CN103365083B - Photosensitive polymer combination, the manufacturing method of pattern, the manufacturing method of cured film, organic EL display device and liquid crystal display device - Google Patents

Photosensitive polymer combination, the manufacturing method of pattern, the manufacturing method of cured film, organic EL display device and liquid crystal display device Download PDF

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Publication number
CN103365083B
CN103365083B CN201310105324.7A CN201310105324A CN103365083B CN 103365083 B CN103365083 B CN 103365083B CN 201310105324 A CN201310105324 A CN 201310105324A CN 103365083 B CN103365083 B CN 103365083B
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general formula
alkyl
photosensitive polymer
polymer combination
pattern
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CN103365083A (en
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中村秀之
藤本进二
山下史绘
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from JP2012083123A external-priority patent/JP5462904B2/en
Priority claimed from JP2013005568A external-priority patent/JP5589101B2/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
    • G03F7/203—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure comprising an imagewise exposure to electromagnetic radiation or corpuscular radiation
    • 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

Abstract

The present invention provides the manufacturing method of a kind of photosensitive polymer combination, the manufacturing method of pattern, cured film, organic EL display device and liquid crystal display device.The present invention provides a kind of sensitivity, analyticity and the excellent photosensitive polymer combination of rectangularity.Photosensitive polymer combination of the invention contains (A-1) and contains the polymer of structural unit represented by structural unit and general formula (a-1) with acidic group, (A-2) polymer, (B) photoacid generator and (C) solvent containing structural unit represented by general formula (a-2).General formula (a-1) general formula (a-2)

Description

Photosensitive polymer combination, the manufacturing method of pattern, cured film, organic EL display dress It sets and the manufacturing method of liquid crystal display device
Technical field
A kind of manufacturing method of pattern the present invention relates to photosensitive polymer combination and using this composition.In turn, originally Invention is related to a kind of organic electroluminescent (EL (Electroluminescence)) display device comprising the method for manufacturing pattern Or pattern manufactured by the manufacturing method and utilization method of manufacturing pattern of liquid crystal display device.In more detail, the present invention relates to And a kind of resist of electronic component suitable for liquid crystal display device, organic EL display device etc. etches (resist etching) Formation positive type photosensitive organic compound and using this composition pattern manufacturing method.
Background technique
In organic EL display device or liquid crystal display device etc., the tin indium oxide for having formd pattern is set The metal wiring pattern of (Indium Tin Oxide, ITO) film etc..In the pattern formation of the ito film etc., following methods are widely People knows: photosensitive resin coating composition and removing solvent in ito film, is exposed, develops, will be formed by pattern work Ito film is etched for mask, implements processing.
In addition, in recent years, in order to make organic EL display device or liquid crystal display device that there is the display characteristic of fine, and It is required that the high analyticity of ITO processing.In order to carry out the microfabrication of fine to ITO, function is played as mask when to etching The photosensitive polymer combination of energy requires high analyticity.
As the photosensitive polymer combination that can obtain fine pattern form in high-precision, such as in Japanese Patent Laid-Open A kind of radiation-sensitive resin composition is disclosed in flat 9-325473 bulletin, this radiation-sensitive resin composition contains packet The structural unit for the hydroxystyrene monomer that the structural unit and hydroxyl of hydroxyl styrene monomer are protected through sour decomposability base Copolymer.In addition, disclosing a kind of eurymeric light resistance composition, this eurymeric in Japanese Patent Laid-Open 10-326015 bulletin Light resistance composition is in the resin due to effect of acid from becoming alkali-soluble for insoluble or slightly solubility state relative to alkali In, it deploys photoacid generator and the tertiary amine compounds with ehter bond forms.
Summary of the invention
Here, as the tendency developed in recent years, there is the shortwave along with exposure wavelength and pursuing has under shortwave The tendency of the composition of absorption region, in addition, having the tendency that demand does not have the material of absorbability in visibility region.But This composition must use expensive as the i ray stepper and parsing good exposure sources of power.The present invention be in view of The actual conditions form, and its purpose is to provide a kind of photosensitive polymer combinations, even if this photosensitive polymer combination makes With cheap gh ray scanner or low numerical aperture (Numerical Aperture, NA) exposure sources (NA=0.1 or less), Sensitivity is also high, and same analyticity and rectangularity are excellent with i ray stepper.
Present inventor is based on the situation and has carried out making great efforts research, as a result by that will contain the structure list with acidic group The polymer of member and the acidic group through protecting blends, phase with 4-Vinyl phenol (p-hydroxy styrene, PHS) based polymer It separates the state of (state of entwining of the polymer chain in resist film) and these structural units is made all to be contained in a kind of polymer In situation (single binder system) or each polymer the case where containing 3 kinds of structural units respectively (three binder systems) it is different, success Ground improves sensitivity and analyticity.In turn, it has therefore been surprisingly found that blend system by being set as, rectangularity also improves, thus complete At the present invention.
It has carried out making great efforts research in addition, present inventor is based on the situation, as a result, it has been found that, increase by using specific Feel agent, can solve the project.This sensitizer has absorption region under long wave (ghi ray, gh ray), and has height I ray, gh radioactive ray absorbent, and then electron-transport efficiency is good, therefore can suitably make contributions to photoacid generator, Improve sensitivity, analyticity and rectangularity.
Specifically, the project is solved by following means<1>, preferred means<2>~means<24>.
<1>a kind of photosensitive polymer combination, contains:
(A-1) polymer containing structural unit represented by structural unit and general formula (a-1) with acidic group；
(A-2) polymer containing structural unit represented by general formula (a-2)；
(B) photoacid generator；And
(C) solvent,
General formula (a-1)
(in general formula (a-1), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of be alkyl Or aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can also link and form cyclic ether, R4Indicate hydrogen atom or methyl, X table Show singly-bound or arlydene)；
General formula (a-2)
(in general formula (a-2), R4For hydrogen atom or methyl).
<2>photosensitive polymer combination according to documented by<1>, wherein (A-2) polymer further contains general formula (a-3) Represented structural unit；
General formula (a-3)
(in general formula (a-3), R4For hydrogen atom or methyl；R5For straight chain, branch or cricoid alkyl, contain in the alkyl At least one-O-).
<3>photosensitive polymer combination according to documented by<2>, the R of formula of (a-3)5It is by general formula (a-4) or to lead to Formula (a-5) is represented；
General formula (a-4)
(in general formula (a-4), R2Indicate the straight chain of carbon number 1~5 or the alkyl of branch；On the position of asterisk with general formula (a- 3) it is bonded)；
General formula (a-5)
(in general formula (a-5), being bonded on the position of asterisk with general formula (a-3)).
<4>photosensitive polymer combination according to documented by any one of<1>to<3>further contains (D) and increases sense Agent.
<5>photosensitive polymer combination according to documented by<4>, wherein (D) sensitizer is the following general formula (O) or general formula (P) compound represented by；
General formula (O)
(R1)n-L1-(R2)m
(in general formula (O), R1And R2Respectively indicate the heterocycle structure of aryl or the ethylenic linkage with 1 or more；L1Indicate tool There is divalent~4 valences concatenating group of 2~4 ethylenic linkages；N and m respectively indicates 1 or 2)；
General formula (P)
(in general formula (P), R is respectively the alkyl of carbon number 1~8).
<6>photosensitive polymer combination according to documented by any one of<1>to<5>, wherein (B) photoacid generator is oxime Sulfonate compound.
<7>photosensitive polymer combination according to documented by any one of<1>to<6>, further contains epoxy resin.
<8>a kind of manufacturing method of pattern comprising:
(1) photosensitive polymer combination according to documented by any one of<1>to<6>is applied into the process on substrate；
(2) process of solvent is removed from applied photosensitive polymer combination；
(3) process being exposed using active radioactive ray；
(4) process developed using aqueous developer；
(5) process that the substrate is etched as mask using resist pattern is formed by；And
(6) process for removing the resist pattern.
<9>manufacturing method of the pattern according to documented by<8>, wherein after the developing procedure, before etching work procedure, including The process toasted after being carried out at 100 DEG C~160 DEG C to the resist pattern.
<10>manufacturing method of the pattern according to documented by<8>or<9>, wherein the substrate be ito substrate, molybdenum base plate, Silicon substrate, Cu substrate, A1 substrate or single crystal sapphire substrate.
<11>a kind of cured film is to harden the photosensitive polymer combination according to documented by any one of<1>to<7> It forms.
<12>a kind of organic EL display device or the manufacturing method of liquid crystal display device, it includes bases<8>into<10> The manufacturing method of pattern documented by any one.
In addition, the embodiment being different from the present invention is it is also preferred that following implementation.
<13>a kind of photosensitive polymer combination, contains:
(A) containing the component of polymer of polymer, the polymer contains the monomeric unit protected through sour decomposability base；
(B) photoacid generator；
(C) compound represented by the following general formula (O)；And
(D) solvent,
General formula (O)
(R1)n-L1-(R2)m
(in general formula (O), R1And R2Respectively indicate the heterocycle structure of aryl or the ethylenic linkage with 1 or more；L1Indicate tool There is divalent~4 valences concatenating group of 2~4 ethylenic linkages；N and m respectively indicates 1 or 2).
<14>photosensitive polymer combination according to documented by<13>, wherein L1At least contain-(R is hydrogen to (CR=CR) p- Atom or methyl, p be 2 or more integer) or the ethylenic linkage with 1 or more heterocycle structure.
<15>photosensitive polymer combination according to documented by<13>or<14>, wherein chemical combination represented by (C) general formula (O) The number of ethylenic linkage in object is 4~14.
<16>photosensitive polymer combination according to documented by any one of<13>to<15>, wherein R1And R2Aryl or Heterocycle structure with 1 or more ethylenic linkage only contains monocycle as cyclic structure respectively.
<17>photosensitive polymer combination according to documented by any one of<13>~<16>, wherein R1And R2Respectively may be used Group represented by phenyl or the following general formula (O-1) with substituent group,
General formula (O-1)
(in general formula (O-1), R indicates substituent group, the integer that r is 0~2).
<18>photosensitive polymer combination according to documented by any one of<13>to<17>, wherein L1For the following general formula (O-2) or group represented by general formula (O-3),
General formula (O-2)
(in general formula (O-2), S1 be 1~6 integer)；
General formula (O-3)
(in general formula (O-3), S2 be 2~4 integer).
<19>photosensitive polymer combination according to documented by any one of<13>to<18>, wherein R1And R2Respectively may be used Group represented by phenyl or the following general formula (O-1) with substituent group, L1For the following general formula (O-2) or general formula (O-3) institute table The group shown,
General formula (O-1)
(in general formula (O-1), R is the alkyl of halogen atom or carbon number 1~3, the integer that r is 0~2)；
General formula (O-2)
(in general formula (O-2), S1 be 1~6 integer)；
General formula (O-3)
(in general formula (O-3), S2 be 2~4 integer).
<20>photosensitive polymer combination according to documented by any one of<13>to<19>is that chemical amplification type is photosensitive Property resin combination.
<21>photosensitive polymer combination according to documented by any one of<13>to<20>, wherein (A) contains through acid point The polymer of the monomeric unit of Xie Xingji protection contain the monomeric unit from the hydroxy styrenes protected through sour decomposability base, Or the monomeric unit with the protection carboxyl protected through sour decomposability base.
<22>photosensitive polymer combination according to documented by any one of<13>to<21>, wherein (A) contains through acid point The polymer of the monomeric unit of Xie Xingji protection contains the following general formula (I)~logical formula (III) at least one,
Logical formula (I) leads to formula (II) and leads to formula (III)
(in logical formula (I), R2、R3、R4Respectively indicate hydrogen atom or methyl, R5Indicate straight chain, the branch that there can be substituent group Or the alkyl of cricoid carbon number 1~6；
In logical formula (II), Ra1~Ra6Respectively indicate hydrogen atom, the carbon number 1~20 that can have substituent group alkyl or can have The aryl of substituted base, Ra2With Ra3、Ra4With Ra5It can also be mutually bonded and form ring；Ra7Indicate hydrogen atom or methyl, Ra8 Indicate that the alkyl of halogen atom, hydroxyl or carbon number 1~3, n1 indicate 0~4 integer；
In logical formula (III), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of for alkyl or Aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can also link and form cyclic ether；R4Indicate that hydrogen atom or methyl, X indicate Singly-bound or arlydene).
<23>photosensitive polymer combination according to documented by any one of<13>to<22>, wherein (A) contains through acid point The polymer of the monomeric unit of Xie Xingji protection further contains the monomeric unit from hydroxy styrenes.
<24>photosensitive polymer combination according to documented by any one of<13>to<23>, wherein (B) photoacid generator For oxime sulfonate compounds or salt compound.
<25>a kind of manufacturing method of pattern comprising:
(1) photosensitive polymer combination according to documented by any one of<13>to<24>is applied into the work on substrate Sequence；
(2) process of solvent is removed from applied photosensitive polymer combination；
(3) process being exposed using active radioactive ray；
(4) process developed using aqueous developer；
(5) process that the substrate is etched as mask using resist pattern is formed by；And
(6) process for removing the resist pattern.
<26>manufacturing method of the pattern according to documented by<25>, wherein after the developing procedure, before etching work procedure, packet Include the process toasted after carrying out at 100 DEG C~160 DEG C to the resist pattern.
<27>manufacturing method of the pattern according to documented by<25>or<26>, wherein the substrate is ito substrate, molybdenum base Plate, silicon substrate, Cu substrate, A1 substrate or single crystal sapphire substrate.
<28>a kind of cured film is to keep the photosensitive polymer combination according to documented by any one of<13>to<24>hard Change.
<29>a kind of organic EL display device or the manufacturing method of liquid crystal display device comprising according to<25>into<27> The manufacturing method of pattern documented by any one.
[The effect of invention]
According to the present invention it is possible to provide the photosensitive polymer combination that a kind of sensitivity is high, analyticity and rectangularity are excellent.It is special Even if not being without using expensive as the i ray stepper and good exposure sources of parsing power or without using the exposure of shortwave Radiant can also reach these performances even with cheap low NA (numerical aperture) exposure sources (NA=0.1 or less), from Value of the invention is high in this respect.
Detailed description of the invention
Fig. 1 shows the composition concept maps of an example of organic EL display device, indicate organic EL display dress of bottom emission type The schematic sectional view of substrate in setting has planarization film 4.
Fig. 2 indicates the composition concept map of an example of liquid crystal display device, indicates the active matrix base in liquid crystal display device The schematic sectional view of plate has the cured film 17 as interlayer dielectric.
The explanation of symbol:
1:TFT (thin film transistor (TFT))
2: wiring
3: insulating film
4: planarization film
5: first electrode
6: glass substrate
7: contact hole
8: insulating film
10: liquid crystal display device
12: back light unit
14,15: glass substrate
16:TFT
17: cured film
18: contact hole
19:ITO transparent electrode
20: liquid crystal
22: colored filter
Specific embodiment
Hereinafter, the contents of the present invention will be described in detail.In addition, "~" is comprising before it in present specification Documented numerical value is used as the connotation of lower limit value and upper limit value afterwards.In addition, the organic EL display device in the present invention is Refer to organic electroluminescence display device and method of manufacturing same.Polydispersity in the present invention refers to the value of Mw/Mn.
1st implementation form:
Photosensitive polymer combination of the invention be characterized in that containing: (A-1) contain with acidic group structural unit and The polymer of polymer, (A-2) containing structural unit represented by general formula (a-2) of structural unit represented by general formula (a-1),
(B) photoacid generator and (C) solvent.
General formula (a-1)
(in general formula (a-1), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of be alkyl Or aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can also link and form cyclic ether, R4Indicate hydrogen atom or methyl, X table Show singly-bound or arlydene)
General formula (a-2)
(in general formula (a-2), R4For hydrogen atom or methyl)
In the past, the structural unit with acidic group, structural unit and general formula (a-2) represented by general formula (a-1) were represented Structural unit be usually the situation (single binder system) for being contained in these structural units all in a kind of polymer, but the present invention In, by be set as (A-1) contain with acidic group structural unit and general formula (a-1) represented by structural unit polymer, The blending system of polymer with (A-2) containing structural unit represented by general formula (a-2), the state mutually separated is different, successfully Improve sensitivity, analyticity and rectangularity.
Photosensitive polymer combination of the invention can preferably act as chemical amplification positive photosensitive polymer combination.
Hereinafter, composition of the invention is described in detail.
<(A) component of polymer>
In photosensitive polymer combination of the invention, as component of polymer, as an essential component by (A-1) and (A-2), And then other polymers (A-3) can also be contained.Hereinafter, being illustrated to these component of polymer.In this specification, " (A) at Point ", " component of polymer " as long as without being particularly described, refer to the admixture of (A-1), (A-2) and (A-3).
(A) component of polymer is preferably alkali-insoluble, and is preferably the structural unit represented by general formula (a-1) Resin when sour decomposability base is decomposed as alkali-soluble.Here, so-called sour decomposability base, referring to can be in the presence of acid The connotation of the functional group of lower decomposition.That is, general formula (a-1) is the structure list for the protection carboxyl protected with carboxyl through sour decomposability base Member, thus Protecting gene acid and decompose, it is possible thereby to generate carboxyl.Here, so-called " alkali-soluble " of the invention, refers to the change The solution coating of object (resin) is closed on substrate, is heated 2 minutes at 90 DEG C, the painting of the resulting compound (resin) Film (3 μm of thickness) is 0.01 μm/second or more, institute for the solution rate of 0.4% tetramethyl ammonium hydroxide aqueous solution at 23 DEG C It calls " alkali-insoluble ", refers to the solution coating by the compound (resin) on substrate, heat 2 minutes at 90 DEG C, thus institute The film (with a thickness of 3 μm) of the compound (resin) formed is for 0.4% tetramethyl ammonium hydroxide aqueous solution at 23 DEG C Solution rate is less than 0.01 μm/second.
(A-1) polymer containing structural unit represented by structural unit and general formula (a-1) with acidic group
Polymer (A-1) of the invention contains structural unit represented by structural unit and general formula (a-1) with acidic group.
(acidic group)
Polymer (A-1) contains acidic group.By containing acidic group, it is easily dissolved in the developer solution of alkalinity, more effectively sends out Wave effect of the invention.So-called acidic group in the present invention refers to proton dissociation base of the pKa less than 7.Acidic group usually uses can shape The monomer of acid-forming group, group enters into resin in the form of the structural unit with acidic group.By making this structure containing acidic group Unit is contained in resin, there is alkali-soluble bigger tendency.
Acidic group used in the present invention may be exemplified the acidic group from carboxylic acid group, from sulfoamido (sulfonamido) acidic group, from the acidic group of phosphonic acid base, from sulfonic acidic group, from the acid of phenolic hydroxyl group Base, sulfoamido, sulfonyl imide (sulfonylimido) etc., are preferably derived from the acidic group of carboxylic acid group and/or derive from The acidic group of phenolic hydroxyl group.
Structural unit used in the present invention with acidic group more preferably derives from structural unit or the source of styrene In the structural unit of vinyl compound, from the structural unit of (methyl) acrylic acid and/or its ester.
In the present invention, from the viewpoint of sensitivity, particularly preferably containing the structural unit with carboxyl or with phenol Property hydroxyl structural unit, and then preferably with carboxyl structural unit.
It rubs 1 mole of %~80 that structural unit with acidic group is preferably the structural unit of polymer (A-1) ingredient You are %, more preferable 1 mole of %~50 mole %, and then preferably 5 moles of %~40 mole %, and particularly preferred 5 moles of %~30 are rubbed You are %, particularly preferred 5 moles of %~20 mole %.
(polymer with structural unit represented by general formula (a-1))
(A-1) polymer used in the present invention includes the polymer containing structural unit represented by general formula (a-1).
General formula (a-1)
(in general formula (a-1), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of be alkyl Or aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can also link and form cyclic ether, R4Indicate hydrogen atom or methyl, X table Show singly-bound or arlydene)
In R1And R2In the case where for alkyl, preferably carbon number be 1~10 alkyl.In R1And R2It is excellent in the case where for aryl Select phenyl.R1And R2The alkyl of preferred hydrogen atom or carbon number 1~4 respectively.
R3Indicate alkyl or aryl, the preferably alkyl of carbon number 1~10, the alkyl of more preferable carbon number 1~6.
X indicates singly-bound or arlydene, preferably singly-bound.
The preferred concrete example of structural unit represented by general formula (a-1) may be exemplified following structural units.In addition, R is indicated Hydrogen atom or methyl.
Structural unit represented by general formula (a-1) is preferably 10 moles of % of the structural unit of polymer (A-1) ingredient ~80 moles of %, more preferable 20 moles of %~80 mole %, and then preferably 30 moles of %~70 mole %.
(A-1) polymer of the invention can also contain other structures unit in the range of without departing from purport of the invention (wherein, will be equivalent to except the structural unit of general formula (a-2)).
From the viewpoint of adhesion, other structures unit preferably (methyl) alkyl acrylate.It can specifically enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate etc., it is more excellent Select (methyl) methyl acrylate.
Constitute polymer (A-1) structural unit in, the containing ratio of the other structures unit preferably 60 moles of % hereinafter, More preferable 50 moles of % are hereinafter, preferably 40 moles of % or less in turn.Lower limit value may be 0 mole of %, but for example, it can be set to For 1 mole of % or more, and then it can be set as 5 moles of % or more.If the containing ratio of the other structures unit is in the numerical value In range, then become good by each characteristic of the resulting cured film of photosensitive polymer combination.
(A-1) protective rate of polymer preferably 1%~60%, more preferable 5%~50%, and then preferably 10%~40%. By being set as this range, sensitivity is improved, in addition the deliquescent difference of exposure portion and unexposed portion (discrimination) it becomes apparent from.So-called protective rate refers to all structural units in (A-1) polymer being set as 100 When mole %, the molar ratio of protected group.
The range of the weight average molecular weight (Mw) preferably 2000~15000 of (A-1) polymer, more preferable 5000~ 12000, and then preferably 7500~12000.By being set as 2000 or more, it can obtain and be formed by pixel adding in rear baking Also the effect that rectangularity can be maintained after heat, by being set as 15000 hereinafter, postponing (post after sensitivity, exposure can be obtained Exposure delay, PED) characteristic improve effect.Here, weight average molecular weight is according to gel permeation chromatography (Gel Permeation Chromatography, GPC) polystyrene scaled value define.
The polydispersity (weight average molecular weight (Mw)/number average molecular weight (Mn)) of (A-1) polymer is preferred 1.0~4.0, more preferable 1.5~3.5, and then preferably 2.0~3.0.By being set as this range, rectangularity is excellent.
(A-2) polymer containing structural unit represented by general formula (a-2)
(A-2) polymer used in the present invention includes the polymer containing structural unit represented by general formula (a-2).
General formula (a-2)
(in general formula (a-2), R4For hydrogen atom or methyl)
R4It is preferred that hydrogen atom.
OH base can be it is p-, m-, o- any, be preferably bonded in contraposition.
Structural unit represented by general formula (a-2) is preferably 5.0 moles of % of the structural unit of polymer (A-2) ingredient ~30 moles of %, more preferable 10 moles of %~20 mole %.Effect can not be obtained by leading to the problem of if being less than minimum, if mistake It is more, generate the problems such as sensitivity is excessively high, exposure technology tolerance (process margin) narrows.
(A-2) polymer of the invention can also contain other structures unit in the range of without departing from present subject matter. But other structures unit not has structural unit represented by the structural unit and general formula (a-1) of acidic group.Other structures list Member preferably has structural unit represented by general formula (a-3).
General formula (a-3)
(in general formula (a-3), R4For hydrogen atom or methyl.R5For straight chain, branch or cricoid alkyl, contain in the alkyl At least one-O-)
R5It is preferred that the alkyl of straight chain, branch or cricoid carbon number 1~10.In addition, R5Preferably contain 1 in the alkyl A-O-.
The R of general formula (a-3)5Preferably by general formula (a-4) or general formula (a-5) represented by.
General formula (a-4)
(in general formula (a-4), R2Indicate the straight chain of carbon number 1~5 or the alkyl of branch.On the position of asterisk with general formula (a- 3) it is bonded)
R2It is preferred that the straight chain of carbon number 1~3 or the alkyl of branch, more preferable methyl or ethyl.
General formula (a-5)
(in general formula (a-5), being bonded on the position of asterisk with general formula (a-3))
Hereinafter, being preferably illustrated in for structural unit represented by general formula (a-3) is following.But the present invention is certainly unlimited Due to these preferences.
In the structural unit for constituting polymer (A-2), structural unit represented by general formula (a-3) is preferably polymer (A-2) 5 moles of %~40 mole % of the structural unit of ingredient, more preferable 10 moles of %~40 mole %, and then preferably 20 rub You are %~35 mole %.
Polymer (A-2) can also further contain other structures unit, other structures unit for example: benzene second Alkenes, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxyl Acid diesters, bicyclic unsaturated compound class, maleimide compound class, unsaturated aromatic compound, conjugated diene Close object, unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.
Alternatively, it is also possible to enumerate the structural unit with acidic group or the structural unit with bridging property base.
The blending amount of these structural units be preferably 30 moles of % of all structural units of polymer (A-2) hereinafter, More preferable 10 moles of % or less.
(A-2) protective rate of polymer preferably 1%~60%, more preferable 5%~50%, and then preferably 10%~40%. By being set as such range, image reduction (decrease) and sensitivity, analyticity become good.So-called protective rate refers to (A- 2) when all structural units in polymer are set as 100 moles of %, the molar ratio of protected group.
The range of the weight average molecular weight (Mw) preferably 2000~15000 of (A-2) polymer, more preferable 5000~ 12000, and then preferably 7500~12000.By being set as 2000 or more, pixel is formed by rear baking even if can obtain Heating after can also maintain the effect of rectangularity, by being set as 15000 hereinafter, sensitivity can be obtained, the effect that PED characteristic improves Fruit.Here, weight average molecular weight is defined according to the polystyrene scaled value of gel permeation chromatography.
The polydispersity (weight average molecular weight (Mw)/number average molecular weight (Mn)) of (A-2) polymer is preferred 1.0~4.0, more preferable 1.5~3.5, and then preferably 2.0~3.0.By being set as this range, rectangularity optimization.
(A-1) with the allotment ratio of (A-2) ingredient
Photosensitive polymer combination of the invention contains (A-1) and (A-2) as component of polymer, the quality of these ingredients Than preferably 1: 6~6: 1, more preferable 2: 5~8: 1.By being set as this range, has and more effectively play effect of the invention Tendency.
Other polymers (A-3)
In the present invention, other polymers (A-3) can also be contained other than the polymer.Such as it may be exemplified benzene second Alkene based polymer.These polymer are preferably the 10 weight % or less of all component of polymer.
Composition of the invention is preferably relative to total solid content and in the composition with the ratio of 60 weight % or more Example contains (A) component of polymer, more preferably contains (A) component of polymer with the ratio of 80 weight % or more.
<(B) photoacid generator>
Photosensitive polymer combination of the invention contains (B) photoacid generator.Photoacid generator used in the present invention (also referred to as " (B) ingredient ") is preferably the actinic ray for incuding wavelength 300nm or more, preferably incuding wavelength 300nm~450nm And the compound of acid is generated, there is no restriction for chemical structure.In addition, being penetrated about not directly induction the photochemical of wavelength 300nm or more The photoacid generator of line, as long as the change for incuding the actinic ray of wavelength 300nm or more and being used in combination with sensitizer, generating acid Object is closed, then can combine and be preferably used with sensitizer.Photoacid generator used in the present invention preferably generates pKa The photoacid generator that the photoacid generator of 4 acid below, more preferably generation pKa are 3 acid below, most preferably generates The photoacid generator of 2 acid below.
The example of photoacid generator can be enumerated: trichloromethyl-s-triazine, sulfonium salt Huo Iodonium salt (iodonium Salt), quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc..In these, From the viewpoint of insulating properties, it is preferred to use salt compound and oxime sulfonate compounds, more preferable oxime sulfonates chemical combination Object.Using oxime sulfonate compounds, compared with the case where using salt compound, it can obtain obvious excellent Effect.These photoacid generators can be used alone or be applied in combination two or more.Trichloromethyl-s-triazine, two Fragrant base Iodonium salt, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative concrete example may be exemplified Japan Patent The compound recorded in 0083~numbered paragraphs of numbered paragraphs 0088 of special open 2011-221494 bulletin.
Oxime sulfonate compounds, the i.e. compound with oxime sulfonates structure can preferably be illustrated containing the following general formula (B-1) compound of the oxime sulfonates structure represented by.
General formula (B-1)
(in general formula (B-1), R21Indicate alkyl or aryl.Swash expression is bonded with other groups)
Any group can be substituted, R21Alkyl can be straight-chain, or branch-like, or cyclic annular. The substituent group allowed is illustrated below.
R21The preferred carbon number 1~10 of alkyl straight-chain or branch-like alkyl.R21Alkyl can also through halogen atom, The aryl of carbon number 6~11, the alkoxy of carbon number 1~10 or naphthenic base (include the bridge joint such as 7,7- dimethyl -2- oxo norborny Formula alcyl, preferably bicyclic alkyl etc.) it is replaced.
R21The preferred carbon number 6~11 of aryl aryl, more preferable phenyl or naphthyl.R21Aryl can also be through lower alkyl Replaced base, alkoxy or halogen atom.
The compound containing oxime sulfonates structure represented by the general formula (B-1) is it is also preferred that the following general formula (B-2) Represented oxime sulfonate compounds.
General formula (B-2)
(in general formula (B-2), R42Indicate that the alkyl or aryl that can be substituted, X indicate alkyl, alkoxy or halogen atom, m4 The integer for indicating 0~3, when m4 is 2 or 3, multiple X can be the same or different)
R42Preferred scope and the R21Preferred scope it is identical.
As the alkyl of X, the preferably straight-chain or branch-like alkyl of carbon number 1~4.
As the alkoxy of X, the preferably straight-chain of carbon number 1~4 or branch-like alkoxy.
As the halogen atom of X, preferably chlorine atom or fluorine atom.
M4 preferably 0 or 1.
In the general formula (B-2), particularly preferred m4 is that 1, X is methyl, and the position of substitution of X is ortho position, R42For carbon number 1~10 Straight-chain alkyl, 7,7- dimethyl -2- oxo norbornylmethyl or the compound to toluyl groups (p-toluyl).
Compound containing oxime sulfonates structure represented by the general formula (B-1) also more preferable the following general formula (B-3) institute The oxime sulfonate compounds of expression.
General formula (B-3)
(in general formula (B-3), R43With the R in formula (B-2)42For synonymous, X1Indicate halogen atom, hydroxyl, carbon number 1~4 Alkyl, carbon number 1~4 alkoxy, cyano or nitro, n4 indicate 0~5 integer)
R in the general formula (B-3)43It is preferred that methyl, ethyl, n-propyl, normal-butyl, n-octyl, trifluoromethyl, five fluorine second Base, perfluor n-propyl, perfluoro-n-butyl group, p-methylphenyl, 4- chlorphenyl or pentafluorophenyl group, particularly preferred n-octyl.
X1It is preferred that the alkoxy of carbon number 1~5, more preferable methoxyl group.
N4 preferably 0~2, particularly preferred 0~1.
The concrete example of compound represented by the general formula (B-3) can be enumerated: α-(methyl sulphonyl oxygroup imino group) Benzonitrile (α-(methylsulfonyloxyimino) benzyl cyanide), α-(ethylsulfonyl oxygroup imino group) benzonitrile, α-(n-propyl sulfonyl oxygroup imino group) benzonitrile, α-(normal-butyl sulfonyl oxygroup imino group) benzonitrile, α-(4- tosyl Oxygroup imino group) benzonitrile, α-[(methyl sulphonyl oxygroup imino group) -4- methoxyphenyl] acetonitrile (α - [(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile), [(ethylsulfonyl oxygroup is sub- by α - Amino) -4- methoxyphenyl] acetonitrile, α-[(n-propyl sulfonyl oxygroup imino group) -4- methoxyphenyl] acetonitrile, α-[(just Butyl sulfonyl oxygroup imino group) -4- methoxyphenyl] acetonitrile, α-[(4- tosyl oxygroup imino group) -4- methoxyl group Phenyl] acetonitrile.
The concrete example of preferred oxime sulfonate compounds can enumerate following compounds (i)~compound (viii) etc., can It is a kind of or and with two or more to be used alone.Compound (i)~compound (viii) can be used as commercially available product and obtain.Separately Outside, it can also be applied in combination with other kinds of (B) photoacid generator.
Compound containing oxime sulfonates structure represented by the general formula (B-1) is it is also preferred that the following general formula (OS-1) institute table The compound shown.
In the general formula (OS-1), R101Indicate hydrogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl, acyl group, ammonia first Acyl group (carbamoyl), sulfamoyl (sulfamoyl), sulfo group, cyano, aryl or heteroaryl.R102Indicate alkyl or aryl.
X101Expression-O- ,-S- ,-NH- ,-NR105-、-CH2-、-CR106H- or-CR105R107, R105~R107Indicate alkyl 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 also be mutually bonded respectively And form ring.
R121~R124It is preferred that hydrogen atom, halogen atom and alkyl, alternatively, it is also possible to preferably enumerate R121~R124In extremely Few 2 are mutually bonded and are formed the aspect of aryl.Wherein, from the viewpoint of sensitivity, preferably R121~R124It is hydrogen original The aspect of son.
The functional group can further have substituent group.
Compound represented by more preferable the following general formula of compound (OS-2) represented by the general formula (OS-1).
In the general formula (OS-2), R101、R102、R121~R124Respectively with the R in formula (OS-1)101、R102、R121~R124For Synonymous, it is additionally preferred to which example is also identical.
R in these, in the more preferably described general formula (OS-1) and the general formula (OS-2)101For cyano or aryl Aspect, most preferably by represented by the general formula (OS-2) and R101For the aspect of cyano, phenyl or naphthyl.
In addition, the stereochemical structure (E, Z etc.) of oxime or benzothiazole ring can be respectively to appoint in the oxime sulfonate compounds It is a kind of, or mixture.
The concrete example of compound represented by the general formula (OS-1) that can be suitably used in the present invention can be enumerated The compound recorded in 0128~numbered paragraphs of numbered paragraphs 0132 of Japanese Patent Laid-Open 2011-221494 bulletin (illustrates Compound b-1~exemplary compounds b-34), but the present invention is not limited thereto.
In the present invention, preferred the following general formula of compound containing oxime sulfonates structure represented by the general formula (B-1) (OS-3), oxime sulfonate compounds represented by the following general formula (OS-4) or the following general formula (OS-5).
(in general formula (OS-3)~general formula (OS-5), R22、R25And R28Separately indicate alkyl, aryl or heteroaryl, R23、R26And R29Separately indicate hydrogen atom, alkyl, aryl or halogen atom, R24、R27And R30Separately indicate halogen Plain atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X1~X3Separately indicate oxygen atom Or sulphur atom, n1~n3Separately indicate 1 or 2, m1~m3Separately indicate 0~6 integer)
In the general formula (OS-3)~general formula (OS-5), R22、R25And R28Alkyl, aryl or heteroaryl can have substitution Base.
In the formula (OS-3)~formula (OS-5), R22、R25And R28Alkyl can preferably have total carbon number 1 of substituent group~ 30 alkyl.
In addition, in the general formula (OS-3)~general formula (OS-5), R22、R25And R28Aryl can preferably have substituent group The aryl of total carbon number 6~30.
In addition, in the general formula (OS-3)~general formula (OS-5), R1Heteroaryl can preferably have total carbon number 4 of substituent group ~30 heteroaryl.
In the general formula (OS-3)~general formula (OS-5), R22、R25And R28As long as heteroaryl at least one ring be that heteroaryl is fragrant Ring, such as heteroaryl perfume (or spice) ring and phenyl ring contracting ring can also be made.
In the general formula (OS-3)~general formula (OS-5), R23、R26And R29It is preferred that hydrogen atom, alkyl or aryl, more preferable hydrogen Atom or alkyl.
In the general formula (OS-3)~general formula (OS-5), there are 2 or more R in compound23、R26And R29In, preferably Be 1 or 2 for alkyl, aryl or halogen atom, more preferably 1 is alkyl, aryl or halogen atom, particularly preferably Be 1 be alkyl and remaining be hydrogen atom.
R23、R26And R29Alkyl can preferably have substituent group total carbon number 1~12 alkyl, can more preferably have substitution The alkyl of total carbon number 1~6 of base.
R23、R26And R29Aryl can preferably have substituent group total carbon number 6~30 aryl.
In the general formula (OS-3)~general formula (OS-5), X1~X3Separately indicate O or S, preferably O.
In the general formula (OS-3)~general formula (OS-5), contain X1~X3Ring as ring person is 5 Yuans rings or 6 Yuans rings.
In the general formula (OS-3)~general formula (OS-5), n1~n31 or 2 is separately indicated, in X1~X3For the feelings of O Under condition, preferably n1~n3It is each independently 1, in addition, in X1~X3In the case where for S, preferably n1~n3Independently It is 2.
In the general formula (OS-3)~general formula (OS-5), R24、R27And R30Separately indicate halogen atom, alkyl, alkane Oxygroup, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.These, it is preferred to R24、R27And R30Be each independently alkyl or Alkoxy.
R24、R27And R30Alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl can have substituent group.
In the general formula (OS-3)~general formula (OS-5), R24、R27And R30Alkyl can preferably have total carbon number of substituent group 1~30 alkyl.
In the general formula (OS-3)~general formula (OS-5), R24、R27And R30Alkoxy can preferably have the total carbon of substituent group The alkoxy of number 1~30.
In addition, in the general formula (OS-3)~general formula (OS-5), m1~m3The separately integer of expression 0~6, preferably 0 ~2 integer, more preferable 0 or 1, particularly preferred 0.
In addition, each substituent group about (OS-3)~(OS-5), Japanese Patent Laid-Open 2011-221494 bulletin (OS-3) recorded in numbered paragraphs 0092~0109~(OS-5) substituent group preferred scope is similarly preferred.
In addition, particularly preferred the following general formula of compound containing oxime sulfonates structure represented by the general formula (B-1) (OS-6) oxime sulfonate compounds represented by either one or two of~general formula (OS-11).
(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, chloromethane Base, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, R311And R314Separately indicate that hydrogen atom, halogen are former Son, methyl or methoxy, R312、R315、R317And R319Separately indicate hydrogen atom or methyl)
The general formula (OS-6)~general formula (OS-11) preferred scope and Japanese Patent Laid-Open 2011-221494 bulletin 0110~numbered paragraphs of numbered paragraphs 0112 in the preferred scope of (OS-6)~(OS-11) recorded it is identical.
The concrete example of oxime sulfonate compounds represented by the general formula (OS-3)~general formula (OS-5) can be enumerated The compound recorded in 0114~numbered paragraphs of numbered paragraphs 0120 of Japanese Patent Laid-Open 2011-221494 bulletin, but this Invention is not limited to these compounds.
In photosensitive polymer combination of the invention, relative to all resin components in photosensitive polymer combination (preferably solid component, the total amount of more preferable copolymer) 100 mass parts, (B) photoacid generator is preferably with 0.1 mass Part~10 mass parts more preferably use 0.5 mass parts~10 mass parts.Also it can be used together two or more.
<(C) solvent>
Photosensitive polymer combination of the invention contains (C) solvent.Photosensitive polymer combination of the invention is preferably Made of (A) ingredient and (B) ingredient, aftermentioned other compositions for being prepared into as an essential component are dissolved in (C) solvent Solution.The solvent for being used to prepare composition of the invention can be used equably dissolve essential component and any ingredient and not with The solvent of each ingredient reaction.
Well-known solvent can be used in (C) solvent used in photosensitive polymer combination of the invention, can example Show: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, Propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalky lether second Esters of gallic acid, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone Class, amides, lactone etc..In addition, the concrete example of solvent used in photosensitive polymer combination of the invention can also be lifted The solvent recorded in 0174~numbered paragraphs of numbered paragraphs 0178 of Japanese Patent Laid-Open 2011-221494 bulletin out, Japan The solvent recorded in 0167~numbered paragraphs of numbered paragraphs 0168 of open patent 2012-194290 bulletin, by these contents It is incorporated into present specification.
The concrete example of (C) solvent used in photosensitive polymer combination of the invention is for example, Japan Patent is special Open the solvent etc. recorded in numbered paragraphs [0174]~numbered paragraphs [0178] of 2011-221494 bulletin.
In addition, in these solvents, further can also optionally add benzylisoeugenol, two hexyl ethers, ethylene glycol list benzene Ether acetic acid ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone (isophorone), caproic acid (caproic Acid), octanoic acid (caprylic acid), 1- octanol, 1 nonyl alcohol, benzylalcohol, methyl phenyl ethers anisole (anisol), benzyl acetate, benzoic acid second Ester, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, propylene carbonate equal solvent.These solvents can be used alone one Kind is used in mixed way two or more.The solvent that can be used in the present invention be preferably used alone it is a kind of or and with two kinds, more Preferably and with two kinds, and then it is preferably and uses propylene-glycol monoalky lether acetate esters or dialkyl ether, diacetate esters Class and diethylene glycol dialkyl ether class or esters and butanediol alkylether acetates class.
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 that (C) ingredient, which is preferably boiling point, Solvent or these solvents mixture, more preferably boiling point is 130 DEG C of solvent, boiling points 160 more than and less than 160 DEG C DEG C or more and 200 DEG C of solvents below or these solvent mixtures, and then preferably boiling point is 130 DEG C more than and less than 160 DEG C solvent and boiling point be 160 DEG C or more and 200 DEG C solvents below mixture.
Boiling point is that 130 DEG C of solvents more than and less than 160 DEG C may be exemplified: propylene glycol methyl ether acetate (boiling point 146 DEG C), propylene glycol monoethyl ether acetate (158 DEG C of boiling point), propylene glycol methyl n-butyl ether (155 DEG C of boiling point), propylene glycol methyl just Propyl ether (131 DEG C of boiling point).
160 DEG C of boiling point or more of solvent may be exemplified: 3- ethoxyl ethyl propionate (170 DEG C of boiling point), diethylene glycol methyl Ethylether (176 DEG C of boiling point), propylene glycol monomethyl ether propionate (160 DEG C of boiling point), dipropylene glycol methyl ether acetic acid esters (boiling point 213 DEG C), 3- methoxybutyl ether acetic acid ester (171 DEG C of boiling point), diethylene glycol diethyl ether (189 DEG C of boiling point), diethylene glycol dimethyl ether (162 DEG C of boiling point), propylene-glycol diacetate (190 DEG C of boiling point), diethylene glycol monoethyl ether acetic acid esters (220 DEG C of boiling point), dipropyl two Diethylene glycol dimethyl ether (175 DEG C of boiling point), 1,3-BDO diacetate esters (232 DEG C of boiling point).
Relative to all resin components (preferably solid component, more preferably described (A) polymerization in photosensitive polymer combination Object) 100 parts by weight, content preferably 50 parts by weight~3,000 weight of (C) solvent in photosensitive polymer combination of the invention Part, more preferable 100 parts by weight~2,000 parts by weight, and then preferably 150 parts by weight~1,500 parts by weight.
<other compositions>
In positive type photosensitive organic compound of the invention, other than (A) ingredient, (B) ingredient and (C) ingredient, depending on needing It is anti-oxidant to want preferably to add (D) sensitizer, (E) alkali compounds, (F) contiguity modifying agent, (G) interfacial agent, (H) Agent.In turn, in positive type photosensitive organic compound of the invention, plasticiser, hot radical producing agent, anti-oxidant can be added Agent, thermal acid generator, ultraviolet absorbing agent, thickener and organic or inorganic the well-known additive such as antisettling agent.
<(D) sensitizer>
In photosensitive polymer combination of the invention, in order to promote its decomposition when combining with (B) photoacid generator, preferably Be containing sensitizer.Sensitizer absorbs actinic ray or radioactive ray and becomes electron excitation state.As electron excitation state Sensitizer contacted with photoacid generator, generate the effects of electronics is mobile, energy is mobile, fever.Photoacid generator occurs as a result, Chemical change and decompose, generate acid.The example of preferred sensitizer can be enumerated: belong to compounds below and in 350nm Any place of the wavelength region of~450nm has the compound of absorbing wavelength.
The polynuclear aromatic same clan (such as pyrene, triphenylene (triphenylene), anthracene, 9,10- dibutoxy anthracene, 9,10- Diethoxy anthracene, 3,7- dimethoxy anthracene, 9,10- dipropoxy anthracene), xanthene (xanthene) class (such as fluorescein (fluorescein), eosin (eosin), erythrosine (erythrosine), rose red 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 Class (such as thionine (thionine), methylenum careuleum (methylene blue), toluidine blue (toluidine blue)), acridine (such as acridine orange, chloroflavin (chloroflavin), acriflavine (acriflavine)), acridine ketone (such as acridone, 10- butyl -2- chloro-acridine ketone), Anthraquinones (such as anthraquinone), square acid compound (squarylium) class (such as close by side's acidification Object), styryl (styryl) class, basicity styrene base class (such as 2- [2- [4- (dimethylamino) phenyl] vinyl] benzene And oxazole), Coumarins (such as 7- diethylamino -4- methylcoumarin, Hymecromone, 2,3,6,7- tetra- Hydrogen -9- methyl-1 H, 5H, 11H [1] chromene simultaneously [6,7,8-ij] quinolizine -11- ketone (2,3,6,7-tetrahydro-9- Methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non)).
In these sensitizers, preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, tonka-bean Plain class, the more preferable polynuclear aromatic same clan.In the polynuclear aromatic same clan, most preferably chemical combination represented by the following general formula (O) or general formula (P) Object.About the details of general formula (O), illustrated in the 2nd implementation form as be described hereinafter, preferred scope is also identical.
General formula (O)
(R1)n-L1-(R2)m
(in general formula (O), R1And R2Respectively indicate the heterocycle structure of aryl or the ethylenic linkage with 1 or more.L1Indicate tool There is divalent~4 valences concatenating group of 2~4 ethylenic linkages.N and m respectively indicates 1 or 2)
General formula (P)
(in general formula (P), R is respectively the alkyl of carbon number 1~8)
(compound represented by general formula (P))
In general formula (P), R is respectively the alkyl of carbon number 1~8, the alkyl of more preferable carbon number 2~6.
Relative to 100 parts by weight of photoacid generator of photosensitive polymer combination, photosensitive polymer combination of the invention In sensitizer additive amount preferably 0 parts by weight~1000 parts by weight, more preferable 10 parts by weight~500 parts by weight, so preferably 50 parts by weight~200 parts by weight.Also it can be used together two or more.
<(E) alkali compounds>
Photosensitive polymer combination of the invention can also contain alkali compounds.Alkali compounds used in the present invention It can chemically arbitrarily selection uses in alkali compounds used in amplification resist.For example, aliphatic amine, virtue Fragrant race's amine, hetero ring type amine, hydroxide level Four ammonium, quarternary ammonium salt of carboxylic acid etc..
The concrete example of alkali compounds may be exemplified the numbered paragraphs 0052 of Japanese Patent Laid-Open 2009-98616 bulletin The content is incorporated into present specification by the compound recorded in~numbered paragraphs 0056.
The alkali compounds that can be used in the present invention can be used alone, also can be used together it is two or more, preferably Be and with two or more, more preferably and with two kinds, and then be preferably and use two kinds of hetero ring type amine.
In the present invention, chemical combination represented by preferred the following general formula of alkali compounds (Q-a), general formula (Q-b) and general formula (Q-c) At least one of object.
General formula (Q-a)
(in general formula (Q-a), R2Indicate the naphthenic base for the alkyl or carbon number 3~10 that carbon number is 1~6.X indicate oxygen atom or Sulphur atom.Y1Indicate oxygen atom or-NH- base.P1 indicates 1~3 integer)
Alkali compounds used in the present invention is the compound with the feature in structure below: being had in the molecule At least one contains morpholinyl or piperazinyl by the part-structure represented by urea or thiourea bond.
It is sulphur atom that alkali compounds, which is preferably the X, and is thiocarbamide chemical combination represented by the following general formula (Q-a2) Object has part-structure represented by thiourea bond.
General formula (Q-a2)
(in general formula (Q-a2), R3Indicate the naphthenic base for the alkyl or carbon number 3~10 that carbon number is 1~6.Y2Indicate oxygen atom Or-NH- base.P2 indicates 1~3 integer)
Thiourea compound represented by alkali compounds and then more preferably the following general formula (Q-a3), that is, contain morpholine Base.
General formula (Q-a3)
(in general formula (Q-a3), R4Indicate the naphthenic base for the alkyl or carbon number 3~10 that carbon number is 1~6.P3 indicates 1~3 Integer)
The R of compound represented by the general formula (Q-a)~general formula (Q-a3)2~R4Carbon number be 1~6 alkyl it is preferred The alkyl of the carbon numbers such as methyl, ethyl, propyl, normal-butyl, sec-butyl, tert-butyl 1~4, the alkane of the carbon number 1~4 of more preferable straight chain Base, particularly preferred methyl.
The R of compound represented by the general formula (Q-a)~general formula (Q-a3)2~R4Carbon number 3~10 naphthenic base it is preferred The naphthenic base of the carbon numbers such as cyclopropyl, cyclobutyl, cyclohexyl, adamantyl 3~10, the naphthenic base of more preferable carbon number 5~10, especially It is preferred that cyclohexyl.
The concrete example of alkali compounds represented by the general formula (Q-a) can enumerate compound shown below (C-1) ~compound (C-7), but the present invention is not limited to these compounds.
These alkali compounds may be used alone or in combination two or more.
General formula (Q-b)
In general formula (Q-b), R8、R9、R10Separately indicate the alkane of hydrogen atom, the carbon number 1~6 that there can be substituent group The naphthenic base of base, the aryl that can have substituent group or the carbon number 3~10 that can have substituent group.
The R of compound represented by the general formula (Q-b)8~R10Carbon number be 1~6 alkyl, the preferred methyl of aryl, second Base, propyl, normal-butyl, sec-butyl, tert-butyl, amyl, neopentyl, hexyl etc., the alkyl of the carbon number 1~4 of more preferable straight chain, Particularly preferred methyl.
The R of compound represented by the general formula (Q-b)8~R10Carbon number 3~10 the preferred cyclopropyl of naphthenic base, ring fourth The naphthenic base of the carbon numbers such as base, cyclohexyl, adamantyl 3~10, the naphthenic base of more preferable carbon number 5~10, particularly preferred cyclohexyl.
The R of compound represented by the general formula (Q-b)8~R10Alkyl, the aryl substituent group and general formula (Q- that can have A2 R)3The preferred substituents that can have of alkyl it is identical.
General formula (Q-c)
In the present invention, about the additive amount of alkali compounds, from the viewpoint of meeting sensitivity and analyticity whole, with sense On the basis of all resin components (preferably solid component, more preferably described (A) polymer) in photosensitive resin composition, usually It is used in the range of the 0.001 weight % of weight %~20, preferably in 0.005 weight of weight %~10 %, most preferably 0.01 It is used in the range of the weight of weight %~5 %.
<(F) touches modifying agent>
Photosensitive polymer combination of the invention can also contain contiguity modifying agent.Photosensitive polymer combination of the invention In the contiguity modifying agent that can be used be become substrate inorganic matter (such as silicon compounds such as silicon, silica, silicon nitride, gold, The metals such as copper, aluminium) compound that is improved with the adhesion of insulating film.Silane coupling agent, mercaptan based compound can specifically be enumerated Deng.Silane coupling agent used in the present invention as contiguity modifying agent is not particularly limited for the purpose of the modification at interface, Well-known silane coupling agent can be used.
Preferred silane coupling agent can for example refer to the numbered paragraphs of Japanese Patent Laid-Open 2012-042837 bulletin The content is incorporated into present specification by 0175 record.These silane coupling agents can be used alone or combine Using two or more.These coupling agents are effective in improving with the adhesion of substrate, and are also had in adjustment and the cone angle of substrate Effect.
Relative to all resin components (the preferably solid component, more preferably described (A) copolymerization in photosensitive polymer combination Object) 100 parts by weight, content preferably 0.1 parts by weight~20 weights of the contiguity modifying agent in photosensitive polymer combination of the invention Measure part, more preferable 0.5 parts by weight~10 parts by weight.
<(G) interfacial agent>
Photosensitive polymer combination of the invention can also contain interfacial agent.Anion can be used in interfacial agent System, cationic system, nonionic system or both sexes it is any, preferred interfacial agent is alcohol nonionic surfactant.
The preference of interfacial agent can for example refer to the numbered paragraphs of Japanese Patent Laid-Open 2012-042837 bulletin The content is incorporated into present specification by the record of 0184~numbered paragraphs 0196.
These interfacial agents can be used alone or be used in mixed way two or more.
Relative to all resin components (the preferably solid component, more preferably described (A) copolymerization in photosensitive polymer combination Object) 100 parts by weight, additive amount preferably 10 parts by weight of (G) interfacial agent of photosensitive polymer combination of the invention hereinafter, More preferable 0.01 parts by weight~10 parts by weight, and then preferably 0.01 parts by weight~1 parts by weight.
<(H) antioxidant>
Photosensitive polymer combination of the invention can also contain antioxidant.As antioxidant, many institutes can be contained Known antioxidant.By adding antioxidant, there is the coloring that can prevent cured film or can reduce as caused by decomposing Film thickness reduction, the in addition excellent advantage of heat resistant transparent.
This antioxidant for example can with reference to Japanese Patent Laid-Open 2012-042837 bulletin numbered paragraphs 0194~ The content is incorporated into present specification by the record of numbered paragraphs 0196.
Relative to the total solid content of photosensitive polymer combination, the content of antioxidant preferably 0.1 weight of weight %~6 Measure %, the more preferable 0.2 weight weight of %~5 %, the particularly preferred 0.5 weight weight of %~4 %.It, can by being set as the range To obtain the sufficient transparency 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 " new expansion (the daily magazine industry of polymeric additive Newspaper office's (stock)) " in the various ultraviolet absorbing agents recorded or matal deactivator etc. be added to photosensitive resin composition of the invention In object.
2nd implementation form:
Photosensitive polymer combination (hereinafter also referred to " composition of the invention ") of the invention be characterized in that containing: (A) comprising the component of polymer of polymer, the polymer contains the monomeric unit protected through sour decomposability base；(B) light acid produces Raw agent；(O) compound represented by the following general formula (O)；And (C) solvent.Photosensitive polymer combination of the invention can be preferred Ground is used as chemical amplification positive photosensitive polymer combination.
Hereinafter, composition of the invention is described in detail.
(A) comprising the component of polymer of polymer, the polymer contains the monomeric unit protected through sour decomposability base
Composition of the invention includes that polymer is used as (A) component of polymer, and the polymer contains through sour decomposability base The monomeric unit of protection.
(A) component of polymer is preferably insoluble or slightly solubility for alkali, and is had in the monomeric unit through protecting The component of polymer when group (sour decomposability base) through protecting played the role of is decomposed because of acid as alkali-soluble.Here, " alkali-soluble " so-called in the present invention refers to the solution coating by the component of polymer on substrate, and 2 points are heated at 90 DEG C Clock, the film (3 μm of thickness) of the resulting polymer is for 2.38% tetramethyl ammonium hydroxide aqueous solution at 23 DEG C Solution rate is 0.01 μm/second or more, so-called " alkali-insoluble ", refers to the solution coating by the polymer on substrate, 90 It is heated 2 minutes at DEG C, the film (3 μm of thickness) of the resulting polymer is for 2.38% tetramethylphosphonihydroxide hydroxide at 23 DEG C The solution rate of base aqueous ammonium is less than 0.01 μm/second.
(A) ingredient used in the present invention contains polymer, which contains the monomer list protected through sour decomposability base First (a1) (hereinafter sometimes referred to simply as " monomeric unit (a1) ").Monomeric unit (a1) through the protection of sour decomposability base preferably comes Derived from the monomeric unit for the hydroxy styrenes protected through sour decomposability base or with the protection carboxyl protected through sour decomposability base Monomeric unit.
<from the monomeric unit for the hydroxy styrenes protected through sour decomposability base>
Skeleton from the monomeric unit of hydroxy styrenes can be for o-hydroxystyrene, hydroxy styrenes or to hydroxyl Base styrene it is any, from the viewpoint of the pattern form after development, preferred 4-Vinyl phenol skeleton.It is described to derive from The skeleton of the monomeric unit of hydroxy styrenes can also be local hydrogenated.
In turn, the skeleton of the monomeric unit from hydroxy styrenes can have hydroxyl (hydroxy) and through acid Substituent group other than the hydroxyl of decomposability base protection.This substituent group can enumerate alkyl, alkoxy, aralkyl, aryl etc..
Here, the alkyl preferably as methyl, ethyl, propyl, normal-butyl, sec-butyl, tert-butyl carbon number 1~ 4 groups, the naphthenic base is carbon number 3~10 preferably as cyclopropyl, cyclobutyl, cyclohexyl, adamantyl Group, alkenyl carbon number 2~4 groups preferably as vinyl, acrylic, allyl, cyclobutenyl, the virtue Base carbon number 6~14 groups preferably as phenyl, xylyl, toluyl groups, cumenyl, naphthalene, anthryl.
In addition, the substituent group of the substituent group other than hydroxyl (hydroxy) and the hydroxyl protected through sour decomposability base can be lifted Out: hydroxyl, halogen atom (fluorine, chlorine, bromine, iodine), nitro, cyano, the alkyl, methoxyl group, ethyoxyl, hydroxyl-oxethyl, third The alkoxies such as oxygroup, hydroxy propyloxy group, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methoxycarbonyl, ethyoxyl The alkoxy carbonyls such as carbonyl, the aralkyl such as benzyl, phenethyl, cumyl, aralkoxy, formoxyl, acetyl group, bytyry, benzene first The acyl groups such as acyl group, cinnamoyl, valeryl, the acyloxy such as butyryl acyloxy, the alkenyl, ethyleneoxy, propenyloxy group, allyl oxygen The alkenyloxy groups such as base, butenyloxy, the aryl, the aryloxy group such as phenoxy group, the aryloxycarbonyls such as benzoyloxy.
In the present invention, from the monomer for the hydroxy styrenes protected through sour decomposability base contained in (A) ingredient In unit (a1), protecting the protecting group of hydroxyl, there is no particular restriction.The preferred silylation of protecting group, the cumyl carbonyl of the protection hydroxyl Base, acetal group (acetal group), THP trtrahydropyranyl, tetrahydrofuran base, enol base, enolic carbonyl group, three-level alkyl, three-level Alkyl-carbonyl, three-level alkoxy carbonyl etc..More preferable three-level alkyl-carbonyl, three-level alkoxy carbonyl, cumyl carbonyl, acetal Base, THP trtrahydropyranyl, tetrahydrofuran base.Most preferably acetal group.
Described (A) ingredient used in the present invention can obtain in the following manner: as European Patent 254853, Japan Open patent is No. 2-25850 flat, disclosed in Japanese Patent Laid-Open 3-223860, Japanese Patent Laid-Open 4-251259 etc. Like that, the predecessor of group for making to can use acid and decomposing is reacted with alkali soluble resin, or is made to be bonded and be can use acid And the alkali soluble resin monomer and various monomer copolymerizables of the group decomposed.
<monomeric unit with the protection carboxyl protected through sour decomposability base>
Monomeric unit with the protection carboxyl protected through sour decomposability base is the monomeric unit with protection carboxyl, described Protection carboxyl is to be formed the carboxy protective of the monomeric unit with carboxyl using sour decomposability base.
It can be used for the list with carboxyl through the monomeric unit of protection carboxyl made of the protection of sour decomposability base There is no particular restriction for body unit, and well-known monomeric unit can be used.For example: from unsaturated monocarboxylic, The monomeric unit or one of unsaturated carboxylic acid in the molecules such as unsaturated dicarboxylic, unsaturated tricarboxylic acids at least one carboxyl etc. And the monomeric unit with ethylene unsaturated group with the structure from acid anhydrides.
Acid relatively easy to use can be used and the group (such as THP trtrahydropyranyl ester group or four that decompose in sour decomposability base The acetals system functional group such as hydrogen furyl ester group) or group (such as tert-butyl ester base etc. three for being decomposed using acid of relative difficult The three-levels alkylcarbonic acid ester groups such as grade alkyl, tert-butyl carbonate base).
The details for the other monomers unit that carboxyl is protected through sour decomposability base can refer to Japanese Patent Laid-Open 2011- The record of 0029~numbered paragraphs of numbered paragraphs 0044 of No. 215580 bulletins.
(A) monomeric unit (a1) preferably the following general formula (I)~logical formula (III) at least one through the protection of sour decomposability base, At least one of more preferably logical formula (I) or logical formula (II).
Logical formula (I) leads to formula (II) and leads to formula (III)
(in logical formula (I), R2、R3、R4Separately indicate hydrogen atom or methyl, R5Expression can have the straight of substituent group The alkyl of chain, branch or cricoid carbon number 1~6；
In logical formula (II), Ra1~Ra6Separately indicate the alkyl of hydrogen atom, the carbon number 1~20 that there can be substituent group Or can have the aryl of substituent group, Ra2With Ra3、Ra4With Ra5It can also be mutually bonded and form ring.Ra7Indicate hydrogen atom or first Base, Ra8Indicate that the alkyl of halogen atom, hydroxyl or carbon number 1~3, n1 indicate 0~4 integer；
In logical formula (III), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of for alkyl or Aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can also link and form cyclic ether, R4Indicate that hydrogen atom or methyl, X indicate Singly-bound or arlydene)
(logical formula (I))
R2For hydrogen atom or methyl, preferably hydrogen atom.
R3And R4Preferably one be hydrogen atom and another be methyl.
R5Can enumerate: methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl, sec-butyl, tert-butyl, neopentyl, Sec-amyl, tertiary pentyl, Sec-Hexyl, tertiary hexyl, Zhong Gengji, tertiary heptyl, cyclopenta, cyclohexyl etc., preferably methyl, ethyl, propyl, Tert-butyl, cyclohexyl.
R5The substituent group that can have can be enumerated: alkyl, alkoxy, aryl, hydroxyl, halogen atom, nitro, acyl group, acyl Oxygroup, acyl amino (acylamino), sulfuryl amino, alkylthio group, arylthio, aromatic alkylthio, thiophene carbonyloxy group, thiophene first Heterocycle residues such as base carbonyloxy group, pyrrolidones residue etc..The carbon number of these substituent groups preferably 12 or less.In addition, these groups It can be further as replaced these groups.R5Do not have substituent group preferably.
(logical formula (II))
Ra1~Ra7It is preferred that hydrogen atom.
Ra8It is preferred that halogen atom.
N1 preferably 0 or 1, more preferable 0.
(logical formula (III))
In R1And R2In the case where for alkyl, preferably carbon number be 1~10 alkyl.In R1And R2It is excellent in the case where for aryl Select phenyl.R1And R2The alkyl of preferred hydrogen atom or carbon number 1~4 respectively.
R3Indicate alkyl or aryl, the preferably alkyl of carbon number 1~10, more preferable 1~6 alkyl.
X indicates singly-bound or arlydene, preferably singly-bound.
The protective rate of A ingredient preferably 1%~60%, more preferable 5%~50%, and then preferably 10%~40%.By setting It is set to this range, sensitivity improves, and deliquescent poor (discrimination) in exposure portion and unexposed portion becomes good.It is so-called Protective rate, when referring to that the total amount by the monomeric unit in polymer is set as 100 moles of %, the ratio of protected group.
<other monomers unit (a2)>
Composition of the invention, which is preferably, contains (A ') containing the poly- of the monomeric unit (a1) protected through sour decomposability base It closes the polymer that object and (A ＂) contain other monomers unit (a2) and is used as (A) component of polymer.
The polymer (A ') and contain that photosensitive polymer combination of the invention can contain monomeric unit (a1) containing described in There are two kinds of ingredients such as the polymer (A ＂) of other monomers unit (a2) as mutually different polymer, it can also be described containing single The polymer (A ') of body unit (a1) is same copolymer (A) with the polymer (A ＂) containing other monomers unit (a2).In addition, In this specification, if in advance without special instruction, the case where " ingredient A " comprising the polymer (A ') and polymer (A ＂), And both copolymers (A).
Photosensitive polymer combination of the invention is preferably the polymer (A ') containing monomeric unit (a1) and contains The polymer (A ＂) for having other monomers unit (a2) is same copolymer (A).
That is, (A) copolymer that photosensitive polymer combination of the invention preferably comprises is the copolymer containing following component:
(a1) through sour decomposability base protection monomeric unit (hereinafter also referred to " monomeric unit (a1) ") and
(a2) other monomers unit (hereinafter also referred to " monomeric unit (a2) ").
Other monomers unit (a2) can be only a kind of, or two or more.
Other monomers unit for example: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid are cyclic annular Arrcostab, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, bicyclic unsaturated compound class, maleimide chemical combination Species, unsaturated aromatic compound, conjugated diene based compound, unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxyl Acid anhydrides, other unsaturated compounds.
Alternatively, it is also possible to enumerate the monomeric unit with acidic group or the monomeric unit with bridging property base.
In the present invention, other monomers unit (a2) is preferably derived from the monomeric unit of hydroxy styrenes, can be adjacent hydroxyl Styrene, hydroxy styrenes or 4-Vinyl phenol it is any, it is preferably right from the viewpoint of the pattern form after development Hydroxy styrenes skeleton.The skeleton of the monomeric unit of hydroxy styrenes can also be local hydrogenated.The list of the hydroxy styrenes The skeleton of body unit can also have the substituent group other than hydroxyl.This substituent group can be enumerated: hydroxyl, halogen atom (fluorine, chlorine, Bromine, iodine), nitro, cyano, the alkyl, methoxyl group, ethyoxyl, hydroxyl-oxethyl, propoxyl group, hydroxy propyloxy group, positive fourth oxygen The alkoxies such as base, isobutoxy, sec-butoxy, tert-butoxy, the alkoxy carbonyls such as methoxycarbonyl, ethoxy carbonyl, benzyl, The aralkyl such as phenethyl, cumyl, aralkoxy, formoxyl, acetyl group, bytyry, benzoyl, cinnamoyl, valeryl etc. Acyl group, the acyloxy such as butyryl acyloxy, the alkenyl, the alkenyloxy groups such as ethyleneoxy, propenyloxy group, allyloxy, butenyloxy, institute State aryl, the aryloxy group such as phenoxy group, the aryloxycarbonyls such as benzoyloxy.It is preferred, however, that not having substituent group.
Namely it is preferred that at least one kind of of other monomers unit (a2) is following monomeric units.
The ratio preferably 1/99~60/40, more preferable 5/95~50/50 of monomeric unit (a1) and monomeric unit (a2), into And it is preferred that 10/90~40/60.
The range of the weight average molecular weight (Mw) preferably 2000~15000 of the A ingredient, more preferable 5000~ 12000, and then preferably 7500~12000.By being set as 2000 or more, pixel is formed by rear baking even if can obtain Heating after can also maintain the effect of rectangularity, by being set as 15000 hereinafter, sensitivity can be obtained, the effect that PED characteristic improves Fruit.Here, weight average molecular weight is defined according to the polystyrene scaled value of gel permeation chromatography.
The polydispersity (weight average molecular weight (Mw)/number average molecular weight (Mn)) preferably 1.0 of the A ingredient~ 4.0, more preferable 1.0~3.0, and then preferably 1.0~1.5.By being set as this range, the dissolution of exposure portion and unexposed portion Property difference (discrimination) increase, in addition rectangularity also becomes good.
The preference of component of polymer (A) used in the present invention described below, but the present invention is not limited to these certainly Preference.
Composition of the invention is preferably relative to total solid content and in the composition with the ratio of 60 weight % or more Example contains (A) component of polymer, more preferably contains (A) component of polymer with the ratio of 80 weight % or more.
<(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 ") it is identical as photoacid generator used in the 1st implementation form, preferred scope is also identical.
<compound represented by (O) general formula (O)>
Photosensitive polymer combination of the invention contains compound represented by general formula (O).In the present invention, general formula (O) institute The compound of expression as photoacid generator sensitizer and play a role.All the time, in the field of organic EL display device In, using the approximate compound of compound represented by general formula (O) used in structure and the present invention, but unlike the present invention that Sample is used as the sensitizer of photoacid generator.In addition, though using structure and general formula (O) in the field entirely different with the present invention The approximate compound of represented compound, but purpose pursued etc. is also different.
General formula (O)
(R1)n-L1-(R2)m
(in general formula (O), R1And R2Respectively indicate the heterocycle structure of aryl or the ethylenic linkage with 1 or more.L1Indicate tool There is divalent~4 valences concatenating group of 2~4 ethylenic linkages.N and m respectively indicates 1 or 2)
R1And R2Respectively indicate the heterocycle structure of aryl or the ethylenic linkage with 1 or more, preferably R1And R2At least One indicates the heterocycle structure of the ethylenic linkage with 1 or more, more preferably R1And R2The two indicates the second with 1 or more The heterocycle structure of ethylene linkage.Heterocycle preferably contains sulphur atom.
R1And R2Possessed cyclic structure can be monocycle, or condensed ring.In the present invention, R1And R2Aryl Or the heterocycle structure with 1 or more ethylenic linkage preferably only contains monocycle as cyclic structure respectively.In this case, single Ring can be only 1, or 2 or more, preferably 1~4, more preferable 1.
R1And R2Contained ring may be exemplified 2 or more condensed rings of 5 Yuans rings, 6 Yuans rings, 5 Yuans rings and 6 Yuans rings, and preferably 5 Member's ring or 6 Yuans rings.
R1And R2Can preferably have respectively substituent group phenyl or the following general formula (O-1) represented by group.
General formula (O-1)
(in general formula (O-1), R indicates substituent group, the integer that r is 0~2)
The substituent group of substituent group and general formula (O-1) that the phenyl can have is preferably 1 substitution base portion of every 1 molecule The quality divided is 250 hereinafter, more preferable 100 or less.The substituent group of substituent group and general formula (O-1) that the phenyl can have point Not preferred halogen atom, alkoxy, alkyl or amino, more preferable alkoxy, alkyl, and then preferably carbon number 1~3 alkoxy or The alkyl of carbon number 1~4.
Phenyl does not have substituent group preferably.
R preferably 0 or 1, more preferable 0.
R1And R2Preferably same group.
N and m respectively indicates 1 or 2, and difference preferably 1, more preferably the two are 1.
L1Also it can have cyclic structure, ethylenic linkage can also be contained in cyclic structure.L1Preferably at least have- (CR=CR) heterocycle structure of p- (R is hydrogen atom or methyl, the integer that p is 2 or more) or the ethylenic linkage with 1 or more, more It is preferred that group represented by the following general formula (O-2) or general formula (O-3), so preferably by general formula (O-2) represented by.
L1Number preferably 2 or 3, more preferable 2 of ethylenic linkage.
General formula (O-2)
(in general formula (O-2), S1 be 1~6 integer)
The integer of S1 preferably 1~4, more preferable 1.
General formula (O-3)
(in general formula (O-3), S2 be 2~4 integer)
S2 preferably 2 or 3.
(C) any formula institute table of compound represented by general formula (O) and then preferably the following general formula (O-4)~general formula (O-6) The compound shown.
General formula (O-4)
General formula (O-5)
General formula (O-6)
(in general formula (O-4)~general formula (O-6), R1~R6Respectively hydrogen atom or substituent group)
In general formula (O-4)~general formula (O-6), R1~R6More preferable hydrogen atom, halogen atom, alkoxy, alkyl respectively, point The alkyl of other and then preferred hydrogen atom, the alkoxy of carbon number 1~3 or carbon number 1~4, the particularly preferred hydrogen atom of difference.
In general formula (O), the number of ethylenic linkage preferably 4~14, more preferable 5~10.
Hereinafter, illustrating compound represented by the general formula (O) preferably used in the present invention, but the present invention is certainly unlimited Due to these compounds.In following, Me indicates methyl.
Relative to all resin components (preferably conjunction of solid component, more preferable copolymer in photosensitive polymer combination Metering) 100 mass parts, compound represented by (O) the following general formula (O) is preferably with 0.1 mass parts~10 mass parts, more Preferably with 0.5 mass parts~5.0 mass parts.By the additive amount use with this range, this hair can be effectively played Bright effect, even if in addition there is the influence of the absorption of sensitizing coloring matter, light can also reach film bottom, therefore rectangularity is good.It can also With and with two or more.
<(C) solvent>
Photosensitive polymer combination of the invention contains (C) solvent.Solvent and solvent phase used in the 1st implementation form Together, preferred scope is also identical.
<other compositions>
Positive type photosensitive organic compound of the invention other than (A) ingredient, (B) ingredient, (C) ingredient and (O) ingredient, It optionally can also preferably add alkali compounds, contiguity modifying agent, interfacial agent, antioxidant.These additives can It is excellent to use additive identical with the alkali compounds of the 1st implementation form, contiguity modifying agent, interfacial agent, antioxidant Select range also identical.In turn, plasticiser can be added in positive type photosensitive organic compound of the invention, hot radical generates Agent, antioxidant, thermal acid generator, ultraviolet absorbing agent, the antisettling agent etc. of thickener and organic or inorganic are well-known Additive.
In the present invention, the sensitizer other than compound represented by general formula (O) also can be used together, preferably substantially not Contain the sensitizer.It is so-called to contain substantially no, such as refer to including deploying in the range of not influencing effect of the invention Situation etc..
[manufacturing method of pattern]
Then, the manufacturing method of pattern of the invention is illustrated.
The manufacturing method of pattern of the invention be characterized in that include (1) below~(6) process.
(1) photosensitive polymer combination of the invention is applied to the process on substrate；
(2) process of solvent is removed from applied photosensitive polymer combination；
(3) process being exposed using active radioactive ray；
(4) process developed using aqueous developer；
(5) process that the substrate is etched as mask using resist pattern is formed by；And
(6) process for removing the resist pattern.
Next coming in order are illustrated each process.
(1) in process, preferably positive type photosensitive organic compound of the invention is applied on substrate, is made and contains There is the wet film of solvent.
(2) in process, solvent is removed from the applied film by decompression (vacuum) and/or heating, in substrate Upper formation dry coating.
(3) in the process being exposed, to the actinic ray of resulting film illumination wavelength 300nm~450nm.The process In, in the 1st implementation form, (B) photoacid generator decomposes and generates acid.By the catalytic action of generated acid, make (A-1) The hydroxyl through sour decomposability base (protection carboxyl) protection of structural unit (a-1) contained in ingredient with acidic group hydrolyzes, raw At phenolic hydroxyl group.In the 2nd implementation form, (B) photoacid generator decomposes and generates acid.Made by the catalysis of generated acid With, make the monomeric unit (a1) of hydroxy styrenes contained in (A) ingredient through sour decomposability base protection hydroxyl hydrolyze, generate Phenolic hydroxyl group.
In the region for generating acid catalyst, in order to accelerate the hydrolysis, heated after being optionally exposed It handles (postexposure bake (Post Exposure Bake), hereinafter also referred to " PEB ").By PEB, can promote to decompose from acid The property carboxyl of base or the generation of phenolic hydroxyl group.In the manufacturing method of pattern of the invention, preferably in the developing procedure Afterwards, before etching work procedure, the process comprising toasting and making resist pattern thermmohardening after carrying out to the resist pattern.
The hydroxyl of the structural unit (A-2) of hydroxy styrenes contained in (A) ingredient of 1st implementation form is decomposed due to acid Activation evergy it is low, be easy because being decomposed by exposure from the acid of photoacid generator, generation phenolic hydroxyl group, therefore not PEB is necessarily carried out, eurymeric image can also be formed by developing, in the manufacturing method of pattern of the invention, preferably It is to carry out the post-bake process using photosensitive polymer combination of the invention.
In 2nd implementation form, the monomeric unit (a1) of hydroxy styrenes contained in (A) ingredient is protected through sour decomposability base The hydroxyl of shield is easy to decompose because by exposing from the acid of photoacid generator since the activation evergy that acid decomposes is low, Phenolic hydroxyl group is generated, therefore is not necessarily required to carry out PEB, eurymeric image, but pattern of the invention can also be formed by developing Manufacturing method in and it is nonessential.
In the manufacturing method of pattern of the invention, PEB is preferably carried out at relatively low temperature, thus not Cause the hydrolysis for promoting sour decomposability base in the case where cross-linking reaction.Carry out the temperature preferably 30 DEG C~130 in the case where PEB DEG C, more preferable 40 DEG C~110 DEG C, particularly preferred 50 DEG C~100 DEG C.Heating time can suitably set according to heating temperature etc. It is fixed, but it is preferred that being set as in the range of 1 minute~60 minutes.
(4) in the process developed, using alkaline-based developer to the copolymer with free carboxyl or phenolic hydroxyl group Develop.By the exposure that will contain the resin combination being easily soluble in alkaline-based developer and with carboxyl or phenolic hydroxyl group Portion region removes, and forms eurymeric image.
PEB is preferably carried out at relatively low temperature, thus promotes acid in the case where not causing cross-linking reaction The hydrolysis of decomposability base.At preferably 30 DEG C~130 DEG C of temperature, more preferable 40 DEG C~110 DEG C in the case where progress PEB, especially It is preferred that 50 DEG C~80 DEG C.Heating time can suitably set according to heating temperature etc., but it is preferred that be set as 10 minutes~ In the range of 90 minutes.
In the manufacturing method of pattern of the invention, aftermentioned etching work preferably is played from the process that (4) develop It include post-bake process between until sequence, more preferably after the process that (4) develop, before etching work procedure, including The process toasted after being carried out at 100 DEG C~160 DEG C to the resist pattern.Rear baking after the process that (4) develop In roasting process, by heating to resulting eurymeric image, the effect that etching dimensional stability improves can be obtained.
More preferable 120 DEG C of post-bake process after the process that (4) develop, before the process that (5) are etched~ 150℃.By carrying out PEB at relatively low temperature, can obtain not makes resist pattern heat flow and improves etching ruler The effect of very little stability.
Heating time can suitably set according to heating temperature etc., preferably be set as 1 minute~60 minutes models In enclosing.
Then, the forming method for the cured film for using photosensitive polymer combination of the invention is illustrated.
<preparation method of photosensitive polymer combination>
By the essential component and any ingredient of the 1st implementation form and the 2nd implementation form with set ratio and using arbitrarily Method mixing, stirring and dissolving and prepare photosensitive polymer combination.For example, it is also possible to which being made makes the dissolution in advance respectively of each ingredient After the solution in above-mentioned solvent, by these solution with set ratio mixes and prepares resin combination.Such as it can also make For using after being filtered with 0.2 μm filter in aperture etc. to the composition solution prepared as described above.
<process that photosensitive polymer combination is applied the process and (2) removing solvent on substrate by (1)>
Photosensitive polymer combination is applied on set substrate, is removed and depressurizing and/or heating (prebake conditions) Thus solvent can form required dry coating.It, can example as the substrate, such as in the manufacture of liquid crystal display element Show: equipped with polarizer and then being optionally equipped with black-matrix layer and color filter layers and then be equipped with transparent conductive circuit layer Glass plate etc..Photosensitive polymer combination is applied to the method on substrate, and there is no particular restriction, wherein preferred in the present invention It is to base plate coating photosensitive polymer combination.The coating method of substrate is not particularly limited, slit painting can be used for example The methods of cloth method, spray-on process, rolling method, method of spin coating.Wherein, from the viewpoint of being suitable for large substrate, preferably slit is applied Cloth method.It is preferred because of productivity height if being manufactured with large substrate.Here, so-called large substrate refers to that each side is 1m or more Size substrate.
In addition, the heating condition of the process of (2) is acid point in the structural unit (a-1) in (A) ingredient in unexposed portion Xie Xingji decomposes and (A) ingredient is made to be in alkaline developer the simultaneously range of non-solubility, also according to the type of each ingredient Or allotment ratio and it is different, preferably 80 DEG C~130 DEG C, 30 seconds~120 seconds or so.
<process (pattern forming method) that the process and (4) that (3) are exposed are developed>
In the process of (3), actinic ray is irradiated across the mask with predetermined pattern to the substrate for being equipped with film.It exposes After light process, after optionally being heated (PEB), exposure portion region is removed using alkaline-based developer in the process of (4) It goes and forms picture pattern.
Using in photoactinic exposure, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, change can be used Lamp, light emitting diode (Light Emitting Diode, LED) light source, excimer laser generation device etc. are learned, it can be preferably The actinic ray of wavelength using g ray (436nm), i ray (365nm), h ray (405nm) etc. with 300nm~450nm. In addition, can also optionally pass through the light splitting as long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter Filter adjusts irradiation light.
(3) mask used in process is preferably with can disposably obtain half of the pattern with multi-thickness Tone (halftone) phase mask.
(4) in developer solution used in process, preferably contain alkali compounds.Alkali compounds can for example make With: the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide；The alkali carbonates such as sodium carbonate, potassium carbonate Class；The alkaline metal bicarbonates class such as sodium bicarbonate, potassium bicarbonate；Tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide gallbladder The ammonium hydroxide classes such as alkali (choline hydroxide)；The aqueous solution of sodium metasilicate, sodium metasilicate etc..Alternatively, it is also possible to use The water of the water-miscible organic solvents such as methanol or the ethyl alcohol of appropriate amount or interfacial agent is added in the aqueous solution of the bases Solution is as developer solution.
The pH value of developer solution preferably 10.0~14.0.
Developing time preferably 30 seconds~180 seconds, in addition, the method for development is puddle formula (puddle) development method, leaching Stain method etc. it is any.After development, flowing water cleaning in 30 seconds~90 seconds can be carried out and form required pattern.
<process that (5) are etched>
The manufacturing method of pattern of the invention includes that (5) will be formed by resist pattern as mask to the base The process that plate is etched.
Using the resist pattern as mask, to the method that the substrate is etched, there is no particular restriction, can be used Well-known method.
<process that (6) remove resist pattern>
The manufacturing method of pattern of the invention includes the process that (6) remove the resist pattern.
There is no particular restriction for the method that the resist pattern is removed, and well-known method can be used.
<substrate>
There is no particular restriction for substrate used in the manufacturing method of pattern of the invention, can be used for example: chromium film, molybdenum Film, molybdenum alloy film, tantalum film, tantalum alloy film, indium oxide (ITO) film or tin oxide film for being doped with tin oxide, Ni, Cu, Fe, Al etc. Metal substrate；It is quartz, glass, silicon nitride film, silicone, nitridation silicone, silicone, oxidation silicone, amorphous silicone film, spin-coating Glass (Spin on glass, SOG), the silicon wafer of semiconductor element manufacture, liquid crystal cell manufacture glass square substrate Equal silicon substrates；Paper, polyester film, polycarbonate membrane, polyimide film, other polymers substrate used in organic EL display device Equal polymeric substrates；Ceramic material, Ti substrate, Al substrate, single crystal sapphire substrate used in LED illumination etc..Wherein, this hair Preferred ito substrate, molybdenum base plate, silicon substrate, Cu substrate, Al substrate or single crystal sapphire substrate, more preferable ito substrate, molybdenum in bright Substrate, silicon substrate or single crystal sapphire substrate, and then preferably ito substrate or single crystal sapphire substrate.
The shape of substrate can be plate, or web-like.
[cured film]
In the present invention, after the process that (4) develop, to passing through the resulting pattern corresponding with unexposed area of developing Using heating devices such as hot plate or baking ovens, at a temperature of set, at such as 180 DEG C~250 DEG C, carried out with the set time Heat treatment, such as heated if on hot plate with 5 minutes~60 minutes, if baking oven with 30 minutes~90 points Clock is heated, it is possible thereby to form the cured films such as the excellent protective film such as heat resistance, hardness or interlayer dielectric.
In addition, by carrying out in a nitrogen environment, can also be improved the transparency of cured film when being heated.
Moreover it is preferred that before heat treatment, using actinic ray to the substrate for having formd pattern-like cured film After being exposed again, heated.
That is, when forming cured film of the invention, preferably in the process developed and the process for carrying out thermmohardening Between, the process that is exposed again including the use of actinic ray.
As long as the exposure in the process exposed again is carried out using method same as the process being exposed , in the process exposed again, preferably being formed by photosensitive polymer combination of the invention to substrate The side of film carries out blanket exposure.The preferred light exposure of the process exposed again is 100mJ/cm2~1,000mJ/cm2。
[pattern]
Pattern of the invention be use photosensitive polymer combination of the invention harden resulting resist pattern as Mask is etched resulting pattern to the substrate.Pattern of the invention can preferably act as ITO pattern, molybdenum pattern or Silicon pattern can more preferably be used as ITO pattern.
Photosensitive polymer combination of the invention can obtain square since sensitivity, analyticity and exposure tolerance are excellent The excellent resist pattern of shape.Pattern of the invention is the manufacture using the pattern of the invention using the resist pattern Obtained by method, therefore microfabrication can be carried out, can make organic EL display device or liquid crystal display device that there is fine Display characteristic.
[organic EL display device, liquid crystal display device]
Photosensitive polymer combination of the invention is also used as interlayer dielectric, can use the system of pattern of the invention Method is made to manufacture organic EL display device and liquid crystal display device.Organic EL display device and liquid crystal display device of the invention Preferably there is ITO pattern.
Organic EL display device or liquid crystal display device of the invention uses the photonasty tree of the invention in addition to having Oil/fat composition and other than the planarization film or interlayer dielectric that are formed, there is no particular restriction, can enumerate using various structures Well-known various organic EL display devices or liquid crystal display device.
In addition, photosensitive polymer combination of the invention and cured film of the invention are not limited to the purposes, Ke Yiyong In various uses.Such as other than planarization film or interlayer dielectric, the protection of colored filter can also be suitably used for Film or for by the liquid crystal layer in liquid crystal display device remain certain thickness spacer (spacer) or solid photographic member The lenticule (microlens) etc. of colorized optical filtering on piece is set in part.
Fig. 1 shows the composition concept maps of an example of organic EL display device, indicate bottom-emission (bottom emitting) The schematic sectional view of substrate in the organic EL display device of type has planarization film 4.
The TFT1 that bottom grid (bottom gate) type is formed on glass substrate 6, is formed with covering the state of the TFT1 Insulating film 3 comprising Si3N4.After forming the contact hole of illustration omitted here in insulating film 3, formed on the insulating film 3 via The contact hole and the wiring 2 (height 1.0 μm) for being connected to TFT1.Wiring 2 is for will be formed in process between TFT1 or hereafter The line that is connect with TFT1 of organic EL element.
In turn, in order to make the concave-convex planarization generated because forming wiring 2, to fill the concave-convex shape caused by wiring 2 State forms planarization film 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, via contact hole 7 It is connected to wiring 2 and forms the first electrode 5 comprising ITO.In addition, first electrode 5 is equivalent to the anode of organic EL element.
The insulating film 8 for the shape for forming the edge of covering first electrode 5 can prevent first by the way that the insulating film 8 is arranged The short circuit between second electrode formed in electrode 5 and process hereafter.
In turn, in Fig. 1 and not shown, but be sequentially deposited across required pattern mask and hole transmission layer, organic is set Luminescent layer, electron transfer layer then form the second electrode comprising A1 in the entire surface above substrate, are used by using sealing Glass plate and ultraviolet ray hardening type epoxy resin are bonded and are sealed, and are obtained the connection in each organic EL element and are used to drive this The organic EL display device of active array type made of the TFT1 of organic EL element.
Fig. 2 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 the liquid crystal display panel on the back side with back light unit 12, and the element of TFT16 is configured in liquid crystal display panel, should The element of TFT16 is corresponding in the 2 sheet glass substrates 14 for having attached light polarizing film, all pixels between glass substrate 15 with configuration. By the contact hole 18 formed in cured film 17, to be formed to each element formed on the glass substrate the ITO of pixel electrode The wiring of transparent electrode 19.On ito transparent electrode 19, layer equipped with liquid crystal 20 and the RGB color filter for being configured with black matrix" Mating plate 22.
Embodiment
Embodiment is enumerated below to be more particularly described the present invention.Material, usage amount shown in following embodiment, ratio Example, process content, processing sequence etc. can then be suitably changed without departing from purport of the invention.Therefore, the scope of the present invention is not It is defined in concrete example as shown below.In addition, the embodiment of the 2nd implementation form is reference example.
The embodiment of 1st implementation form:
In following synthesis example, symbol below respectively indicates compound below.
V-65:2,2 '-azo are bis- (2,4- methyl pentane nitrile) (and Wako Pure Chemical Industries Manufacturing)
V-601: dimethyl -2,2 '-azo is bis- (2 Methylpropionic acid ester) (and Wako Pure Chemical Industries Manufacturing)
MAEVE: methacrylic acid -1- ethoxy ethyl ester
MATHF: methacrylic acid tetrahydro -2H- furans -2- base ester
MATHP: methacrylic acid -2- tetrahydropyrans ester (manufacture of chemical company, the village Xin Zhong)
StOEVE:4- (1- ethoxy ethoxy) styrene
THFFMA: tetrahydrofurfuryl methacrylate
MMA: methyl methacrylate
MAA: methacrylic acid
(synthesis (MATHF/MMA/MAA=60/15/25) of synthesis example 1:a-1-1)
<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 equivalents) are added dropwise in solution.It after stirring 1 hour, adds saturated sodium bicarbonate (500mL), benefit It is extracted with ethyl acetate (500mL), after being dried using magnesium sulfate, is depressurized after filtering insoluble matter at 40 DEG C or less dense The yellow oil of residue is evaporated under reduced pressure by contracting, obtained in the form of colorless oil boiling point (bp.) be 54 DEG C~56 DEG C/ Methacrylic acid tetrahydro -2H- furans -2- base ester (MATHF) 125g (yield 80%) of 3.5mm Hg fraction.
<synthesis of a-1-1>
Mixed methyl acrylic acid 50.33g (0.585mol), camphorsulfonic acid 0.27g (0.2mol%) be simultaneously in three-necked flask It is cooled to 15 DEG C.2,3-dihydrofuran 41.00g (0.585mol) is added dropwise in the solution.Unsaturated carbonate hydrogen is added to reaction solution Sodium water solution (500mL) is extracted using ethyl acetate (500mL), is dried using magnesium sulfate.After insoluble matter is filtered It is concentrated under reduced pressure at 40 DEG C or less, the colorless oil of residue is evaporated under reduced pressure, thus to obtain boiling point (bp.) be 54 DEG C~56 DEG C/ The MATHF of the 73.02g of 3.5mm Hg fraction.
It is put into PGMEA (29.6g) in three-necked flask, is warming up to 80 DEG C in a nitrogen environment.Make MATHF (28.1g), MMA (7.51g), MAA (3.87g), V-601 (1.93g is 2.8mol% relative to monomer) are dissolved in PGMEA (29.6g) In, it was added drop-wise in the solution with 2 hours.It is stirred 4 hours after completion of dropwise addition, reaction was completed.Thus to obtain a-1-1.Weight is flat Average molecular weight is 15,000.Polydispersity is 2.60.
(synthesis of synthesis example 2:a-1-2)
In synthesis example 1, in addition to so that the ratio of MATHF, MAA and MMA become 15 moles, 15 moles and 70 moles of side Formula changes other than molar ratio, is carried out similarly operation.
(synthesis of synthesis example 3:a-1-3)
In synthesis example 1, in addition to so that the ratio of MATHF, MAA and MMA become 25 moles, 15 moles and 60 moles of side Formula changes other than molar ratio, is carried out similarly operation.
(synthesis of synthesis example 4:a-1-4)
In synthesis example 1, in addition to so that the ratio of MATHF, MAA and MMA become 35 moles, 15 moles and 50 moles of side Formula changes other than molar ratio, is carried out similarly operation.
(synthesis of synthesis example 5:a-1-5)
In synthesis example 1, in addition to so that the ratio of MATHF, MAA and MMA become 45 moles, 15 moles and 40 moles of side Formula changes other than molar ratio, is carried out similarly operation.
(synthesis (THF/EVE/PHS/MAA=33/15/37/15) of synthesis example 6:a-1-6)
<synthesis of resin (R-1)>
Third will be dissolved in acetoxy-styrene 110.3g (0.68 mole), methacrylic acid 10.3g (0.12 mole) In glycol monomethylether acetate (PGMEA) 140g, dimethyl -2,2 '-is put at 65 DEG C~75 DEG C under nitrogen stream and stirring The PGMEA solution of bis- (2 Methylpropionic acid ester) (V-601) 6.5g (0.028 mole) of azo, and then persistently stir 6 hours, thus Carry out polymerization reaction.It is dissolved in methanol 200ml, adds methoxylation sodium methanol solution (SM-28) 14g, react 3 hours.It utilizes Hydrochloric acid is neutralized, and addition water 200ml is diluted, and addition ethyl acetate 300ml carries out liquid separation operation, is washed with water 3 times.So Afterwards, the resin of white is precipitated.The resin is separated by filtration, washed, dried.And then be dissolved in acetone 200ml, on one side Stirring is added drop-wise on one side in hexane/ethyl acetate=10/1 solution of 3L, carries out reprecipitation.Resulting resin is done in vacuum It is 24 hours dry at 40 DEG C in dry device, obtain poly- (4-Vinyl phenol)/MAA alkali soluble resin (R-1).Resulting resin Weight average molecular weight be 15000, polydispersity 2.60.
<synthesis of polymer THF/EVE/PHS/MAA>
Resulting alkali soluble resin (R-1) 23.0g and propylene glycol methyl ether acetate (PGMEA) 94.4g is molten Solution is evaporated under reduced pressure in flask, and water and PGMEA azeotropic distillation are removed.Addition 2 after water content is sufficiently lower is confirmed, 3- dihydrofuran 4.17g, ethyl vinyl ether 2.08g, p-methyl benzenesulfonic acid 0.025g are stirred at room temperature 4 hours.It adds thereto Triethylamine 0.090g and stop reacting.Ethyl acetate is added in reaction solution, and then after being washed, pass through vacuum distillation removal By ethyl acetate, water distillation removal, obtaining THF protective rate is that the conduct that 33 moles of %, EVE protective rates are 15 moles of % is soluble The polymer (a-1-6) of resin.
(synthesis example 7: the synthesis of polymer P HS-EVE)
By alkali soluble resin, (Ma Lukalinka (Maruka Lyncur) M S-4P, ball are apt to the limited public affairs of petrochemistry share Department's manufacture) 20g and propylene glycol methyl ether acetate (PGMEA) 320g be dissolved in flask, be evaporated under reduced pressure, by water with PGMEA azeotropic distillation removal.It confirms after water content is sufficiently lower, adds ethyl vinyl ether 4.48g and p-methyl benzenesulfonic acid 0.35g is stirred at room temperature 1 hour.It adds triethylamine 0.28g thereto and stops reacting.Acetic acid second is added in reaction solution Ester, and then after being washed, the PGMEA of ethyl acetate, water, azeotropic ingredient is distilled by removal by vacuum distillation removal, is obtained Polymer P HS-EVE.The weight average molecular weight of gained resin is 11,000.In addition, polydispersity is 2.6.
The structure of PHS-EVE is 1- ethoxyethyl group protective/4-Vinyl phenol copolymer (30 of 4-Vinyl phenol Mole %/70 mole %).
PHS-EVE
(synthesis example 8: the synthesis of polymer P HS-THF)
By alkali soluble resin (manufacture of Ma Lukalinka M S-4P, Wan Shan chemical industry limited liability company) 15.6g and Propylene glycol methyl ether acetate (PGMEA) 100g is dissolved in flask, is evaporated under reduced pressure, water and PGMEA azeotropic distillation are gone It removes.It confirms after water content is sufficiently lower, adds 2,3-dihydrofuran 2.7g and p-methyl benzenesulfonic acid 0.015g, be stirred at room temperature 2 hours.It adds triethylamine 0.090g thereto and stops reacting.Ethyl acetate is added in reaction solution, and then after being washed, By vacuum distillation removal by ethyl acetate, water distillation removal, obtaining protective rate is 25 moles of % as soluble resin Polymer P HS-THF.The weight average molecular weight of gained resin is 12,000.In addition, polydispersity is 2.6.
The structure of PHS-THF is 2- tetrahydrofuran base protective/4-Vinyl phenol copolymer (25 of 4-Vinyl phenol Mole %/75 mole %).
PHS-THF
(synthesis example 9: the synthesis (MATHP/MAA/MMA=60/15/25) of polymer a-1-7)
In the synthesis of polymer a-1-1, MATHF is changed to MATHP, and adjust according to the molar ratio of subject polymer Save additive amount, in addition to this, similarly synthetic polymer a-1-7 (MATHP/MAA/MMA=60/15/25).
(synthesis example 10: the synthesis (MAEVE/MAA/MMA=60/15/25) of polymer a-1-8)
In the synthesis of polymer a-1-1, MATHF is changed to MAEVE, and adjust according to the molar ratio of subject polymer Save additive amount, in addition to this, similarly synthetic polymer a-1-8 (MAEVE/MAA/MMA=60/15/25).
Polymer a-1-9:BuVE/MAA/MMA=60/15/25 (following structures)
Polymer a-1-10:CyHexVE/MAA/MMA=60/15/25 (following structures)
The manufacture of polymer P HS:(Wan Shan chemical industry limited liability company, Ma Lukalinka MS-4P)
Photoacid generator
(B-1) following compounds
α-is synthesized according to the method recorded in the numbered paragraphs [0108] of Japanese patent special table 2002-528451 bulletin (p-toluenesulfonyl oxygroup imino group) phenylacetonitrile.
(B-2) following compounds (manufacture of BASF (BASF) company, CGI-1397)
(B-3) following structures (BASF AG's manufacture, Yi Luka (Irgacure) 250)
Yi Luka 250
Sensitizer
DBA: An Tuolaka (Anthracure) (manufacture of Kawasaki chemical conversion industry)
O-1 (manufacture of Tokyo chemical conversion industry, D2077)
O-2 (manufacture of Tokyo chemical conversion industry, T1196)
Epoxy resin
JER157S65, Japanese epoxy resin (Japan epoxy resin) manufacture
Epiclon (EPICLON) N-695, DIC (DIC) manufacture
(preparation of photosensitive polymer combination)
Each ingredient is dissolved in the way of becoming and being formed shown in following tables and is mixed, the polytetrafluoro for being 0.2 μm using bore Ethylene filter is filtered, and obtains the photosensitive polymer combination of Examples and Comparative Examples.In addition, allotment is than being as following Table is set like that.
(A) polymer is blended (A-1) and (A-2) with ratio shown in table (weight ratio).
(B) photoacid generator is 2.7 parts by weight relative to 100 parts by weight of (A) polymer
Sensitizer deploys the amount as recorded in following tables relative to 100 parts by weight of (A) polymer.
Epoxy resin (JER157S65, Japanese epoxy resin manufacture) is 2.7 relative to 100 parts by weight of (A) polymer Parts by weight
Solvent PGMEA is adjusted more than to passing through in a manner of becoming 10 weight % by nonvolatile component relative to composition Operation and obtain each embodiment, each comparative example photosensitive polymer combination carry out each evaluation as shown below.
<evaluation of sensitivity>
By each photosensitive polymer combination slot coated, in glass substrate, (healthy and free from worry (Corning) 1737,0.7mm is thick (healthy and free from worry (Corning) company manufactures)) on after, with 90 DEG C, 120 seconds conditions on hot plate prebake conditions and so that solvent is volatilized, form film thickness For 1.5 μm of photosensitive polymer combination layer.
Then, the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) manufactured using Canon (Canon) (stock), by set Mask is exposed resulting photosensitive polymer combination layer.Then, the alkaline developer (hydroxide four of 2.38 mass % is utilized Methyl aqueous ammonium) developed with the condition of 23 DEG C, 60 seconds to the photosensitive composition layer after exposure after, utilize ultrapure water Elution 20 seconds.
It will be by these operations and with the line of 1: 1 10 μm of parsing and Optimum i ray when gap (line and space) Light exposure (Eopt) is used as sensitivity.
It is evaluated according to following benchmark.
1:100mJ/cm2More than
2:45mJ/cm2More than and less than 100mJ/cm2
3:2.0mJ/cm2More than and less than 45mJ/cm2
4:1.0mJ/cm2More than and less than 2.0mJ/cm2
5:0.01mJ/cm2More than and less than 1.0mJ/cm2
<evaluation of resolution>
Cleaned, hexamethyldisilazane (hexamethyldisilazane, HMDS) processing glass substrate on 1.3 μm of film thickness photosensitive resin coating composition, is exposed development by mask, by what can be parsed in line and space pattern Minimum pattern is as resolution.
1 point: resolution is 5 μm or more
2 points: 3.0 μm of parsings, but 2.5 μm do not parse
3 points: 2.5 μm of parsings, but 2.0 μm do not parse
4 points: 2.0 μm of parsings, but 1.5 μm do not parse
5 points: 1.5 μm of parsings.
<evaluation of rectangularity>
With 1.3 μm of film thickness photosensitive resin coating group on cleaned, hexamethyldisilazane processing glass substrate Object is closed, development is exposed by mask, is toasted after then being carried out at 140 DEG C, to 2.5 μm of the line and gap figure after rear baking The rectangularity of the shape of case part is evaluated.
1 point: cross sectional shape is acerous for arch (dome), and cone angle is less than 45 °
2 points: cross sectional shape is acerous for arch, and cone angle is 45 ° more than and less than 60 °
3 points: cross sectional shape is acerous for arch, and cone angle is 60 ° more than and less than 75 °
4 points: cross sectional shape has angle, and cone angle is 60 ° more than and less than 75 °
4.5 points: cross sectional shape has angle, and cone angle is 75 ° more than and less than 80 °
5 points: cross sectional shape has angle, and cone angle is 80 ° or more
<comprehensive performance>
The numerical value of the evaluation of sensitivity, analyticity and rectangularity is added up to respectively, is comprehensive performance according to following benchmark evaluation.
5: the level that can be used without problems completely.
4.5: the level that can without further problem use.
4: the level that can be used without problems.
3: the level that can be used by technique reply.
2: intolerant to the level used.
1: completely intolerant to the level used.
As shown in the table, learn the photosensitive polymer combination of each embodiment in the photonasty tree with each comparative example In the comparison of oil/fat composition, any evaluation of sensitivity, analyticity and rectangularity can get excellent result.Especially contain only one Under the case where kind polymer (comparative example 4), effect of the invention is not reached completely.
(embodiment 100)
<organic EL display device>
The organic EL display device (referring to Fig.1) for having ITO pattern is made using following methods.
The TFT1 of bottom gate type is formed on glass substrate 6, is formed with covering the state of the TFT1 comprising Si3N4It is exhausted Velum 3.Then, it after forming the contact hole of illustration omitted here in the insulating film 3, is formed connect by this on the insulating film 3 Contact hole and the wiring 2 (being highly 1.0 μm) for being connected to TFT1.The wiring 2 is for will be formed in process between TFT1 or hereafter The line that is connect with TFT1 of organic EL element.
In turn, in order to make because of the concave-convex planarization caused by forming wiring 2, to fill the concave-convex state caused by wiring 2 Planarization film 4 is formed on the insulating film 3.The formation of planarization film 4 on the insulating film 3 is by Japanese Patent Laid-Open 2009- The photosensitive polymer combination rotary coating recorded in the embodiment 1 of No. 98616 bulletins carries out preliminary drying on substrate on hot plate After roasting (90 DEG C, 2 minutes), using high-pressure mercury-vapor lamp with 45mJ/cm from mask2(illumination 20mW/cm2) irradiate i ray After (365nm), developed using aqueous alkali and form pattern, heat treatment in 60 minutes is carried out at 230 DEG C.
Coating when photosensitive resin coating composition is good, after exposure, development, calcining in resulting cured film, sees not To fold or the generation of 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, on planarization film 4 Wiring 2 is connected to via contact hole 7 and forms the first electrode 5 comprising ITO.Then, by the photosensitive resin composition of embodiment 1 Object rotary coating on an ito substrate, after carrying out prebake conditions (90 DEG C, 2 minutes) on hot plate, uses high-pressure mercury-vapor lamp from mask With 20mJ/cm2(illumination 20mW/cm2) after irradiating i ray (365nm), developed using aqueous alkali and form pattern. Thereafter, rear Baking out processing in 3 minutes is carried out at 140 DEG C before etching work procedure.Using the resist pattern as mask, It impregnates 1 minute at 40 DEG C in ITO etchant (3% oxalic acid aqueous solution), adds from there through wet etching to carry out the pattern of ITO Work.Thereafter, in anticorrosive additive stripping liquid controlling (MS2001, Fujiphoto electronic material (FUJIFILM Electronics Materials) company manufacture) in impregnated 7 minutes at 70 DEG C, the resist pattern is removed.The obtained like this One electrode 5 is equivalent to the anode of organic EL element.
Then, the insulating film 8 of the shape at the edge of covering first electrode 5 is formed.For insulating film 8, Japan Patent is used The photosensitive polymer combination recorded in the embodiment 1 of special open 2009-98616 bulletin, utilizes side same as described above Method forms insulating film 8.By the way that the insulating film 8 is arranged, the second electricity formed in first electrode 5 and process hereafter can be prevented Short circuit between pole.
In turn, it in vacuum deposition apparatus, is sequentially deposited across required pattern mask and hole transmission layer, organic is set Luminescent layer, electron transfer layer.Then, the second electrode comprising A1 is formed in the entire surface above substrate.It will be resulting described Substrate takes out from evaporator, is bonded and is sealed by using glass for sealing plate and ultraviolet ray hardening type epoxy resin.
As the above, obtains the connection in each organic EL element and be used to that the TFT1 of organic EL element is driven to form Active array type the organic EL display device for having ITO pattern.Apply voltage through overdrive circuit, as a result learns that it is Show good display characteristic, and the organic EL display device of high reliablity.
(embodiment 101)
<liquid crystal display device>
The liquid crystal display device for having ITO pattern is made using following methods.
In the active array type LCD recorded in Fig. 1 of No. 3321003 bulletins of Japanese Patent No., as following Cured film 17 is formed like that as interlayer dielectric, obtains the liquid crystal display device of embodiment 101.
That is, utilizing side identical with the forming method of planarization film 4 of organic EL display device in the embodiment 100 Method forms cured film 17 and is used as interlayer dielectric.
Driving voltage is applied to the resulting liquid crystal display device for having ITO pattern, it is good to show as a result to learn it Display characteristic, and the liquid crystal display device of high reliablity.
(embodiment 102)
<patterned (patterned) sapphire substrate>
Using spin coater in single crystal sapphire substrate after the photosensitive polymer combination of coating Examples 4, with 90 DEG C, 120 seconds conditions carry out prebake conditions on hot plate and solvent made to volatilize, form the photosensitive resin composition that film thickness is 2.5 μm Nitride layer.Then, the i ray stepper exposure machine (NSR-2005i9C) manufactured using Nikon (Nikon) company, across set Mask is exposed resulting photosensitive polymer combination layer.Then, the alkaline developer (hydroxide of 2.38 mass % is utilized Tetramethyl-ammonium aqueous solution) developed with the condition of 23 DEG C, 60 seconds to the photosensitive composition layer after exposure after, utilize ultrapure water Elution 20 seconds obtains 1.0 μm of line and space pattern.Pattern is rectangle, residual film ratio 100%.In addition, by the substrate 140 After toasting after carrying out 3 minutes at DEG C, BCl is used3The mixed gas of/HBr/Ar carries out the dry-etching of sapphire substrate, obtains Must have 1.0 μm of line and the sapphire substrate of space pattern.The shape of gained pattern is good.
The embodiment (reference example) of 2nd implementation form:
Polymer P HS-EVE is synthesized in the same manner as the synthesis example 7 in the embodiment of the 1st implementation form.Polymer P HS- THF is synthesized in the same manner as the synthesis example 8 in the embodiment of the 1st implementation form.
(synthesis example 11: the synthesis of polymer P HS-THP)
By alkali soluble resin (manufacture of Ma Lukalinka M S-4P, Wan Shan petrochemistry limited liability company) 15.6g and Propylene glycol methyl ether acetate (PGMEA) 100g is dissolved in flask, is evaporated under reduced pressure, water and PGMEA azeotropic distillation are gone It removes.It confirms after water content is sufficiently lower, adds 2,3- dihydropyran 3.4g and p-methyl benzenesulfonic acid 0.015g, be stirred at room temperature 2 hours.It adds triethylamine 0.10g thereto and stops reacting.Ethyl acetate is added in reaction solution, and then after being washed, By vacuum distillation removal by ethyl acetate, water distillation removal, obtaining protective rate is 25 moles of % as soluble resin PHS-THP.The weight average molecular weight of gained resin is 12,000.In addition, polydispersity is 2.6.
The structure of PHS-THP is 2- THP trtrahydropyranyl protective/4-Vinyl phenol copolymer (25 of 4-Vinyl phenol Mole %/75 mole %).
(synthesis example 12:THF/MAA/MMA=60/15/25)
<synthesis of MATHF>
MATHF is synthesized in the same manner as the synthesis example 1 in the embodiment of the 1st implementation form.
<synthesis of MATHF/MAA/MMA=60/15/25>
It is put into PGMEA (29.6g) in three-necked flask, is warming up to 80 DEG C in a nitrogen environment.Make MATHF (28.1g), MMA (7.51g), MAA (3.87g), V-601 (1.93g is 2.8mol% relative to monomer) are dissolved to PGMEA (29.6g) In, it was added dropwise in the solution with 2 hours.It is stirred 4 hours after completion of dropwise addition, reaction was completed.Thus to obtain polymer.Weight is flat Average molecular weight is 11,000.
(synthesis example 13: polymer A)
By alkali soluble resin (manufacture of Ma Lukalinka M S-4P, Wan Shan petrochemistry limited liability company) 15.6g and Propylene glycol methyl ether acetate (PGMEA) 100g is dissolved in flask, is evaporated under reduced pressure, water and PGMEA azeotropic distillation are gone It removes.It confirms after water content is sufficiently lower, adds 2,3- dihydropyran 3.4g and p-methyl benzenesulfonic acid 0.015g, be stirred at room temperature 2 hours.It adds triethylamine 0.10g thereto and stops reacting.Ethyl acetate is added in reaction solution, and then after being washed, By vacuum distillation removal by ethyl acetate, water distillation removal, obtaining protective rate is 25 moles of % as soluble resin Polymer A.The weight average molecular weight of gained resin is 12,000.In addition, polydispersity is 2.6.
The structure of polymer A is 2- THP trtrahydropyranyl protective/4-Vinyl phenol copolymer (25 of 4-Vinyl phenol Mole %/75 mole %).
(synthesis example 14: polymer B)
It is synthesized according to well-known synthetic method (functional material, 17 (12), 16 (1997)).
The structure of polymer B be 4-Vinyl phenol tert-butyl carboxylic acid protective/(25 rub 4-Vinyl phenol copolymer You are %/75 mole %).
(synthesis example 15: polymer C)
It is synthesized according to well-known synthetic method (functional material, 17 (12), 16 (1997)).
The structure of polymer A is t-Boc protective/4-Vinyl phenol copolymer (25 moles of %/75 mole %) of MMA.
(synthesis example 16:EVE/MMA/HEMA=60/15/25)
<synthesis of MAEVE>
Phenthazine (0.5 part) is added in ethyl vinyl ether (144.2 parts, 2 molar equivalents), it on one side will be cold in reaction system But it after methacrylic acid (86.1 parts, 1 molar equivalent) being added dropwise to 10 DEG C or less one sides, is stirred 4 hours under room temperature (25 DEG C).Add After adding p-methyl benzenesulfonic acid pyridine (5.0 parts), it is stirred at room temperature 2 hours, places a night at room temperature.It is added in reaction solution 5 parts of sodium bicarbonate and sodium sulphate (5 parts), are stirred at room temperature 1 hour, at 40 DEG C or less depressurize after insoluble matter is filtered dense The yellow oil of residue is evaporated under reduced pressure by contracting, and it is 43 DEG C~45 DEG C/7mm that boiling point (bp.) is obtained in the form of colorless oil Methacrylic acid -1- the ethoxy ethyl ester (MAEVE) (134.0 parts) of Hg fraction.
MMA (methyl methacrylate) is using the product with Wako Pure Chemical Industries Manufacturing.HEMA (methacrylic acid -2- hydroxyl Base ethyl ester) it is using the product with Wako Pure Chemical Industries Manufacturing.
<synthesis of MAEVE/MMA/HEMA=60/15/25>
In the synthesis example 12, in addition to other than changing material and molar ratio, being carried out similarly as described above It operates and obtains polymer.
(synthesis example 17:MATHF/MMA/MAA/HEMA=60/10/5/25)
MAA (methacrylic acid) is using the product manufactured with Wako Pure Chemical Industries company.
In the synthesis example 12, in addition to other than changing material and molar ratio, being carried out similarly as described above It operates and obtains polymer.
(B) photoacid generator
(B-1) following compounds
α-is synthesized according to the method recorded in the numbered paragraphs [0108] of Japanese patent special table 2002-528451 bulletin (p-toluenesulfonyl oxygroup imino group) phenylacetonitrile.
(B-2) CGI-1397 (BASF AG's manufacture)
(B-4) following compounds
(Ts indicates tosyl (tosyl, p-toluenesulfonyl))
It is synthesized according to following methods.
Beta naphthal (10g), chlorobenzene (30mL) suspension solution in add aluminium chloride (10.6g), 2- chlorpromazine chloride Mixed liquor is heated to 40 DEG C and reacted 2 hours by (10.1g).Under ice cooling, 4,4N HCL aqueous solution is added dropwise in reaction solution (60mL), addition ethyl acetate (50mL) carry out liquid separation.Potassium carbonate (19.2g) is added in organic layer, it is small that 1 is reacted at 40 DEG C Shi Hou, addition 2N HCL aqueous solution (60mL) carries out liquid separation, after organic layer is concentrated, will be crystallized again using diisopropyl ether (10mL) Slurrying (reslurry), filtering are dried and obtain ketone compound (6.5g).
Resulting ketone compound (3.0g), methanol (30mL) suspension solution in add acetic acid (7.3g), 50 weight % Aqueous hydroxylamine (8.0g), is heated to reflux.It after placing cooling, adds water (50mL), the crystallization of precipitation is filtered, cold first is carried out After alcohol cleaning, is dried 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) reacts 1 hour after being warming up to room temperature.Water (50mL) is added in reaction solution, will be precipitated Crystallization filtering after, using methanol (20mL) repulping, filtering, B-4 that is dry and obtaining 2.3g.
In addition, B-31H-NMR spectrum (300MHz, CDCl3) be 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).
(B-5) following compounds
(B-6)
It is synthesized according to following methods.
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), the crystallization of precipitation is filtered, washes and obtains carboxylic acid crude product 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, and silica gel column chromatography (Silicagel column is utilized after organic layer is concentrated Chromatography it) is purified, is obtained ketone compound (10g).
Resulting ketone compound (10.0g), methanol (100mL) suspension 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) is carried out liquid separation and is purified, obtained using silica gel column chromatography after concentration using water 80mL by organic layer liquid separation 4 times It obtains oxime compound (5.8g).
It is dissolved in resulting oxime compound (1.8g) in acetone (20mL), triethylamine is added dropwise under ice cooling, 4 (1.5g), paratoluensulfonyl chloride (2.4g) reacts 1 hour after being warming up to room temperature.Water (50mL) is added in reaction solution, will be precipitated Crystallization filtering after, utilize methanol (20 mL) to carry out repulping, filtering, B-6 that is dry and obtaining 3.2g.
In addition, B-51H-NMR spectrum (300MHz, CDCl3) be 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).
(B-7) following compounds
(B-8) following compounds
(B-9) following compounds
(B-10) following compounds
(O-1) following compounds (manufacture of Tokyo chemical conversion industry limited liability company, D2077)
(O-2) following compounds (manufacture of Tokyo chemical conversion industry, T1196)
(O-3) following compounds
It is synthesized using following methods.
2,4- dimethoxy-benzyl chlorine (0.19mol, l eq), triphenylphosphine (PPh3) are added in 300ml three-necked flask (0.19mol, 1eq), N-Methyl pyrrolidone (NMP) (100ml), heating stirring 4 hours at 140 DEG C.Then, water is put into In, it adds KPF6 (0.23mol, 1.2eq), is stirred at room temperature 1 hour, as a result solid is precipitated, therefore solid is filtered, in turn It is cleaned using water, and is subject to drying, this Huo get phosphonium salt (phosphonium salt) A of You.
Tian Jia phosphonium salt A (37.8mmol, 1eq), THF (100ml), are stirred on ice bath in 500ml three-necked flask.Xiang Qi In slowly add NaH (56.7mmol, 1.5eq)/THF (20ml), stir 15 minutes, be then return on ice bath after addition Room temperature.Trans-cinnamic aldehyde (37.8mmol, 1eq) is added thereto, is heated to reflux 4 hours.Then, it puts into ice water, as a result Solid is precipitated, and is filtered, and then cleaned using methanol, thus to obtain compound (O-3).
(O-4) following compounds
(O-5) following compounds
In the synthesis example of (O-3), 2,4- dimethoxy-benzyl chlorine is changed to 4- methoxy-benzyl chlorine, in addition to this, Similarly obtain compound (O-5).
(O-6) following compounds (manufacture of capital chemical conversion industry, D0879)
(O-7) following compounds
It is synthesized using following methods.
In 500ml three-necked flask add NaH (sodium hydroxide, 78.6mmol, 1.5eq), phosphonium salt B (52.4mmol, 1eq), THF (tetrahydrofuran, 100ml), is stirred on ice bath.Sulfonium salt (52.4mmol, 1eq) slowly is added thereto, addition knot It is stirred 15 minutes on ice bath after beam, is then return to room temperature.Trans-cinnamic aldehyde (52.4mmol, 1eq) is added thereto, is heated back Stream 3 hours.Then it puts into ice water, as a result solid is precipitated, and is filtered, and then carry out methanol repulping, thus to obtain change It closes object (O-7).
Phosphonium salt B
(O-8) following compounds (manufacture of Tokyo chemical conversion industry, T0168)
(O-9) following compounds
(O-10) following compound DBA (trade name, 9,10- dibutoxy anthracenes, the manufacture of Kawasaki chemical conversion industry)
(C) solvent
Propylene glycol methyl ether acetate (PGMA) (Mitsui Chemicals, Inc.'s system is made)
Alkali compounds
Following compounds (manufacture of Japan's chemical conversion industry, CMTU)
(preparation of photosensitive polymer combination)
Each ingredient is dissolved in the way of becoming and being formed shown in following tables and is mixed, 0.2 μm of polytetrafluoroethyl-ne of bore is utilized Alkene filter is filtered, and obtains the photosensitive polymer combination of Examples and Comparative Examples.
(A) polymer
(B) photoacid generator is 2.7 parts by weight relative to 100 parts by weight of (A) polymer
(C) compound represented by general formula (O) is 1.3 parts by weight relative to 100 parts by weight of (A) polymer
Alkali compounds is 0.2 parts by weight relative to 100 parts by weight of (A) polymer
Interfacial agent Mei Jiafa (Megafac) F-554 (manufacture of DIC limited liability company) 0.10 parts by weight
Solvent PGMEA is prepared in a manner of becoming 10 weight % by nonvolatile component relative to composition
The photosensitive polymer combination of resulting each embodiment in the above manner, each comparative example is carried out as shown below Each evaluation.
<evaluation of sensitivity>
Evaluation with the sensitivity in the embodiment of the 1st implementation form is carried out similarly evaluation.
<evaluation of resolution>
Evaluation with the resolution in the embodiment of the 1st implementation form is carried out similarly evaluation.
<evaluation of rectangularity>
Photosensitive resin coating is come with 1.3 μm of film thickness on cleaned, hexamethyldisilazane processing glass substrate Composition is exposed development by mask, then at 140 DEG C carry out after toast, to after rear baking 2.5 μm of line and The rectangularity of the shape of gap pattern part is evaluated.
1 point: cross sectional shape is acerous for arch, and cone angle is less than 45 °
2 points: cross sectional shape is acerous for arch, and cone angle is 45 ° more than and less than 60 °
3 points: cross sectional shape is acerous for arch, and cone angle is 60 ° more than and less than 75 °
4 points: cross sectional shape has angle, and cone angle is 60 ° more than and less than 75 °
5 points: cross sectional shape has angle, and cone angle is 75 ° or more
<comprehensive performance>
The numerical value of the evaluation of sensitivity, analyticity and rectangularity is added up to respectively, is comprehensive performance according to following benchmark evaluation.
5: the level that can be used without problems completely.
4: the level that can be used without problems.
3: the level that can be used by technique reply.
2: intolerant to the level used.
1: completely intolerant to the level used.
As shown in the table, learn the photosensitive polymer combination of each embodiment in the photonasty tree with each comparative example In the comparison of oil/fat composition, excellent result can be obtained in any evaluation of sensitivity, analyticity and rectangularity.Especially Know that there is the monomeric unit through the protection of sour decomposability base represented by either one or two of logical formula (I)~logical formula (III) in polymer In the case of, more effectively play effect of the invention.
(embodiment 200)
<organic EL display device>
Photonasty tree in embodiment 100, in addition to the photosensitive polymer combination of embodiment 1 to be set as to embodiment 1A Other than oil/fat composition, the organic EL display device of embodiment 200 is made in the same manner as embodiment 100.It is applied by driving circuit As a result making alive learns it to show good display characteristic, and the organic EL display device of high reliablity.
(embodiment 201)
<liquid crystal display device>
The liquid crystal display device for having ITO pattern is made using following methods.
In the active array type LCD recorded in Fig. 1 of No. 3321003 bulletins of Japanese Patent No., as following Cured film 17 is formed like that as interlayer dielectric, obtains the liquid crystal display device of embodiment 201.
That is, utilizing side identical with the forming method of planarization film 4 of organic EL display device in the embodiment 200 Method forms cured film 17 and is used as interlayer dielectric.
Driving voltage is applied to the resulting liquid crystal display device for having ITO pattern, it is good to show as a result to learn it Display characteristic, and the liquid crystal display device of high reliablity.
[industrial availability]
As exploitation tendency in recent years, there is the shortwave along with exposure wavelength and pursue under shortwave with uptake zone In addition the tendency of the composition in domain requires the tendency of the material in visibility region without absorbability.There is use as i ray Valuableness as stepper and the good exposure sources of parsing power are absorbed using the exposure light source of shortwave, using in exposure fields The tendency of few photoacid generator.But the present invention in, by using under long wave (ghi ray, gh ray) have uptake zone The sensitizer in domain can also provide a kind of sensitivity even with cheap low NA (numerical aperture) exposure sources (NA=0.1 or less) High, analyticity and the excellent photosensitive polymer combination of rectangularity.This photosensitive polymer combination also has and can use existing dress The advantages of improvement version set.Although in addition, sensitizer used in the present invention colours in visibility region, but as long as being used as etching Material then no problem.

Claims (12)

1. a kind of photosensitive polymer combination, which is characterized in that contain:
Polymer A-1, containing structural unit represented by the structural unit and general formula (a-1) from (methyl) acrylic acid, and And without containing structural unit represented by general formula (a-2)；
Polymer A-2 contains structural unit represented by structural unit represented by general formula (a-2) and general formula (a-3)；
Photoacid generator B；And
Solvent C；
General formula (a-1)
In general formula (a-1), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of be alkyl or aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can also link and form cyclic ether, R4Indicate that hydrogen atom or methyl, X indicate singly-bound Or arlydene；
General formula (a-2)
In general formula (a-2), R4For hydrogen atom or methyl；
General formula (a-3)
In general formula (a-3), R4For hydrogen atom or methyl；R5For straight chain, branch or cricoid alkyl, at least 1 is contained in the alkyl A-O-.
2. photosensitive polymer combination according to claim 1, it is characterised in that: the R of general formula (a-3)5It is by general formula (a- 4) or general formula (a-5) is represented；
General formula (a-4)
In general formula (a-4), R2Indicate the straight chain of carbon number 1~5 or the alkyl of branch；On the position of asterisk with general formula (a-3) key It closes；
General formula (a-5)
In general formula (a-5), it is bonded on the position of asterisk with general formula (a-3).
3. photosensitive polymer combination according to claim 1 or 2, which is characterized in that further contain sensitizer D.
4. photosensitive polymer combination according to claim 3, it is characterised in that: the sensitizer D is the following general formula (O) Or compound represented by general formula (P)；
General formula (O)
(R1)n-L1-(R2)m
In general formula (O), R1And R2Respectively indicate group represented by the phenyl that there can be substituent group or the following general formula (O-1)；L1Table Show divalent~4 valences concatenating group with 2~4 ethylenic linkages；N and m respectively indicates 1 or 2；
General formula (O-1)
In general formula (O-1), R indicates substituent group, the integer that r is 0~2；
The substituent group of substituent group and general formula (O-1) that the phenyl can have is respectively halogen atom, alkoxy, alkyl or ammonia Base；
General formula (P)
In general formula (P), R is respectively the alkyl of carbon number 1~8.
5. photosensitive polymer combination according to claim 1 or 2, it is characterised in that: the photoacid generator B is oxime sulphur Ester compound.
6. photosensitive polymer combination according to claim 1 or 2, which is characterized in that further contain epoxy resin.
7. a kind of manufacturing method of pattern characterized by comprising
Process photosensitive polymer combination according to claim 1 or 2 being applied on substrate；
The process of solvent is removed from applied photosensitive polymer combination；
The process being exposed using active radioactive ray；
The process developed using aqueous developer；
The process that the substrate is etched as mask using resist pattern is formed by；And
The process that the resist pattern is removed.
8. the manufacturing method of pattern according to claim 7, it is characterised in that: after the developing procedure, the etching Before process, the process including being toasted after being carried out at 100 DEG C~160 DEG C to the resist pattern.
9. the manufacturing method of pattern according to claim 7 or 8, it is characterised in that: the substrate be tin indium oxide substrate, Molybdenum base plate, silicon substrate, Cu substrate, Al substrate or single crystal sapphire substrate.
10. a kind of cured film, it is characterised in that: its be make photosensitive polymer combination as claimed in claim 1 or 2 harden and At.
11. a kind of manufacturing method of organic electroluminescence display device and method of manufacturing same, it is characterised in that: contain figure as claimed in claim 7 The manufacturing method of case.
12. a kind of manufacturing method of liquid crystal display device, it is characterised in that: the manufacture containing pattern as claimed in claim 7 Method.
CN201310105324.7A 2012-03-30 2013-03-28 Photosensitive polymer combination, the manufacturing method of pattern, the manufacturing method of cured film, organic EL display device and liquid crystal display device Expired - Fee Related CN103365083B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08101507A (en) * 1994-09-30 1996-04-16 Japan Synthetic Rubber Co Ltd Radiation sensitive resin composition
CN101093355A (en) * 2006-06-23 2007-12-26 富士胶片株式会社 Compound, photosensitive combination, solidified combination, solidified combination for filter, color filter and manufacturing method thereof
TW200844122A (en) * 2006-10-27 2008-11-16 Shinetsu Chemical Co Sulfonium salt having polymerizable anion, polymer, resist composition, and patterning process
JP2011017921A (en) * 2009-07-09 2011-01-27 Panasonic Corp Pattern formation method
EP2420890A1 (en) * 2010-08-20 2012-02-22 Fujifilm Corporation Positive photosensitive resin composition, method for forming cured film, cured film, organic el display device and liquid crystal display device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP5486521B2 (en) * 2010-03-15 2014-05-07 富士フイルム株式会社 Positive photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08101507A (en) * 1994-09-30 1996-04-16 Japan Synthetic Rubber Co Ltd Radiation sensitive resin composition
CN101093355A (en) * 2006-06-23 2007-12-26 富士胶片株式会社 Compound, photosensitive combination, solidified combination, solidified combination for filter, color filter and manufacturing method thereof
TW200844122A (en) * 2006-10-27 2008-11-16 Shinetsu Chemical Co Sulfonium salt having polymerizable anion, polymer, resist composition, and patterning process
JP2011017921A (en) * 2009-07-09 2011-01-27 Panasonic Corp Pattern formation method
EP2420890A1 (en) * 2010-08-20 2012-02-22 Fujifilm Corporation Positive photosensitive resin composition, method for forming cured film, cured film, organic el display device and liquid crystal display device

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