray；
(4) the step of being developed using aqueous developer to exposed photosensitive polymer combination；
(5) the rear baking procedure of thermmohardening is carried out to developed photosensitive polymer combination.
Each step is successively illustrated below.
(1) in application step, preferably photosensitive polymer combination of the invention is coated on substrate and packet is made Solvent-laden wet film.Alkali cleaning or plasma are carried out preferably before photosensitive polymer combination is coated on substrate The cleaning of the substrates such as cleaning more preferably after base-plate cleaning and then is handled substrate surface with hexamethyldisilazane. By carrying out the processing, there are the tendencies that adhesion of the photosensitive polymer combination to substrate improves.With hexamethyldisilazane The method handled substrate surface is not particularly limited, such as can be enumerated and be exposed the substrate to hexamethyldisilazane in advance Method etc. in steam.
Aforesaid substrate can enumerate inorganic substrate, resin, resin composite materials etc..
Inorganic substrate can for example be enumerated: glass, quartz, silicone, silicon nitride, and be vapor-deposited on substrate as described above The composite substrate of molybdenum, titanium, aluminium, copper etc..
As resin, following resin: polybutylene terephthalate, polyethylene terephthalate, poly- naphthalene two can be enumerated Formic acid second diester, poly- naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyether sulfone, polyarylate, allyl glycol carbon Acid esters, polyamide, polyimides, polyamidoimide, polyetherimide, polybenzoxazole (polybenzazole), polyphenylene sulfide The fluororesin such as ether, polycyclic alkene, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, It is silicone resin, ionomeric resins, cyanate ester resin, crosslinking fumaric acid diester, cyclic polyolefin, aromatic ether, suitable The synthetic resin such as butylmaleimide-alkene, cellulose, episulfide (episulfide) compound.
These substrates in the form of above-mentioned directly use the case where it is few, generally according to final product form and formed for example thin The multilayer laminate constructions of film transistor (Thin Film Transistor, TFT) element etc.
The coating method of substrate is not particularly limited, such as can be used: slot coated method, gunite, roller coating method, rotation Turn the methods of rubbing method, cast coating method, slit and rotary process (slit-and-spin method).It in turn, can also be using such as The so-called pre- wet process (pre-wet method) recorded in Japanese Patent Laid-Open 2009-145395 bulletin.
Wet type film thickness when coating is not particularly limited, and can be coated with film thickness depending on the application, usually with 0.5 μm~ 10 μm of range uses.
(2) it in solvent removal step, by decompression (vacuum) and/or heating, is removed from the above-mentioned film being coated with molten Agent and dry coating is formed on substrate.The heating condition of solvent removal step is preferably 70 DEG C~130 DEG C and 30 seconds~300 seconds Left and right.In the case where temperature and time is above range, there are the adhesion of pattern is better, and residue can also further subtract Few tendency.
(3) in step of exposure, to the substrate for being provided with film, photochemical penetrate is irradiated across the mask with predetermined pattern Line.In the step, photoacid generator decomposes and generates acid.Using the catalyst action of generated acid, apply contained in film component Sour decomposability base it is hydrolyzed and generate carboxyl or phenolic hydroxyl group.
It can be used using photoactinic exposure light source: Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemistry Lamp, light emitting diode (light emitting diode, LED) light source, excimer laser generation device etc., it is preferable to use G ray (436nm), i ray (365nm), h ray (405nm) etc. have wavelength 300nm or more, 450nm are below photochemical to penetrate Line.In addition, can also optionally pass through long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter (band pass ) etc filter light splitting filter adjusts irradiation light.
Exposure device can be used: mirror surface projection is directed at exposer (mirror projection aligner), stepper (stepper), scanner (scanner), close induction type (proximity), contact (contact), microlens array The exposure machine of the various modes such as (microlens array), laser explosure.
There is the region of acid catalyst to heat after being exposed to accelerate above-mentioned hydrolysis generating: exposure Toast (Post Exposure Bake) (hereinafter also referred to " PEB ") afterwards.By PEB, it can promote and carboxylic is generated by sour decomposability base Base or phenolic hydroxyl group.Temperature in the case where carrying out PEB is preferably 30 DEG C or more, 130 DEG C hereinafter, more preferably 40 DEG C with It is upper, 110 DEG C hereinafter, particularly preferably 50 DEG C or more, 100 DEG C or less.
Wherein, the activation evergy that the sour decomposability base in the present invention is decomposed due to acid is low, is easy caused by reason exposure Acid from photoacid generator and decompose, generate carboxyl or phenolic hydroxyl group, so PEB can also need not be carried out, and pass through development To form erect image.
(4) in development step, using alkaline-based developer will there is the polymer of free carboxyl or phenolic hydroxyl group to carry out Development.By that will include the exposure with the resin combination for being easy to be dissolved in carboxyl or phenolic hydroxyl group in alkaline-based developer The removal of portion region, and form erect image.
It preferably include alkali compounds in developer solution used in development step.Alkali compounds for example can be used: hydrogen The alkali metal hydroxides such as lithia, sodium hydroxide, potassium hydroxide；The alkali carbonates class such as sodium carbonate, potassium carbonate；Carbonic acid The alkali metal hydrogencarbonates class such as hydrogen sodium, saleratus；Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, bursine Ammonium hydroxide classes such as (choline hydroxide)；The aqueous solution of sodium metasilicate, sodium metasilicate etc..In addition, can also will be in above-mentioned alkali Aqueous solution added with the water-miscible organic solvents such as suitable methanol or ethyl alcohol or surfactant in the aqueous solution of class is used as aobvious Shadow liquid.
Preferred developer solution can be enumerated: 0.4% aqueous solution of tetraethyl ammonium hydroxide, 0.5% aqueous solution, 0.7% water-soluble Liquid, 2.38% aqueous solution.
The pH value of developer solution is preferably 10.0~14.0.
Developing time is preferably 30 seconds~500 seconds, in addition, the gimmick of development can be covering liquid method (puddle method), leaching Stain method (dipping method) etc. it is any.After development, flowing water cleaning in 30 seconds~300 seconds can be usually carried out, institute is formed The pattern needed.
After development, rinsing step can also be carried out.It is clear by being carried out with pure water etc. to the substrate after development in rinsing step It washes, and carries out accompanying developer solution removal, development residue removal.Well known method can be used in ELUTION METHOD.Such as it can enumerate Spray elution or dipping elution etc..
(5) in rear baking procedure, by being heated to resulting erect image, and sour decomposability base is thermally decomposed, Carboxyl or phenolic hydroxyl group are generated, is crosslinked with bridging property base, crosslinking agent etc., thus can form cured film.The heating is preferred To use the heating devices such as heating plate or baking oven, at defined temperature, such as 180 DEG C~250 DEG C, adding for stipulated time is carried out Heat treatment, such as if then being carried out in heating plate 5 minutes~90 minutes, then carried out if baking oven 30 minutes~120 minutes.Pass through Such cross-linking reaction is carried out, the superior protective film such as heat resistance, hardness or interlayer dielectric can be formed.In addition, being heated By carrying out in a nitrogen environment when processing, the transparency also can further improve.
Before rear baking, toast (intermediate baking procedure after carrying out after can also being toasted at relatively low temperatures It is additional).Underway baking in the case where, heated preferably at 90 DEG C~150 DEG C 1 minute~after sixty minutes, at 200 DEG C It is toasted after being carried out at a high temperature of above.In addition, also centre baking, rear baking can be divided into for 3 the multistage more than stage to carry out Heating.By intermediate baking as described above, afterwards the operation toasted, can adjust the cone angle of pattern.Heating can be used in these heating Heating means well known to plate, baking oven, infrared heater etc..
In addition, (rear exposure can be exposed again to figuratum substrate progress is formed using actinic ray before rear baking comprehensively Light) after, it is toasted after progress, thus generates acid by being present in the photoacid generator of unexposed portion, as promotion cross-linking step Catalyst and function, and can promote the sclerous reaction of film.Preferred light exposure in the case where including post-exposure step is excellent It is selected as 100mJ/cm2~3,000mJ/cm2, particularly preferably 100mJ/cm2~500mJ/cm2。
On the other hand, in characteristic (penetrance, chemical-resistant, relative dielectric constant and the basal substrate as cured film Adhesion, resistance to dry-etching etc.) compared with can also omit and expose again the case where exposing again superior situation comprehensively in comprehensively Light step.By omitting comprehensively step of exposure again, productivity also can be improved.
In turn, anti-dry etch also is used as by the cured film that photosensitive polymer combination of the invention obtains.It is inciting somebody to action In the case where being used as anti-dry etch by the rear resulting cured film of baking procedure thermmohardening, etching process can carry out ash The dry-etchings processing such as change, plasma etching, ozone etching.
[cured film]
Cured film of the invention is the cured film of acquisition by photosensitive polymer combination hardening of the invention.
Cured film of the invention can be suitable for use as interlayer dielectric.In addition, cured film of the invention preferably utilizes this hair The forming method of bright cured film and the cured film obtained.
Using photosensitive polymer combination of the invention, it is excellent and in the case where being baked at high temperature to obtain insulating properties Also with the interlayer dielectric of high transparency.There is height using interlayer dielectric made of photosensitive polymer combination of the invention The transparency, and cured film physical properties excellent, therefore can be used for the purposes of organic EL display device or liquid crystal display device.
[liquid crystal display device]
Liquid crystal display device of the invention includes cured film of the invention.
Liquid crystal display device of the invention is formed in addition to having the photosensitive polymer combination using aforementioned present invention Other than planarization film or interlayer dielectric, there is no particular restriction, can enumerate the known liquid crystal display device for taking various structures.
For example, thin film transistor (TFT) included by liquid crystal display device of the invention (Thin-Film Transistor, TFT) Concrete example can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention due to Electrical characteristics are excellent, so be combined into these TFT and be preferably used.
In addition, the liquid crystal drive mode that liquid crystal display device of the invention can be taken can be enumerated: twisted nematic (Twisted Nematic, TN) mode, vertical orientation (Vertical Alignment, VA) mode, coplanar switching (In-Plane- Switching, IPS) mode, fringing field switching (Fringe Field Switching, FFS) mode, optical compensation curved (Optical Compensated Bend, OCB) mode etc..
During panel is constituted, the liquid crystal display of colorful optical filter array (Color Filter on Allay, COA) mode is filled Cured film of the invention can also be used in setting, can be used, for example, as the organic insulation of Japanese Patent Laid-Open 2005-284291 bulletin The organic insulating film (212) of film (115) or Japanese Patent Laid-Open 2005-346054 bulletin.
In addition, the specific of the liquid crystal orientation film that liquid crystal display device of the invention can be taken aligned enumerate friction and takes Xiang Fa, optical alignment method etc..In addition, also using Japanese Patent Laid-Open 2003-149647 bulletin or Japanese Patent Laid-Open 2011- The polymer stabilizing recorded in No. 257734 bulletins is orientated (Polymer Sustained Alignment, PSA) technology and passes through poly- Object orientation is closed to support.
In addition, photosensitive polymer combination of the invention and cured film of the invention are not limited to such use, it can For multiple use.For example, can also be suitable for the protection of colored filter other than planarization film or interlayer dielectric Film is arranged to the distance piece for being kept fixed the thickness of the liquid crystal layer in liquid crystal display device or in solid photographic element In the lenticule etc. of colorized optical filtering on piece.
Fig. 1 is the conceptual sectional view for indicating an example of liquid crystal display device 10 of active matrix mode.The color liquid crystal Display device 10 is liquid crystal display panel overleaf with back light unit 12, and liquid crystal panel has the element of TFT 16, the TFT 16 element is corresponding with all pixels being configured between the 2 pieces of glass substrates 14,15 for being pasted with light polarizing film.It is formed in glass base On each element on plate, by the contact hole 18 being formed in cured film 17, the ito transparent electrode of the tangible pixel electrode of wiring 19.Be provided on ito transparent electrode 19 layer of liquid crystal 20 with configured with black matrix" RGB (red green blue, RGB) colored filter 22.
The light source of backlight is not particularly limited, and well known light source can be used.Such as can enumerate: White LED, blue are red Color green etc. is multi-colored led, fluorescent lamp (cold-cathode tube), organic EL etc..
In addition, liquid crystal display device may be made as three-dimensional (three dimensional, 3D) (stereo vision) type device, Or touch screen type device is made.And then it may be made as flexible type, and can be used as Japanese Patent Laid-Open 2011-145686 bulletin The 2nd interlayer dielectric (48) or Japanese Patent Laid-Open 2009-258758 bulletin interlayer dielectric (520).
[organic EL display device]
Organic EL display device of the invention includes cured film of the invention.
Organic EL display device of the invention is formed in addition to having the photosensitive polymer combination using aforementioned present invention Planarization film or interlayer dielectric other than, there is no particular restriction, can enumerate the well known various organic EL for taking various structures Display device or liquid crystal display device.
For example, thin film transistor (TFT) included by organic EL display device of the invention (Thin-Film Transistor, TFT concrete example) can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention Since electrical characteristics are excellent, so be combined into these TFT and be preferably used.
Fig. 2 is the composition concept map of an example of organic EL display device.Indicate the organic EL display device of bottom emission type In substrate schematic cross sectional view, including planarization film 4.
Bottom-gate (bottom gate) type TFT 1 is formed on glass substrate 6, forms packet to cover the state of the TFT 1 Containing Si3N4Insulating film 3.After forming the contact hole of illustration omitted herein on the insulating film 3, via the contact hole in insulating film 3 It is upper to form the wiring 2 (being highly 1.0 μm) for being connected to TFT 1.Wiring 2 is will be formed between TFT 1 or in later-mentioned step The line that is connect with TFT 1 of organic EL element.
In turn, in order to planarize the bumps as caused by the formation of wiring 2, and it is concave-convex as caused by wiring 2 to be embedded to State forms planarization layer 4 on the insulating film 3.
The organic EL element of bottom emission type is formed on planarization film 4.That is, on planarization film 4, comprising ITO One electrode 5 is to be connected to wiring 2 via contact hole 7 to be formed.In addition, first electrode 5 is equivalent to the anode of organic EL element.
The insulating film 8 for forming the shape of the periphery of covering first electrode 5 can prevent the first electricity by the way that the insulating film 8 is arranged The short circuit between second electrode formed in pole 5 and thereafter step.
In turn, not shown in Fig. 2, across required pattern mask, successively hole transmission layer, organic light emission is arranged in vapor deposition Layer, electron transfer layer, then, the entire surface above substrate form the second electrode comprising Al, by using UV cured Type epoxy resin and be bonded with glass for sealing plate to seal, obtain and connect in each organic EL element to drive it Active matrix organic EL display device made of TFT 1.
Photosensitive polymer combination of the invention is due to hardenability and cured film excellent, so as micro-electro-mechanical systems System (microelectromechanical system, the MEMS) structural elements of element, will use photonasty tree of the invention Oil/fat composition and the resist pattern formed are made dividing wall, or as Mechanical Driven part a part and assembled and It uses.Such MEMS element can for example be enumerated: surface acoustic wave (surface acoustic wave, SAW) filter, body sound Wave (bulk acoustic wave, BAW) filter, gyro sensor (gyro sensor), the micro- shutter of display (microshutter), imaging sensor (image sensor), Electronic Paper, ink gun (inkjet head), biochip (biochip), the parts such as sealant.More specific example is illustrated in Japanese patent special table 2007-522531 bulletin, Japan specially In sharp special open 2008-250200 bulletin, Japanese Patent Laid-Open 2009-263544 bulletin etc..
Photosensitive polymer combination of the invention is since flatness or the transparency are excellent, so for example can also be used for being formed: The stack layer (bank layer) (16) and planarization film recorded in Fig. 2 of Japanese Patent Laid-Open 2011-107476 bulletin The dividing wall (12) and planarization film (102) (57), recorded in Fig. 4 (a) of Japanese Patent Laid-Open 2010-9793 bulletin, The stack layer (221) and the 3rd interlayer dielectric (216b) recorded in Figure 10 of Japanese Patent Laid-Open 2010-27591 bulletin, The 2nd interlayer dielectric (125) and the 3rd interlayer recorded in Fig. 4 (a) of Japanese Patent Laid-Open 2009-128577 bulletin are exhausted Velum (126), Japanese Patent Laid-Open 2010-182638 bulletin Fig. 3 in the planarization film (12) recorded and pixel separation Insulating film (14) etc..
Embodiment
It is exemplified below embodiment, further progress of the present invention is illustrated.Material shown in following embodiment uses Amount, ratio, process content, processing routine etc. can then be suitably changed without departing from purport of the invention.Therefore, of the invention Range is not limited to concrete example as shown below.In addition, as long as no special instructions, then " part ", " % " are quality criteria.
In following synthesis example, following symbol respectively indicates following compound.
MATHF: methacrylic acid tetrahydrofuran -2- base ester (composite)
MAEVE: methacrylic acid 1- ethoxy ethyl ester (and the manufacture of Wako Pure Chemical Industries company)
MACHOE: methacrylic acid 1- (cyclohexyloxy) ethyl ester (composite)
MATHP: methacrylic acid tetrahydro -2H- pyrans -2- base ester (village Xin Zhong chemical industry (stock) manufacture)
GMA: glycidyl methacrylate (and Wako Pure Chemical Industries (stock) manufacture)
OXE-30: methacrylic acid (3- Ethyloxetane -3- base) methyl esters (Osaka Organic Chemical Industry (stock) system It makes)
NBMA: n-butoxy methyl acrylamide (beautiful positive (stock) manufacture of Mitsubishi)
MAA: methacrylic acid (and Wako Pure Chemical Industries (stock) manufacture)
HEMA: 2-hydroxyethyl methacrylate (and Wako Pure Chemical Industries (stock) manufacture)
MMA: methyl methacrylate (and Wako Pure Chemical Industries (stock) manufacture)
St: styrene (and Wako Pure Chemical Industries (stock) manufacture)
DCPM: two ring pentyl ester of methacrylic acid (Hitachi's chemical conversion industry (stock) manufacture)
V-601: 2,2 '-azo of dimethyl-bis- (2 Methylpropionic acid esters) (and Wako Pure Chemical Industries (stock) manufacture)
V-65:2,2 '-azos bis- (2,4- methyl pentane nitriles) (and Wako Pure Chemical Industries (stock) manufacture)
MEDG: diethylene glycol ethyl methyl ether (eastern nation's chemical industry (stock) manufacture, Ha Yisuo (Hisolve) EDM)
PGMEA: acetic acid methoxyl group propyl ester (manufacture of Showa electrician company)
<synthesis of MATHF>
Methacrylic acid (86g, 1mol) is cooled to 15 DEG C in advance, is added camphorsulfonic acid (4.6g, 0.02mol).At this 2- dihydrofuran (71g, 1mol, 1.0 equivalent) is added dropwise in solution.After stirring 1 hour, add saturated sodium bicarbonate (500mL), with Ethyl acetate (500mL) extracts, and after magnesium sulfate drying, insoluble matter is filtered, then depressurize at 40 DEG C or less dense The yellow oil of residue is evaporated under reduced pressure and obtains the metering system that boiling point (bp.) is 54~56 DEG C/3.5mmHg fraction by contracting Sour tetrahydro -2H- furans -2- base ester (MATHF) 125g is as colorless oil (yield 80%).
In addition, other than MACHOE is changed to the compound of corresponding 2- dihydrofuran, with side identical with above-mentioned MATHF Method is synthesized.
[synthesis of polymer A1]
MEDG (89g) is added in three-necked flask, is warming up to 90 DEG C in a nitrogen environment.In the solution dissolve MAA (at For the amount of the 9.5mol% in all monomer components), MATHF (amount as the 43mol% in all monomer components), GMA (phase As the 47.5mol% in all monomer components), V-65 (relative to total 100mol% of all monomer components, is equivalent to 4mol%), spend be added dropwise within 2 hours.It is stirred 2 hours after completion of dropwise addition, terminates reaction.Thus to obtain polymer Al.In addition, will The ratio of the total amount of MEDG and other compositions is set as 60: 40.That is, preparing the polymer solution that solid component concentration is 40%.
The type of used monomer, polymerization initiator etc. are changed to as shown in following tables, Lai Hecheng other polymers.
The numerical value of not especially mark unit in above-mentioned table is as unit of mol%.In addition, the numerical value of polymerization initiator is Mol% monomer component being set as in the case of 100mol%.
Solid component concentration can be calculated using the following formula.
Solid component concentration: monomer weight/(monomer weight+weight of solvent) × 100 (unit: quality %)
In addition, reaction temperature is set as 90 DEG C in the case where using V-601 as initiator, use V-65 as Reaction temperature is set as 70 DEG C in the case where initiator.
<embodiment and comparative example>
(1) preparation of photosensitive polymer combination
The dissolution of each ingredient shown in following table 2, table 3 is mixed in solvent (PGMEA), until solid component concentration reaches Until 32%, uniform solution is made, then using the polytetrafluoroethylene (PTFE) mistake in the aperture (pore size) with 0.1 μm Filter is filtered, and prepares the solution of the photosensitive polymer combination of embodiment and comparative example respectively.In addition, in table 2, table 3 Each component amount additive amount indicate mass parts.
Indicate that the detailed content of the contracted notation of each compound used in embodiment and comparative example is as described below.
<polymer>
A1~A10: the polymer synthesized according to above-mentioned synthesis example
A11: Zhuan Chen (Joncryl) 67 (BASF AG's manufacture)
<photoacid generator>
B1: the compound (composite) of following structures
B2: the compound (composite) of following structures
B3: the compound (composite) of following structures
B4:CGI-1397 (BASF AG's manufacture)
B5: the compound of following structures (is recorded in the paragraph 0108 of foundation Japanese patent special table 2002-528451 bulletin Method synthesize)
[changing 26]
<synthesis of B1>
Beta naphthal (10g), chlorobenzene (30mL) aaerosol solution in add aluminium chloride (10.6g), 2- chlorpromazine chloride Mixed liquor is heated to 40 DEG C by (10.1g), reacts it 2 hours.Under ice cooling, 4,4N HCl/water is added dropwise into reaction solution Solution (60mL), addition ethyl acetate (50mL) carry out liquid separation.Potassium carbonate (19.2g) is added in organic layer, it is anti-at 40 DEG C After answering 1 hour, addition 2N HCL aqueous solution (60mL) carries out liquid separation, will using diisopropyl ether (10mL) after organic layer is concentrated Crystallization progress is slurried again, and filtering is dried and obtains ketone compound (6.5g).
Resulting ketone compound (3.0g), methanol (18mL) aaerosol solution in add acetic acid (7.3g), 50 weight % Aqueous hydroxylamine (8.0g) is heated to reflux 10 hours.It after placing cooling, adds water (50mL), the crystallization being precipitated is carried out After filtering, cold methanol cleaning, dries and obtain oxime compound (2.4g).
It is dissolved in resulting oxime compound (1.8g) in acetone (20mL), adds triethylamine under ice cooling, 4 (1.5g), paratoluensulfonyl chloride (2.4g), is warming up to room temperature and reacts 1 hour.Water (50mL) is added in reaction solution, will be analysed Slurried again with methanol (20mL) progress after crystallization filtering out, filtering is dried and obtains B1 (2.3g).
In addition, B11H-NMR wave spectrum (300MHz, CDCl3) are as follows: 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)。
<synthesis of B2>
It is dissolved in beta naphthal (20g) in n,N-dimethylacetamide (150mL), addition potassium carbonate (28.7g), 2- bromine are pungent Acetoacetic ester (52.2g) reacts 2 hours at 100 DEG C.Water (300mL) is added in reaction solution, ethyl acetate (200mL) carries out Liquid separation after organic layer is concentrated, adds 48 weight % sodium hydrate aqueous solutions (23g), ethyl alcohol (50mL), water (50mL), reaction 2 Hour.Reaction solution is poured into 1N HCL aqueous solution (500mL), by the crystallization being precipitated filtering, washes and obtains carboxylic acid runic Afterwards, polyphosphoric acid 30g is added, is reacted 30 minutes at 170 DEG C.Reaction solution is poured into water (300mL), ethyl acetate is added (300mL) carries out liquid separation, is purified after organic layer is concentrated using silica gel column chromatography, obtains ketone compound (10g).
Resulting ketone compound (10.0g), methanol (100mL) aaerosol solution in add sodium acetate (30.6g), hydrochloric acid Hydroxylamine (25.9g), magnesium sulfate (4.5g), are heated to reflux 24 hours.After placing cooling, water (150mL), ethyl acetate are added (150mL) carries out liquid separation, and organic layer is carried out 4 liquid separations with water 80mL, is purified after concentration using silica gel column chromatography And obtain oxime compound (5.8g).
To gained oxime (3.1g), sulfonic acid esterification is carried out in a manner of identical with B1, is obtained B2 (3.2g).
In addition, B21H-NMR wave spectrum (300MHz, CDCl3) are as follows: δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4~1.2 (m, 8H), 0.8 (t, 3H).
<synthesis of B3>
Other than replacing the paratoluensulfonyl chloride in B1 and using benzene sulfonyl chloride, B3 is synthesized in a manner of identical with B1.
In addition, B31H-NMR wave spectrum (300MHz, CDCl3) are as follows: δ=8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (d, 3H).
<aromatic heterocyclic compounds>
C1: oxazole (and Wako Pure Chemical Industries (stock) manufacture)
C2:2,4,5- trimethyl oxazoles (and Wako Pure Chemical Industries (stock) manufacture)
C3: isoxazole (and Wako Pure Chemical Industries (stock) manufacture)
C4:5- methylisoxazole (and Wako Pure Chemical Industries (stock) manufacture)
C5: thiazole (and Wako Pure Chemical Industries (stock) manufacture)
C6:5- methylthiazol (and Wako Pure Chemical Industries (stock) manufacture)
C7: isothiazole (and Wako Pure Chemical Industries (stock) manufacture)
C8:1,2,3- triazoles (and Wako Pure Chemical Industries (stock) manufacture)
C9:1,2,4- triazoles (and Wako Pure Chemical Industries (stock) manufacture)
C10:1,2,3- oxadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C11:1,2,4- oxadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C12:1,3,4- oxadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C13:1,2,5- oxadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C14:1,2,3- thiadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C15:1,2,4- thiadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C16:1,3,4- thiadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C17:1,2,5- thiadiazoles (and Wako Pure Chemical Industries (stock) manufacture)
C18: pyrimidine (and Wako Pure Chemical Industries (stock) manufacture)
C19:1,2,3- triazines (and Wako Pure Chemical Industries (stock) manufacture)
C20:1,2,4- triazines (and Wako Pure Chemical Industries (stock) manufacture)
C21:1,3,5- triazines (and Wako Pure Chemical Industries (stock) manufacture)
C22:1,2- benzopyrazoles (and Wako Pure Chemical Industries (stock) manufacture)
C23: benzoxazoles (and Wako Pure Chemical Industries (stock) manufacture)
C24:5- methylbenzoxazole (and Wako Pure Chemical Industries (stock) manufacture)
C25:1,2- benzo isoxazole (and Wako Pure Chemical Industries (stock) manufacture)
C26: benzothiazole (and Wako Pure Chemical Industries (stock) manufacture)
C27:2,6- dimethyl-benzothiazole (and Wako Pure Chemical Industries (stock) manufacture)
C28:2,1,3- benzoxadiazole (and Wako Pure Chemical Industries (stock) manufacture)
C29:2,1,3- diazosulfide (and Wako Pure Chemical Industries (stock) manufacture)
C30:1,2,3- benzotriazole (and Wako Pure Chemical Industries (stock) manufacture)
C31: quinazoline (and Wako Pure Chemical Industries (stock) manufacture)
C32: phthalazines (and Wako Pure Chemical Industries (stock) manufacture)
C33:1,10- phenanthroline (and Wako Pure Chemical Industries (stock) manufacture)
C34:5- methyl-1,10- phenanthroline (and Wako Pure Chemical Industries (stock) manufacture)
C35:2,2 '-bipyridyls (and Wako Pure Chemical Industries (stock) manufacture)
C36:4,4 '-bipyridyls (and Wako Pure Chemical Industries (stock) manufacture)
C37:5,5 '-dimethyl -2,2 '-bipyridyls (and Wako Pure Chemical Industries (stock) manufacture)
C38:2- mercaptobenzothiazoler (and Wako Pure Chemical Industries (stock) manufacture)
C39:1- amino benzotriazole (and Wako Pure Chemical Industries (stock) manufacture)
C40:6- amino-2-mercapto phenyl formic benzothiazole (and Wako Pure Chemical Industries (stock) manufacture)
C41: pyrroles's (and Wako Pure Chemical Industries (stock) manufacture)
C42: pyridine (and Wako Pure Chemical Industries (stock) manufacture)
C43: indoles (and Wako Pure Chemical Industries (stock) manufacture)
C44: iso-indoles (and Wako Pure Chemical Industries (stock) manufacture)
The structure of C1~C44 described below.
[changing 27]
[changing 28]
[changing 29]
<silane compound>
E1:3- glycidoxypropyltrimewasxysilane (KBM-403 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture))
E2: bis- (tri-ethoxy silylpropyl) four thioethers (KBE-846 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture))
E3: ruthenium trimethoxysilane (KBM-3103 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture))
<sensitizer>
G1:DBA (9,10- dibutoxy anthracenes, Kawasaki chemical conversion industry (stock) manufacture)
<alkali compounds>
H1:1,5- diazabicyclo [4,3,0] -5- nonene (Tokyo chemical conversion industry (stock) manufacture)
H2: the compound of following structures
[changing 30]
<surfactant>
I1: the compound of following structures
[changing 31]
<crosslinking agent>
F1:JER157S65 (Mitsubishi Chemical's (stock) manufacture)
F2: Duo Naide (Duranate) 17B-60P (Asahi Chemical Industry's chemistry (stock) manufacture)
F3: De Shimo (Desmodur) BL4265SN (firmly change Bayer carbamate (stock) manufacture)
<antioxidant>
Jl: Yi Jialesi (Irganox) 1035FF (antioxidant, BASF AG's manufacture)
J2: Yi Jialesi (Irganox) 1098 (antioxidant, BASF AG's manufacture)
J3: Ai Di Coase tower wave (Adekastab) AO-60 (antioxidant, Ai Dike (stock) manufacture)
(2) evaluation of photosensitive polymer combination
The evaluation of (2-1) sensitivity
By glass substrate (beneficial height (EAGLE) XG, 0.7mm is thick (healthy and free from worry (Corning) company manufacture)) in two silicon of hexamethyl It is exposed 30 seconds under azane (HMDS) steam, it is enterprising in 90 DEG C/120 seconds heating plates after each photosensitive polymer combination of rotary coating Row prebake conditions and so that solvent is volatilized, forming film thickness is 3.0 μm of photosensitive polymer combination layer.
Then, the MPA 5500CF (high-pressure mercury-vapor lamp) manufactured using Canon (Canon) (stock), across defined mask pair Resulting photosensitive polymer combination layer is exposed.Then, using alkaline developer, (0.4% tetramethylammonium hydroxide is water-soluble Liquid) the photosensitive polymer combination layer after exposure is carried out 23 DEG C/60 seconds after developing, it is eluted within 20 seconds with ultrapure water progress.It will lead to Optimum i x ray exposure x amount (Eopt) when crossing these operations and analyzing 5 μm of hole is as sensitivity.
A: less than 20mJ/cm2
B:20mJ/cm2Above, it is less than 40mJ/cm2
C:40mJ/cm2Above, it is less than 80mJ/cm2
D:80mJ/cm2Above, it is less than 160mJ/cm2
E:160mJ/cm2More than
The evaluation of (2-2) chemical-resistant
Glass substrate is exposed 30 seconds under hexamethyldisilazane (HMDS) steam, rotary coating is respectively felt on the substrate After photosensitive resin composition, prebake conditions being carried out in 90 DEG C/120 seconds heating plates and solvent is made to volatilize, forming film thickness is 3.0 μm Photosensitive polymer combination layer.Then, using extra-high-pressure mercury vapour lamp, 300mJ/cm is become with accumulative exposure2(energy intensity: 20mW/cm2, i ray) mode be exposed, after which to be carried out to heating in 230 DEG C/60 minutes in an oven, Jin Er It carries out heating for 230 DEG C/2 hours in baking oven.
The film thickness (T1) of measurement gained cured film.Then, the substrate for being formed with the cured film is made to be controlled in 60 in temperature DEG C dimethyl sulfoxide: monoethanolamine=7: impregnated in 3 solution after ten minutes, measurement dipping after cured film film thickness (t1), Calculating Thickness Variation rate caused by impregnating | t1-T1 |/TI } × 100 [%].
The smaller the better, A, B are the level of practical upper no problem.
A: less than 2%
B:2% is more than and less than 3%
C:3% is more than and less than 4%
D:4% is more than and less than 6%
E:6% or more
The evaluation of display uneven (Display panel is uneven) in (2-3) display device
The liquid crystal display device using thin film transistor (TFT) (TFT) is made using following methods (referring to Fig. 2).Japan Patent In the active array type LCD recorded in Fig. 1 and Fig. 2 of No. 3321003 bulletin, it is formed as follows hardening Film 17 is used as interlayer dielectric, obtains liquid crystal display device.
That is, forming the TFT 1 of bottom gate polar form on glass substrate 6, formed with covering the state of the TFT 1 comprising Si3N4's Insulating film 3.Then, it after forming contact hole on the insulating film 3, is formed on the insulating film 3 via the contact hole and is connected to TFT 1 wiring 2 (being highly 1.0 μm).
In turn, in order to planarize the bumps as caused by the formation of wiring 2, and to be embedded to the bumps as caused by wiring 2 State form planarization film 4 on the insulating film 3.Planarization film 4 is formed on the insulating film 3, is by embodiment and comparative example Each photosensitive polymer combination rotary coating on substrate, after carrying out prebake conditions (90 DEG C × 2 minutes) on hot plate, cover certainly High-pressure mercury light irradiation 25mJ/cm is used on mould2(energy intensity 20mW/cm2) i ray (365nm) after, it is molten using buck Liquid is developed and forms pattern, and heat treatment in 60 minutes is carried out at 230 DEG C.When being coated with above-mentioned photosensitive polymer combination Coating it is good, the cured film obtained after exposure, development, calcining does not confirm the generation of gauffer or cracking.In turn, wiring 2 average scale is 500nm, and the film thickness of made planarization film 4 is 2,000nm.
Driving voltage, the test signal of input gray level, in 60 DEG C, 90% environment are applied to resulting liquid crystal display device Panel is continuously lighted down, the gray scale after lighting 1000 hours with visual observation is shown, display is evaluated according to following evaluation criteria Uneven the presence or absence of generation.
A: do not see completely uneven (very good)
B: unevenness, but display unit no problem (good) are slightly seen in the edge of glass substrate point
C: unevenness is slightly seen in display unit, but is realistic scale (common)
D: there is uneven (slightly worse) in display unit
E: in display unit, there are serious uneven (excessively poor)
[table 4]
Sensitivity Chemical-resistant Display panel is uneven
Embodiment 1 A A A
Embodiment 2 A A A
Embodiment 3 A A A
Embodiment 4 A A A
Embodiment 5 A A A
Embodiment 6 A A A
Embodiment 7 A A A
Embodiment 8 A A A
Embodiment 9 A A A
Embodiment 10 A A A
Embodiment 11 A A A
Embodiment 12 A A A
Embodiment 13 A A A
Embodiment 14 A A A
Embodiment 15 A A A
Embodiment 16 A A A
Embodiment 17 A A A
Embodiment 18 A A A
Embodiment 19 A A A
Embodiment 20 A B B
Embodiment 21 A B B
Embodiment 22 A B B
Embodiment 23 A B B
Embodiment 24 A B B
Embodiment 25 A B B
Embodiment 26 A B B
Embodiment 27 A A A
Embodiment 28 A A A
Embodiment 29 A A A
Embodiment 30 A A A
Embodiment 31 A A A
Embodiment 32 A A A
Embodiment 33 A A A
Embodiment 34 A A A
Embodiment 35 A A A
Embodiment 36 A A A
Embodiment 37 A A A
Embodiment 38 A A A
Embodiment 39 A A A
Embodiment 40 A A A
Embodiment 41 A A A
[table 5]
Sensitivity Chemical-resistant Display panel is uneven
Embodiment 42 A B B
Embodiment 43 A B B
Embodiment 44 A B B
Embodiment 45 A B B
Embodiment 46 A B B
Embodiment 47 A A A
Embodiment 48 A A A
Embodiment 49 A A A
Embodiment 50 A A A
Embodiment 51 A A A
Embodiment 52 A A A
Embodiment 53 A A A
Embodiment 54 A A A
Embodiment 55 A A A
Embodiment 56 A A A
Embodiment 57 A A A
Embodiment 58 A A A
Embodiment 59 A A A
Embodiment 60 A A A
Embodiment 61 A A A
Embodiment 62 A A A
Embodiment 63 A A A
Embodiment 64 A A A
Embodiment 65 A A A
Embodiment 66 A A A
Embodiment 67 A A A
Embodiment 68 A A A
Embodiment 69 C A A
Embodiment 70 C A A
Embodiment 71 C A A
Comparative example 1 E A E
Comparative example 2 A E D
Comparative example 3 E A E
Comparative example 4 A D E
Comparative example 5 A D D
Comparative example 6 A D D
Comparative example 7 A D D
Comparative example 8 A D D
As the above results are expressed, it is known that, the sensitivity of photosensitive polymer combination of the invention is high, the chemically-resistant of cured film Moral character is excellent, inhibits the generation of Display panel unevenness in panel reliability test.In contrast, it is known that, comparative example it is photosensitive Property resin combination is unsatisfactory for all items of sensitivity, chemical-resistant and Display panel unevenness.
<embodiment 74>
Embodiment 74 is in embodiment 1, in addition to exposure machine is changed to Buddhist nun by the MPA 5500CF that Canon's (stock) manufactures Other than the FX-803M (gh-Line, stepper) of health (Nikon) (stock) manufacture, carry out in an identical manner.Sensitivity, chemicals-resistant The evaluation of property and Display panel unevenness is level same as Example 1.
<embodiment 75>
Embodiment 75 is in embodiment 1, in addition to exposure machine to be changed to by the MPA 5500CF that Canon's (stock) manufactures 355nm laser explosure machine carries out other than 355nm laser explosure, in an identical manner carries out.Herein, 355nm laser explosure machine It is to manufacture " Ai Jisi (AEGIS) " using scientific and technological (V-Technology) Co., Ltd. of V (wavelength 355nm, pulse width are 6nsec), light exposure is measured using " PE10B-V2 " that Ao Feier (OPHIR) company manufactures.
The evaluation of sensitivity, chemical-resistant and Display panel unevenness is level same as Example 1.
<embodiment 76>
Embodiment 76 is in embodiment 1, in addition to exposure machine is changed to UV- by the MPA 5500CF that Canon's (stock) manufactures Other than LED light source exposure machine, carry out in an identical manner.The evaluation of sensitivity, chemical-resistant and Display panel unevenness be with The identical level of embodiment 1.
<embodiment 77>
Coating process below is only changed compared with Example 1, obtains same liquid crystal display device.That is, utilizing slit After rubbing method carrys out the photosensitive polymer combination of coating Examples 1, in 90 DEG C/120 seconds heating plates by heating remove it is molten Agent forms the photosensitive polymer combination layer that film thickness is 3.0 μm.Resulting film is flat and without uneven good planar.Separately Outside, also good similarly to Example 1 as the performance of liquid crystal display device.
As indicated above, it is known that no matter the photosensitive polymer combination exposure machine or coating method of embodiment, obtain The liquid crystal display device of sensitivity, good chemical resistance, panel high reliablity.
<embodiment 78>
The organic EL display device using thin film transistor (TFT) (TFT) is made using following methods (referring to Fig. 2).
The TFT 1 of bottom gate polar form is formed on glass substrate 6, is formed with covering the state of the TFT 1 comprising Si3N4It is exhausted Velum 3.Then, it after forming the contact hole of illustration omitted herein on the insulating film 3, is formed on the insulating film 3 via the contact Hole and the wiring 2 (being highly 1.0 μm) for being connected to TFT 1.The wiring 2 is will form between TFT 1 or in later-mentioned step Organic EL element is connect with TFT 1.
In turn, in order to planarize the bumps as caused by the formation of wiring 2, and to be embedded to the bumps as caused by wiring 2 State form planarization film 4 on the insulating film 3.Planarization film 4 is formed on the insulating film 3, is by the photonasty of embodiment 16 Resin combination rotary coating after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, from mask, uses height on substrate Medium pressure mercury lamp irradiates 45mJ/cm2(energy intensity 20mW/cm2) i ray (365nm) after, developed using aqueous alkali And pattern is formed, carry out heat treatment in 230 DEG C/30 minutes.
Coating when photosensitive resin coating composition is good, on the cured film obtained after exposure, development, calcining not really Recognize the generation of gauffer or cracking.In turn, the average scale of wiring 2 is 500nm, and the film thickness of made planarization film 4 is 2, 000nm。
Then, the organic EL element of bottom emission type is formed on resulting planarization film 4.Firstly, in planarization film 4 On, it is connect with wiring 2 via contact hole 7 to form the first electrode 5 comprising ITO.Then, it is coated with resist and carries out preliminary drying It is roasting, it is exposed, develops across the mask of required pattern.Using the resist pattern as mask, by using ITO etchant Wet etching carries out pattern processing.Then, using anticorrosive additive stripping liquid controlling, (remover (Remover) 100 pacifies intelligence electronic material The manufacture of (AZ Electronic Materials) company), above-mentioned resist pattern is removed at 50 DEG C.It obtains in the above described manner First electrode 5 be equivalent to the anode of organic EL element.
Then, the insulating film 8 of the shape of the periphery of covering first electrode 5 is formed.On insulating film 8, embodiment 1 is used Photosensitive polymer combination forms insulating film 8 in the same way as described above.By the way that the insulating film 8 is arranged, the first electricity can be prevented Short circuit between pole 5 and the second electrode formed in the step of thereafter.
In turn, it across required pattern mask in vacuum deposition apparatus, is successively deposited and hole transmission layer, organic is set Luminescent layer, electron transfer layer.Then, the entire surface above substrate forms the second electrode comprising Al.By from evaporator Resulting aforesaid substrate is taken out, and is bonded with glass for sealing plate using ultraviolet ray hardening type epoxy resin to seal.
In the above described manner, the active matrix made of TFT 1 of the connection for driving it in each organic EL element is obtained Type organic EL display device.Apply voltage via driving circuit, as a result known to show good display characteristic and reliable The high organic EL display device of property.

Claims (12)

1. a kind of photosensitive polymer combination, it includes:
Component of polymer A comprising meeting the polymer of at least one in following 1 and 2；
1: including the structural unit a1 of residue protected with acidic group by sour decomposability base and with the structure list of bridging property base The polymer of first a2,
2: the polymer of the structural unit a1 including the residue protected with acidic group by sour decomposability base and including having crosslinking The polymer of the structural unit a2 of property base；
Photoacid generator B；
Selected from by oxazole based compound, isoxazole based compound, thiazole compound, isothiazole based compound, triazole system chemical combination Object, oxadiazoles based compound, thiadiazoles system compound, pyrimidine compound, triazine based compound, quinazoline based compound, phthalein At least one of the group that piperazine based compound, phenanthroline based compound and bipyridyl based compound are constituted aromatic series is miscellaneous Cycle compound C, wherein the triazine based compound is 1,2,3- triazines, 1,2,4- triazines, 1,3,5-triazines, 2,4,6- tri- is chloro- 1,3,5- triazine, 2,4,6- cyanphenine 2,4,6, (the trifluoromethyl) -1,3,5- triazine of 2,4,6- tri- and 2,4- diformazan Oxy-1,3,5- triazines, and the aromatic heterocyclic compounds C are not 2- [2- [4- (dimethylamino) phenyl] vinyl] Benzoxazoles, and without amino as substituent group possessed by the aromatic rings in the aromatic heterocyclic compounds C；And
Solvent D,
The molecular weight of the aromatic heterocyclic compounds C is 1000 or less.
2. photosensitive polymer combination according to claim 1, wherein having in the polymer of the component of polymer A Bridging property base contained in the structural unit a2 of bridging property base is selected from epoxy group, oxetanylmethoxy and-NH-CH2- O-R institute At least one kind of in the group of expression, R is the alkyl of hydrogen atom or carbon number 1~20.
3. photosensitive polymer combination according to claim 1 or 2, wherein the acid decomposability base is with acetal The group for the structure that form is protected.
4. photosensitive polymer combination according to claim 1 or 2, wherein the polymer of the component of polymer A is appointed One is the polymer containing acidic group in turn.
5. photosensitive polymer combination according to claim 3, wherein either one or two of the polymer of the component of polymer A For the polymer containing acidic group in turn.
6. photosensitive polymer combination according to claim 1 or 2, wherein the photoacid generator B is oxime sulfonates Close object.
7. a kind of forming method of cured film comprising:
Application step photosensitive polymer combination according to any one of claim 1 to 6 being coated on substrate；
The solvent removal step of solvent is removed from the photosensitive polymer combination being coated with；
The step of exposure that the photosensitive polymer combination for eliminating solvent is exposed using actinic ray；
The development step developed using aqueous developer to exposed photosensitive polymer combination；And
The rear baking procedure of thermmohardening is carried out to developed photosensitive polymer combination.
8. the forming method of cured film according to claim 7, wherein after the development step, the rear baking procedure Before include the steps that carrying out blanket exposure to developed photosensitive polymer combination.
9. a kind of cured film is the forming method using cured film according to claim 7 and is formed.
10. cured film according to claim 9 is interlayer dielectric.
11. a kind of organic electroluminescence display device and method of manufacturing same comprising cured film according to claim 9 or 10.
12. a kind of liquid crystal display device comprising cured film according to claim 9 or 10.
CN201380049705.6A 2012-09-28 2013-09-17 Photosensitive polymer combination, using its cured film preparation method, cured film, liquid crystal display device and organic EL display device Active CN104685416B (en)

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104460232B (en) * 2013-09-24 2019-11-15 住友化学株式会社 Photo-corrosion-resisting agent composition
JP6318742B2 (en) * 2014-03-18 2018-05-09 Jsr株式会社 Positive photosensitive resin composition
JP6183268B2 (en) * 2014-03-28 2017-08-23 Jsr株式会社 Radiation-sensitive resin composition and resist pattern forming method
JP6672801B2 (en) * 2015-04-09 2020-03-25 Jsr株式会社 Liquid crystal alignment agent
TWI693470B (en) * 2015-06-30 2020-05-11 日商富士軟片股份有限公司 Photosensitive resin composition, method for producing cured film, cured film, and liquid crystal display device
JP6589763B2 (en) * 2015-08-04 2019-10-16 信越化学工業株式会社 Chemically amplified positive resist composition and pattern forming method
JP6809873B2 (en) * 2015-12-28 2021-01-06 旭化成株式会社 Laminate
KR102635564B1 (en) * 2016-05-03 2024-02-08 동우 화인켐 주식회사 Positive photosensitive resist composition and insulation layer prepared from the same
KR102654731B1 (en) * 2017-09-28 2024-04-03 제이에스알 가부시끼가이샤 Radiation-sensitive resin composition and use thereof
JP6925429B2 (en) * 2017-09-29 2021-08-25 富士フイルム株式会社 Photosensitive resin composition, resist film, pattern forming method and manufacturing method of electronic device
WO2019143917A2 (en) 2018-01-18 2019-07-25 Saudi Arabian Oil Company Tracers for petroleum reservoirs
KR102692918B1 (en) 2018-09-11 2024-08-08 스미또모 베이크라이트 가부시키가이샤 Photosensitive resin composition for forming a permanent film, cured film, electronic device, method for producing a cured film, and method for producing an electronic device
WO2021187549A1 (en) * 2020-03-19 2021-09-23 富士フイルム株式会社 Transfer film, photosensitive material, method for forming pattern, method for manufacturing circuit board, and method for manufacturing touch panel
WO2021192058A1 (en) * 2020-03-24 2021-09-30 昭和電工マテリアルズ株式会社 Photosensitive resin composition, photosensitive element, and method for producing wiring board
JP7504659B2 (en) * 2020-05-18 2024-06-24 東京応化工業株式会社 Chemically amplified photosensitive composition, photosensitive dry film, method for producing patterned resist film, method for producing plated object, compound, and method for producing compound
CN114874238A (en) * 2021-02-01 2022-08-09 中国科学院理化技术研究所 Photosensitizer based on thiadiazole [3,4-g ] quinoxaline structure and synthesis method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201217903A (en) * 2010-08-30 2012-05-01 Fujifilm Corp Photosensitive resin composition, oxime sulfonate compound, method for forming cured film, cured film, organic EL display device and liquid crystal display device
US20120107563A1 (en) * 2010-11-02 2012-05-03 Fujifilm Corporation Photosensitive resin composition, method for producing pattern, mems structure, method for producing the structure, method for dry etching, method for wet etching, mems shutter device, and image display apparatus
CN102540726A (en) * 2010-12-13 2012-07-04 富士胶片株式会社 Orthotype photosensitive resin composition, hard coating film and forming method thereof, interlayer insulated film, and display device

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08240908A (en) * 1994-12-29 1996-09-17 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition, photosensitive planographic printing plate using the same and production of printing plate material for planographic printing
JP2004272182A (en) * 2002-04-24 2004-09-30 Mitsubishi Chemicals Corp Method for forming image
JP4683182B2 (en) * 2004-09-28 2011-05-11 山栄化学株式会社 Photosensitive thermosetting resin composition, resist-coated printed wiring board and method for producing the same
WO2006099380A2 (en) * 2005-03-11 2006-09-21 E.I. Dupont De Nemours And Company Photoimageable, thermosettable fluorinated resists
JP2009288343A (en) * 2008-05-27 2009-12-10 Fujifilm Corp Positive type resist composition and pattern forming method using the composition
JP5451570B2 (en) 2009-10-16 2014-03-26 富士フイルム株式会社 Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device
JP5524037B2 (en) * 2010-01-19 2014-06-18 富士フイルム株式会社 Photosensitive resin composition, cured film, method for forming cured film, organic EL display device, and liquid crystal display device
JP5174124B2 (en) * 2010-11-02 2013-04-03 富士フイルム株式会社 Photosensitive resin composition for MEMS structural member, pattern production method, MEMS structure and production method thereof
JP5291744B2 (en) * 2010-11-02 2013-09-18 富士フイルム株式会社 Photosensitive resin composition for etching resist, pattern manufacturing method, MEMS structure and manufacturing method thereof, dry etching method, wet etching method, MEMS shutter device, and image display device
JP5417422B2 (en) * 2010-12-13 2014-02-12 富士フイルム株式会社 Positive photosensitive resin composition
JP5536625B2 (en) * 2010-12-15 2014-07-02 富士フイルム株式会社 Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device
JP5510347B2 (en) * 2011-01-26 2014-06-04 Ｊｓｒ株式会社 Positive radiation-sensitive composition, interlayer insulating film and method for forming the same
JP5642578B2 (en) * 2011-01-28 2014-12-17 富士フイルム株式会社 Photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device
JP5386527B2 (en) * 2011-02-18 2014-01-15 富士フイルム株式会社 Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, and resist film
JP5772181B2 (en) * 2011-04-20 2015-09-02 Jsr株式会社 Radiation sensitive resin composition, interlayer insulating film for display element and method for forming the same
KR101336148B1 (en) * 2011-04-20 2013-12-03 제이에스알 가부시끼가이샤 Positive photosensitive composition, interlayer insulating film for diaplay device and its forming method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201217903A (en) * 2010-08-30 2012-05-01 Fujifilm Corp Photosensitive resin composition, oxime sulfonate compound, method for forming cured film, cured film, organic EL display device and liquid crystal display device
US20120107563A1 (en) * 2010-11-02 2012-05-03 Fujifilm Corporation Photosensitive resin composition, method for producing pattern, mems structure, method for producing the structure, method for dry etching, method for wet etching, mems shutter device, and image display apparatus
CN102540726A (en) * 2010-12-13 2012-07-04 富士胶片株式会社 Orthotype photosensitive resin composition, hard coating film and forming method thereof, interlayer insulated film, and display device

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