CN105531627B - Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device - Google Patents

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

Info

Publication number
CN105531627B
CN105531627B CN201480049945.0A CN201480049945A CN105531627B CN 105531627 B CN105531627 B CN 105531627B CN 201480049945 A CN201480049945 A CN 201480049945A CN 105531627 B CN105531627 B CN 105531627B
Authority
CN
China
Prior art keywords
structural unit
group
polymer
general formula
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201480049945.0A
Other languages
Chinese (zh)
Other versions
CN105531627A (en
Inventor
米泽裕之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN105531627A publication Critical patent/CN105531627A/en
Application granted granted Critical
Publication of CN105531627B publication Critical patent/CN105531627B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Abstract

The present invention provides a kind of good photosensitive polymer combination of adherence, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device.Photosensitive polymer combination of the invention contains: (A-1) includes the component of polymer for meeting the polymer of at least one of following (1) and (2); (1) polymer of the structural unit for the group protected with acidic group through sour decomposability base and the polymer containing the structural unit with bridging property base are contained in the polymer of the structural unit containing the group protected with acidic group through sour decomposability base and the structural unit with bridging property base, (2)；(B-1) photoacid generator；(C-1) solvent；And the polymer of (S) containing structural unit and the structural unit at least one group (X) in the group as composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino with part-structure represented by the following general formula (1).General formula (1)

Description

Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display dress It sets and organic EL display device
Technical field
The present invention relates to a kind of photosensitive polymer combination (hereinafter sometimes referred to simply as " compositions of the invention ").In addition, The present invention relates to a kind of manufacturing method of cured film using the photosensitive polymer combination, make photosensitive composite harden and At cured film, use the various image display devices of the cured film.
More specifically, the present invention relates to one kind to suitably form liquid crystal display device, organic electroluminescent (organic EL (Electroluminescence)) planarization film of the electronic components such as display device, integrated circuit component, solid-state imager, The manufacturing method of the photosensitive polymer combination and the cured film using it of protective film or interlayer dielectric.
Background technique
In thin film transistor (TFT) (hereinafter referred to as " TFT (Thin Film Transistor) ") type liquid crystal display element or magnetic head It is exhausted between the wiring configured with stratiform generally for making in the electronic components such as element, integrated circuit component, solid-state imager Edge and be equipped with interlayer dielectric.Formed interlayer dielectric material preferably to obtain necessary pattern form the number of steps of it is few and And with sufficient flatness, therefore photosensitive polymer combination is widely used (referring for example to patent document 1 and patent document 2)。
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2011-221494 bulletin
Patent document 2: Japanese Patent Laid-Open 2008-286936 bulletin
Summary of the invention
Problems to be solved by the invention
Furthermore in order to ensure the coating of photosensitive polymer combination, inhibit to be penetrated by developer solution to substrate in development The removing of film caused by between photosensitive polymer combination layer (resist) implements hexamethyldisilazane to substrate sometimes The silicic acid anhydrides such as (Hexamethyldisilazane, HMDS) processing, if but carry out the HMDS processing, substrate surface Hydroxyl tails off, and the function of the silane coupling agent (adhesive agent) using siloxanes as junction reduces, sometimes substrate and resist Adherence reduces.
On the other hand, in recent years, at flexible element (flexible device) on the way, it is desirable that further increase close Property.Therefore, status is the good photosensitive polymer combination of demand adherence.
To solve the problem of the present invention, and its purpose is to provide a kind of and substrate good photoresists of adherence Composition.
Technical means to solve problem
The present inventor has carried out making great efforts research according to the situation, as a result, it has been found that, by photosensitive polymer combination Deploy following polymer, can to solve the problem, so as to complete the present invention, the polymer contains with siloxanes position Structural unit and structural unit with the group (X) being crosslinked with resist, and contain multiple each structural units.
Specifically, being solved by solution below<1>, preferably solution<2>~solution<15> The project.
<1>a kind of photosensitive polymer combination, contains:
It (A-1) include the component of polymer for meeting the polymer of at least one of following (1) and (2),
(1) containing (a1-1) structural unit of group that there is acidic group protect through sour decomposability base and (a1-2) with friendship The polymer of the structural unit of connection property base,
(2) polymer containing (a1-1) structural unit of group that there is acidic group to protect through sour decomposability base and contain (a1-2) polymer of the structural unit with bridging property base；
(B-1) photoacid generator；
(C-1) solvent；And
(S) containing with part-structure represented by the following general formula (1) structural unit with have it is at least one be selected from by The structural unit of group (X) in group composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino gathers Close object；
General formula (1)
[changing 1]
In general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.
<2>a kind of photosensitive polymer combination, contains:
It (A-2) include the component of polymer for meeting the polymer of at least one of following (1) and (2),
(1) structural unit containing (a2-1) with acidic group and (a2-2) have the polymerization of the structural unit of bridging property base Object,
(2) polymer containing the structural unit of (a2-1) with acidic group and the knot containing (a2-2) with bridging property base The polymer of structure unit；
(B-2) quinone di-azido compound；
(C-2) solvent；And
(S) containing with part-structure represented by the following general formula (1) structural unit with have it is at least one be selected from by The structural unit of group (X) in group composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino gathers Close object；
General formula (1)
[changing 2]
In general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.
<3>a kind of photosensitive polymer combination, contains:
(A-3) polymerizable monomer；
(B-3) Photoepolymerizationinitiater initiater；
It (A-4) include the component of polymer for meeting the polymer of at least one of following (1) and (2),
(1) structural unit containing (a4-1) with acidic group and (a4-2) have the polymerization of the structural unit of bridging property base Object,
(2) polymer containing the structural unit of (a4-1) with acidic group and the knot containing (a4-2) with bridging property base The polymer of structure unit；
(C-3) solvent；And
(S) containing with part-structure represented by the following general formula (1) structural unit with have it is at least one be selected from by The structural unit of group (X) in group composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino gathers Close object；
General formula (1)
[changing 3]
In general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.
<4>photosensitive polymer combination according to documented by any one of<1>to<3>, wherein group (X) is to select free ring At least one of group composed by oxygroup, sulfydryl and (methyl) acryloyl group.
<5>photosensitive polymer combination according to documented by any one of<1>to<3>, wherein group (X) is epoxy group.
<6>photosensitive polymer combination according to documented by any one of<1>to<5>, wherein (S) polymer contain it is following Structural unit represented by structural unit represented by logical formula (I) and the following general formula (II)；
Logical formula (I) leads to formula (II)
[changing 4]
In logical formula (I), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer；R3And R4Point Do not indicate hydrogen atom or methyl independently；
In logical formula (II), R5Indicate epoxy group, sulfydryl, (methyl) acryloyl group, vinyl or amino, L1And L2It is only respectively On the spot indicate the concatenating group that the atomicity of singly-bound or linking part is 1~6.
<7>photosensitive polymer combination according to documented by<6>, the L in formula of (I)1And L2Separately indicate The concatenating group that the atomicity of linking part is 2~6.
<8>photosensitive polymer combination according to documented by any one of<1>to<7>, wherein relative to total solid content, (S) blending amount of polymer is 0.1 mass of mass %~10 %.
<9>photosensitive polymer combination according to documented by any one of<1>to<8>, wherein the weight of (S) polymer is flat Average molecular weight is 800 or more.
<10>photosensitive polymer combination according to documented by any one of<1>to<9>, wherein the knot with bridging property base Bridging property base in structure unit is selected from by epoxy group, oxetanylmethoxy and-NH-CH2Composed by group represented by-O-R At least one of group；Wherein, R indicates the alkyl of hydrogen atom or carbon number 1~20.
<11>photosensitive polymer combination according to documented by any one of<1>,<4>~<10>, wherein (B-1) light acid produces Raw agent is oxime sulfonate compounds and/or salt compound.
<12>a kind of manufacturing method of cured film, comprising:
(1) photosensitive polymer combination according to documented by any one of<1>to<11>is coated on the step on substrate；
(2) the step of solvent is removed from the photosensitive polymer combination being coated with；
(3) the step of resin combination for eliminating solvent being exposed using active radioactive ray；
(4) the step of being developed using aqueous developer to exposed resin combination；And
(5) the rear baking procedure of thermmohardening is carried out to developed resin combination.
<13>a kind of cured film is to keep the photosensitive polymer combination according to documented by any one of<1>to<11>hard Change.
<14>cured film according to documented by<13>is interlayer dielectric.
<15>a kind of liquid crystal display device or organic EL display device have according to hardening documented by<13>or<14> Film.
The effect of invention
According to the present invention, it is possible to provide a kind of good photosensitive polymer combination of adherence.
Detailed description of the invention
Fig. 1 shows the composition concept maps of an example of organic EL display device.It indicates bottom-emission (bottom Emission) the schematic cross sectional view of the substrate in the organic EL display device of type has planarization film 4.
Fig. 2 indicates the composition concept map of an example of liquid crystal display device.It indicates the active matrix in liquid crystal display device The schematic cross sectional view of substrate 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.The explanation for the constitutive requirements recorded below is sometimes according to this The representative implementation form of invention carries out, but the present invention is not limited thereto kind implementation form.In addition, present specification In, "~" is used using including numerical value documented by its front and back as the connotation of lower limit value and upper limit value.
In the statement of group (atomic group) in the present specification, not recording the statement for being substituted and being unsubstituted includes not Group (atomic group) with substituent group, and also comprising the group (atomic group) with substituent group.Such as so-called " alkyl ", no Only include the alkyl (alkyl being unsubstituted) without substituent group, and includes that the alkyl with substituent group (is substituted Alkyl).
Furthermore in this specification, " (methyl) acrylate " indicates acrylate and methacrylate, " (methyl) third Olefin(e) acid " indicates that acrylic acid and methacrylic acid, " (methyl) acryloyl group " indicate acryloyl group and methylacryloyl.
Composition of the invention contains component of polymer, solvent and aftermentioned (S) polymer, such as can be by by photonasty Resin combination is coated on substrate, and solvent is removed, and is exposed using actinic ray, (preferably using aqueous developer Alkaline developer) develop, and thermmohardening is carried out, and cured film is made.
Composition of the invention contains (S) polymer, and (S) polymer contains structural unit and tool with siloxanes position There is the structural unit of set group (X)., it can be said that at least one group (X) and component of polymer (A- in (S) polymer 1), the bridging property base bond in component of polymer (A-2) and component of polymer (A-4), and a siloxanes in (S) polymer The hydroxyl of position and substrate bond, thus the adherence of substrate and resist improves.That is, it can be said that (S) polymer is with multiple Siloxanes position, even if therefore the number of the hydroxyl of substrate surface is few, the hydroxyl of siloxanes and substrate in (S) polymer is also easy Bond, similarly, the crosslinking in group (X) and component of polymer (A-1), component of polymer (A-2) and component of polymer (A-4) Property base be easy bond, adherence thus can be improved.
In turn, because (S) polymer has siloxanes position, therefore have the effect of promoting baking.As a result, making photoresist Crosslink density when composition hardens improves, and also has the effect that ease gas (out gas) property improves and cone angle improves.In addition, because of silicon Oxygen alkane key is heat-resisting, therefore there are also the effects that bond power improves.
Hereinafter, in the form of the 1st~sequence of the 3rd form is illustrated composition of the invention.Composition of the invention The 1st form and the 2nd form be preferably used as the photosensitive polymer combination of eurymeric.3rd form of composition of the invention Preferably it is used as the photosensitive polymer combination of minus.
[the 1st form of the invention]
Composition of the invention contains:
It (A-1) include the component of polymer for meeting the polymer of at least one of following (1) and (2),
(1) containing (a1-1) structural unit of group that there is acidic group protect through sour decomposability base and (a1-2) with friendship The polymer of the structural unit of connection property base,
(2) polymer containing (a1-1) structural unit of group that there is acidic group to protect through sour decomposability base and contain (a1-2) polymer of the structural unit with bridging property base；
(B-1) photoacid generator；
(C-1) solvent；And
(S) containing with part-structure represented by the following general formula (1) structural unit with have it is at least one be selected from by The structural unit of group (X) in group composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino gathers Close object.
General formula (1)
[changing 5]
(in general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.)
Hereinafter, the 1st form to composition of the invention is described in detail.
<(A-1) component of polymer>
Composition of the invention contains at least one of following polymer as component of polymer: having acid containing (a1-1) The polymer (1) of structural unit of the structural unit and (a1-2) for the group that base is protected through sour decomposability base with bridging property base, And polymer containing (a1-1) structural unit of group that there is acidic group protect through sour decomposability base and contain (a1-2) tool The polymer (2) of the structural unit of crosslinking property base.In turn, containing the polymer other than these.(A-1) of the invention is poly- Polymer component as long as no special instructions, then refers to other than the polymer (1) and/or the polymer (2), needs containing view The other polymers wanted and added.
Comprising (2) containing (a1-1) structural unit of group that there is acidic group to protect through sour decomposability base polymer and When there is the situation of the polymer of the structural unit of bridging property base containing (a1-2), have acidic group through sour decomposability containing (a1-1) The ratio of the polymer of the structural unit of the group of base protection and the polymer of the structural unit containing (a1-2) with bridging property base Example preferably 95: 5~5: 95, more preferably 80: 20~20: 80, and then preferably 70: 30~30: 70.
(A-1) component of polymer is preferably the resin of addition polymerization type, more preferably containing from (methyl) acrylic acid And/or the polymer of the structural unit of its ester.Furthermore contain the structure list from (methyl) acrylic acid and/or its ester Structural unit other than member, such as from the structural unit of styrene or the structural unit from vinyl compound. Furthermore " acrylic acid series structural unit " will be also referred to as " from (methyl) acrylic acid and/or the structural unit of its ester ".
<<structural unit for the group that (a1-1) there is acidic group to protect through sour decomposability base>>
(A-1) component of polymer at least contains the structural unit (a1- for the group protected with acidic group through sour decomposability base 1).Contain structural unit (a1-1) by (A-1) component of polymer, can be made into the high photosensitive polymer combination of sensitivity.
" group that acidic group is protected through sour decomposability base " in the present invention is usable public as acidic group and sour decomposability base The group known, is not particularly limited.
Specific acidic group preferably enumerates carboxyl and the raw hydroxyl of phenol.
In addition, specific acid decomposability base can be used: passing through acid relatively easily decomposed group (such as aftermentioned ester The acetals system functional group such as structure, oxinane ester group or tetrahydrofuran ester group) or pass through acid relative difficult decompose group (such as the carbonic acid three-level alkyl such as the three-levels such as tert-butyl ester base alkyl, t-butyl carbonate base ester group).
Structural unit (a1-1) is preferably with the structural unit for protecting carboxyl protected through sour decomposability base or to have warp The structural unit of the protection phenolic hydroxyl group of sour decomposability base protection.
Hereinafter, to the structural unit (a1-1-1) with the protection carboxyl protected through sour decomposability base and sequentially there is warp The structural unit (a1-1-2) of the protection phenolic hydroxyl group of sour decomposability base protection is illustrated respectively.
<<<structural unit that (a1-1-1) has the protection carboxyl protected through sour decomposability base>>>
Structural unit (a1-1-1) is with the sour decomposability base by will be detailed below by the structure list with carboxyl The structural unit of carboxyl is protected made of the carboxy protective of member.
Can be used for the structural unit with carboxyl of the structural unit (a1-1-1), there is no particular restriction, can be used Well known structural unit.Such as it can enumerate: from molecules such as unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids In unsaturated carboxylic acid etc. at least one carboxyl structural unit (a1-1-1-1).
Hereinafter, being illustrated to the structural unit (a1-1-1-1) for being used as the structural unit with carboxyl.
<<<<structural unit of the unsaturated carboxylic acid of (a1-1-1-1) in molecule at least one carboxyl etc.>>> >
Unsaturated carboxylic acid as act set forth below can be used in unsaturated carboxylic acid used in the present invention.
That is, unsaturated monocarboxylic can for example be enumerated: acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, cinnamic acid, 2- (methyl) acryloyl-oxyethyl-succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) third Alkene trimethylammonium-phthalic acid etc..
In addition, unsaturated dicarboxylic can for example be enumerated: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc..
In addition, the unsaturated polybasic carboxylic acid for obtaining the structural unit with carboxyl can also be its acid anhydrides.It can specifically arrange It lifts: maleic anhydride, itaconic anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid can also be list (the 2- methyl of polybasic carboxylic acid Acryloxyalkyl) ester, such as can enumerate: mono succinate (2- acryloyl-oxyethyl) ester, mono succinate (2- metering system Trimethylammonium) ester, phthalic acid list (2- acryloyl-oxyethyl) ester, phthalic acid list (2- methacryloxy Ethyl) ester etc..In turn, unsaturated polybasic carboxylic acid can also be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, example It can such as enumerate: ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates.In addition, insatiable hunger It also can be used with carboxylic acid: acrylic acid -2- carboxyethyl, methacrylic acid -2- carboxyethyl, maleic acid mono alkyl ester, fumaric acid Monoalkyl ester, 4- carboxyl styrene etc..
Wherein, for the viewpoint of developability, in order to form the structural unit (a1-1-1-1), it is preferable to use propylene Acid, methacrylic acid, 2- (methyl) acryloyl-oxyethyl-succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydro neighbour benzene two Formic acid, 2- (methyl) acryloyl-oxyethyl-phthalic acid or acid anhydrides of unsaturated polybasic carboxylic acid etc., more preferably use third Olefin(e) acid, methacrylic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid.
Structural unit (a1-1-1-1) can be made of individually a kind of, can also be made of two or more.
<<<<the sour decomposability base that can be used for structural unit (a1-1-1)>>>>
Sour decomposability base described above can be used in the sour decomposability base that can be used for structural unit (a1-1-1).
In these sour decomposability bases, it is however preferred to have protect the group of the structure of sour decomposability base in the form of acetal.Example Such as, with regard to the basic physical properties of photosensitive polymer combination, particularly sensitivity or pattern form, the formative of contact hole, photonasty tree For the viewpoint of the storage stability of oil/fat composition, the protection carboxyl of carboxyl is protected preferably in the form of acetal.In turn, just feel For the viewpoint of degree, the protection carboxyl of carboxyl is more preferably protected represented by the following general formula (a1-10) in the form of acetal.Again Person protects carboxyl in the situation of protection carboxyl to protect carboxyl represented by the following general formula (a1-10) in the form of acetal It is overall to become-(C=O)-O-CR101R102(OR103) structure.
General formula (a1-10)
[changing 6]
(in formula (a1-10), R101And R102Separately indicate hydrogen atom or alkyl, wherein by R101With R102It is hydrogen Except the situation of atom.R103Indicate alkyl.R101Or R102With R103It can also link and form cyclic ether.)
In the general formula (a1-10), R101~R103It separately indicates hydrogen atom or alkyl, the alkyl can be straight chain It is shape, branch's chain state, cricoid any.Herein, R101And R102The case where two expression hydrogen atoms, is not present, R101And R102Extremely A few expression alkyl.
The alkyl of the straight-chain or branch's chain state is preferably carbon number 1~12, more preferably carbon number 1~6, and then is preferably Carbon number 1~4.It is specific enumerable: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, positive penta Base, neopentyl, n-hexyl, 2,3- dimethyl -2- butyl (thexyl), n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, just Decyl etc..
In the general formula (a1-10), R101~R103Separately indicate hydrogen atom or a heatable brick bed base.The alkyl can be straight chain It is shape, branch's chain state, cricoid any.Herein, R101And R102The case where two expression hydrogen atoms, is not present, R101And R102Extremely A few expression alkyl.
The alkyl of the straight-chain or branch's chain state is preferably carbon number 1~12, more preferably carbon number 1~6, and then is preferably Carbon number 1~4.It is specific enumerable: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, positive penta Base, neopentyl, n-hexyl, 2,3- dimethyl -2- butyl (thexyl), n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, just Decyl etc..
The cyclic alkyl is preferably carbon number 3~12, more preferably carbon number 4~8, and then preferably carbon number 4~6.It is described Cyclic alkyl can for example be enumerated: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, isoborneol Base etc..
The alkyl can also have substituent group, and substituent group can illustrate halogen atom, aryl, alkoxy.With halogen original When situation as substituent group, R101、R102、R103As halogenated alkyl, in the situation with aryl as substituent group, R101、R102、R103As aralkyl.
The halogen atom can illustrate: fluorine atom, chlorine atom, bromine atom, iodine atom, in these, preferably fluorine atom or Chlorine atom.
In addition, the aryl is preferably the aryl of carbon number 6~20, more preferably carbon number 6~12, can specifically illustrate phenyl, Alpha-Methyl phenyl, naphthalene etc., the alkyl replaced through aryl is overall, i.e. aralkyl can illustrate: benzyl, α-methylbenzyl, phenethyl, Naphthyl methyl etc..
The alkoxy is preferably the alkoxy of carbon number 1~6, more preferably carbon number 1~4, so preferably methoxyl group or Ethyoxyl.
In addition, the alkyl be naphthenic base situation when, the naphthenic base can also have carbon number 1~10 straight-chain or The alkyl of branch's chain state can also have carbon number 3 in the situation for the alkyl that alkyl is straight-chain or branch's chain state as substituent group ~12 naphthenic base is as substituent group.
These substituent groups can also be further substituted with through the substituent group.
In the general formula (a1-10), in R101、R102And R103When indicating the situation of aryl, the aryl is preferably carbon number 6 ~12, more preferably carbon number 6~10.The aryl can also have substituent group, and the substituent group preferably illustrates carbon number 1~6 Alkyl.Aryl can for example illustrate: phenyl, tolyl, xylyl, cumenyl, 1- naphthalene etc..
In addition, R101、R102And R103It can mutually be bonded and the carbon atom being bonded with these is formed together ring.R101With R102、 R101With R103Or R102With R103The ring structure of the situation of bond can for example be enumerated: cyclobutyl, cyclopenta, cyclohexyl, suberyl, four Hydrogen furyl, adamantyl and THP trtrahydropyranyl etc..
Furthermore in the general formula (a1-10), preferably R101And R102Either one or two of be hydrogen atom or methyl.
It is used to form the free-radical polymerised list containing the structural unit for protecting carboxyl represented by the general formula (a1-10) Commercially available product can be used in body, it is possible to use is synthesized using well known method.Such as using Japanese Patent Laid-Open 2011- Synthetic method recorded in 0037~numbered paragraphs of numbered paragraphs 0040 of No. 221494 bulletins etc. synthesizes, its content is incorporated to Into present specification.
First preferred configuration of the structural unit (a1-1-1) is structural unit represented by the following general formula (A2 ').
[changing 7]
(in formula (A2 '), R1And R2Respectively indicate hydrogen atom, alkyl or aryl, at least R1And R2Either one or two of indicate 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.)
In R1And R2For alkyl situation when, preferably carbon number be 1~10 alkyl.In R1And R2For aryl situation when, Preferably phenyl.R1And R2It is respectively preferably the alkyl of hydrogen atom or carbon number 1~4.
R3Indicate alkyl or aryl, the preferably alkyl of carbon number 1~10, more preferably 1~6 alkyl.
X indicates singly-bound or arlydene, preferably singly-bound.
Second preferred configuration of the structural unit (a1-1-1) is structural unit represented by the following general formula (1-12).
General formula (1-12)
[changing 8]
(in formula (1-12), R121Indicate the alkyl of hydrogen atom or carbon number 1~4, L1Indicate carbonyl or phenylene, R122~R128 Separately indicate the alkyl of hydrogen atom or carbon number 1~4.)
R121Preferably hydrogen atom or methyl.
L1Preferably carbonyl.
R122~R128Preferably hydrogen atom.
The preferred concrete example of the structural unit (a1-1-1) can illustrate following structural units.Furthermore following structural units In, R indicates hydrogen atom or methyl.
[changing 9]
<<<structural unit that (a1-1-2) has the protection phenolic hydroxyl group protected through sour decomposability base>>>
Structural unit (a1-1-2) is with the sour decomposability base by will be detailed below by the knot with phenolic hydroxyl group The structural unit (a1-1-2-1) of phenolic hydroxyl group is protected made of structure cell protection.
<<<<structural unit that (a1-1-2-1) has phenolic hydroxyl group>>>>
The structural unit with phenolic hydroxyl group can enumerate hydroxy styrenes architecture unit or novolaks system resin In structural unit, in these, for the viewpoint of sensitivity, preferably derive from hydroxy styrenes or Alpha-Methyl hydroxy styrenes Structural unit.In addition, the structural unit with phenolic hydroxyl group is also preferably the following general formula (a1- for the viewpoint of sensitivity 20) structural unit represented by.
General formula (a1-20)
[changing 10]
(in general formula (a1-20), R220Indicate hydrogen atom or methyl, R221Indicate singly-bound or bivalence linking base, R222Indicate halogen The alkyl of the straight chain or branch's chain state of plain atom or carbon number 1~5, a indicate that 1~5 integer, b indicate 0~4 integer, a+b It is 5 or less.Furthermore there are 2 or more R222Situation when, these R222It can be different also identical.)
In the general formula (a1-20), R220Indicate hydrogen atom or methyl, preferably methyl.
In addition, R221Indicate singly-bound or bivalence linking base.When for the situation of singly-bound, sensitivity can be improved, and then can be improved hard The transparency of change film, therefore it is preferred that.R221Bivalence linking base can illustrate alkylidene, R221It can be enumerated for the concrete example of alkylidene: sub- Methyl, ethylidene, propylidene, isopropylidene, sub- normal-butyl, isobutylidene, sub- tert-butyl, pentylidene, isoamylidene, Asia new penta Base, hexylidene etc..Wherein, R221Preferably singly-bound, methylene, ethylidene.In addition, the bivalence linking base can also have substitution Base, substituent group can enumerate halogen atom, hydroxyl, alkoxy etc..In addition, a indicates 1~5 integer, the just sight of effect of the invention For in terms of point or manufacture readily, a is preferably 1 or 2, and more preferably a is 1.
In addition, the binding site about the hydroxyl on phenyl ring, with R221It is excellent on the basis of the carbon atom of bond when (1) It is selected as being bonded to 4.
R222For the alkyl of the straight chain or branch's chain state of halogen atom or carbon number 1~5.It is specific enumerable: fluorine atom, chlorine Atom, bromine atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, isopentyl, neopentyl etc.. Wherein, for manufacturing readily aspect, preferably chlorine atom, bromine atom, methyl or ethyl.
In addition, b indicates 0 or 1~4 integer.
<<<<the sour decomposability base that can be used for structural unit (a1-1-2)>>>>
It can be used for the sour decomposability base of the structural unit (a1-1-2) and can be used for the structural unit (a1-1- 1) well known group similarly can be used in sour decomposability base, is not particularly limited.In sour decomposability base, with regard to photoresist group Close the formation of the basic physical properties, particularly sensitivity or pattern form, the storage stability of photosensitive polymer combination, contact hole of object Property viewpoint for, it is however preferred to have through acetal protection protection phenolic hydroxyl group structural unit.In turn, in sour decomposability base, For the viewpoint of sensitivity, the guarantor of phenolic hydroxyl group is protected represented by the more preferably described general formula (a1-10) in the form of acetal Protect phenolic hydroxyl group.Furthermore in the protection phenol to protect phenolic hydroxyl group represented by the general formula (a1-10) in the form of acetal When the situation of hydroxyl, protection phenolic hydroxyl group totally becomes-Ar-O-CR101R102(OR103) structure.Furthermore Ar indicates arlydene.
The preference of the acetal ester structure of phenolic hydroxyl group can illustrate: R101=R102=R103=methyl or R101=R102=first Base and R103The combination of=benzyl.
In addition, being used to form oneself of the structural unit with the protection phenolic hydroxyl group for protecting phenolic hydroxyl group in the form of acetal It can for example be enumerated by base polymerizable monomer and be recorded in the numbered paragraphs 0042 of Japanese Patent Laid-Open 2011-215590 bulletin.
In these, for the viewpoint of the transparency, preferably the 1- alkoxyalkyl of methacrylic acid -4- hydroxylphenyl ester is protected The THP trtrahydropyranyl protective of watch box, methacrylic acid -4- hydroxylphenyl ester.
The concrete example of the acetal protecting group of phenolic hydroxyl group can enumerate 1- alkoxyalkyl, such as can enumerate: 1- ethyoxyl second Base, 1- methoxy ethyl, 1- n-butoxyethyl, 1- isobutoxyethy, 1- (2- chloroethoxy) ethyl, 1- (2- ethyl hexyl Oxygroup) ethyl, 1- positive propoxy ethyl, 1- cyclohexyloxy ethyl, 1- (2- cyclohexylethoxy radical) ethyl, 1- Benzyloxyethyl Deng these may be used alone or in combination using two or more.
Commercially available product can be used in the free radical polymerization monomer for being used to form the structural unit (a1-1-2), it is possible to use benefit Synthesized by well known method.For example, can by make to have the compound of phenolic hydroxyl group in the presence of acid catalyst with second Alkene ether reacts to be synthesized.The synthesis can also be such that the monomer with phenolic hydroxyl group is copolymerized in advance with other monomers It closes, is reacted in the presence of acid catalyst with vinyl ethers thereafter.
The preferred concrete example of the structural unit (a1-1-2) can illustrate following structural units, but the present invention is not limited to this A little structural units.
[changing 11]
[changing 12]
[changing 13]
<<<preferred configuration of structural unit (a1-1)>>>
When the polymer containing the structural unit (a1-1) is substantially free of the situation of structural unit (a1-2), poly- It closes in object, the content of structural unit (a1-1) is preferably 20mol% (molar percentage)~100mol%, more preferably 30mol%~90mol%.
When the polymer containing the structural unit (a1-1) contains the situation of structural unit (a1-2), in polymer In, for the viewpoint of sensitivity, the content of structural unit (a1-1) is preferably 3mol%~70mol%, more preferably 10mol% ~60mol%.In addition, being especially with the shape of acetal in the sour decomposability base that can be used for the structural unit (a1-1) When formula protects the situation of the structural unit of the protection carboxyl of carboxyl, preferably 20mol%~50mol%.
The structural unit (a1-1-1) has the characteristics that development is quick compared with the structural unit (a1-1-2).Therefore, When being intended to the situation of rapid development, preferably structural unit (a1-1-1).Otherwise when making to develop slow situation, preferably It uses structural unit (a1-1-2).
<<structural unit that (a1-2) has bridging property base>>
(A-1) component of polymer contains the structural unit (a1-2) with bridging property base.As long as the bridging property base is logical The group for heating and causing sclerous reaction is crossed, then is not particularly limited.The preferred structural unit with bridging property base Form can be enumerated: containing selected from by epoxy group, oxetanylmethoxy ,-NH-CH2(R is the alkane of hydrogen atom or carbon number 1~20 to-O-R Base) represented by group and ethylene unsaturated group composed by least one of group structural unit, be preferably selected from Epoxy group, oxetanylmethoxy and-NH-CH2In group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1~20) extremely Few one kind.Wherein, photosensitive polymer combination of the invention is preferably that (A-1) component of polymer contains with epoxy group and oxa- The structural unit of at least one of cyclobutyl.More specifically, following structural unit can be enumerated.
<<<structural unit that (a1-2-1) has epoxy group and/or oxetanylmethoxy>>>
(A-1) component of polymer is preferably to contain the structural unit with epoxy group and/or oxetanylmethoxy (below Also referred to as structural unit (a1-2-1)).
The structural unit (a1-2-1) is as long as have epoxy group or oxetanylmethoxy at least in a structural unit One kind can have 1 or more epoxy group and 1 or more oxetanylmethoxy, 2 or more epoxy groups or 2 or more Oxetanylmethoxy, be not particularly limited, it is however preferred to have total 1~3 epoxy groups and/or oxetanylmethoxy, it is more excellent It is selected as with total 1 or 2 epoxy group and/or oxetanylmethoxy, and then preferably there is 1 epoxy group or oxa- ring fourth Base.
The concrete example for being used to form the free radical polymerization monomer of the structural unit with epoxy group can for example be enumerated: propylene Acid glycidyl ester, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-propyl acrylic acid shrink sweet Grease, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid -3,4- epoxy butyl ester, methacrylic acid -3,4- epoxy butyl ester, third Olefin(e) acid -3,4- epoxycyclohexanecarboxylate, methacrylic acid -3,4- epoxycyclohexanecarboxylate, α-ethylacrylate -3,4- epoxide ring Hexyl methyl esters, adjacent vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl Ether, No. 4168443 bulletins of Japanese Patent No. 0031~numbered paragraphs of numbered paragraphs 0035 in record containing ester ring type epoxy The compound etc. of skeleton, these contents are incorporated into present specification.
The concrete example for being used to form the free radical polymerization monomer of the structural unit with oxetanylmethoxy can for example be enumerated: That records in 0011~numbered paragraphs of numbered paragraphs 0016 of Japanese Patent Laid-Open 2001-330953 bulletin has oxa- ring fourth The chemical combination recorded in (methyl) acrylate of base or the numbered paragraphs 0027 of Japanese Patent Laid-Open 2012-088459 bulletin These contents are incorporated into present specification by object etc..
It is used to form the free-radical polymerised of the structural unit (a1-2-1) with epoxy group and/or oxetanylmethoxy The concrete example of monomer is preferably the monomer containing metacrylic acid ester structure, the monomer containing acrylate structural.
In these, for improving the viewpoint of various characteristics of copolymerization and cured film, preferably metering system Acid glycidyl ester, acrylic acid 3,4- epoxycyclohexanecarboxylate, methacrylic acid 3,4- epoxycyclohexanecarboxylate, adjacent vinyl benzyl Base glycidol ether, vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, acrylic acid (3- ethyl oxa- Cyclobutane -3- base) methyl esters and methacrylic acid (3- Ethyloxetane -3- base) methyl esters.These structural units can individually make With one kind or it is applied in combination two or more.
The preferred concrete example of the structural unit (a1-2-1) can illustrate following structural units.Furthermore following structural units In, R indicates hydrogen atom or methyl.
[changing 14]
<<<structural unit that (a1-2-2) has ethylene unsaturated group>>>
One kind of the structural unit (a1-2) with bridging property base can enumerate the structure with ethylene unsaturated group Unit (a1-2-2).The structural unit (a1-2-2) is preferably the structural unit on side chain with ethylene unsaturated group, The structural unit of side chain more preferably in end with ethylene unsaturated group and with carbon number 3~16.
In addition to this, about structural unit (a1-2-2), the section of Japanese Patent Laid-Open 2011-215580 bulletin can be enumerated 0013~paragraph of numbered paragraphs of the record and Japanese Patent Laid-Open 2008-256974 that fall 0072~numbered paragraphs of number 0090 is compiled Compound recorded in number 0031 etc. is preferably, being incorporated to these contents into present specification.
< < < (a1-2-3) has-NH-CH2Group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1~20) Structural unit > > >
(A-1) component of polymer used in the present invention, which also preferably contains, has-NH-CH2- O-R (R be hydrogen atom or The alkyl of carbon number 1~20) represented by group structural unit (a1-2-3).By containing structural unit (a1-2-3), can lead to Slowly heat treatment is crossed to cause sclerous reaction, can get the excellent cured film of various characteristics.Herein, R be preferably carbon number 1~ 9 alkyl, the more preferably alkyl of carbon number 1~4.In addition, alkyl can be any of straight chain, branch or cricoid alkyl, it is excellent It is selected as the alkyl of straight chain or branch.Structural unit (a1-2-3) more preferably has group represented by the following general formula (a2-30) Structural unit.
General formula (a2-30)
[changing 15]
(in general formula (a2-30), R1Indicate hydrogen atom or methyl, R2Indicate the alkyl of hydrogen atom or carbon number 1~20.)
R2The preferably alkyl of carbon number 1~9, the more preferably alkyl of carbon number 1~4.In addition, alkyl can be straight chain, branch Or cricoid alkyl is any, the preferably alkyl of straight chain or branch.
R2Concrete example can enumerate: methyl, ethyl, normal-butyl, isobutyl group, cyclohexyl and n-hexyl.Wherein, preferably different Butyl, normal-butyl, methyl.
<<<preferred configuration of the structural unit (a1-2) with bridging property base>>>
When the polymer containing the structural unit (a1-2) is substantially free of the situation of structural unit (a1-1), in institute It states in polymer, the content of structural unit (a1-2) is preferably 5mol%~90mol%, more preferably 20mol%~ 80mol%.
When the polymer containing the structural unit (a1-2) contains the situation of the structural unit (a1-1), described In polymer, for the viewpoint of chemical-resistant, the content of structural unit (a1-2) is preferably 3mol%~70mol%, more Preferably 10mol%~60mol%.
It in the present invention, and then no matter is which form, in all structural units of (A-1) component of polymer, structural unit (a1-2) content is both preferably 3mol%~70mol%, more preferably 10mol%~60mol%.
In the range of being set as the numerical value, the excellent cured film of various characteristics can be formed.
<<(a1-3) other structures unit>>
In the present invention, (A-1) component of polymer is preferably in addition to containing the structural unit (a1-1) and/or structural unit (a1-2) other than, at least contain the structural unit with acidic group as other structures unit (a1-3) in addition to this.It is described poly- Structural unit (a1-3) can also be contained by closing object (1) and/or polymer (2).In addition, the polymer (1) or poly- can also be different from It closes object (2) and separately contains other structures unit (a1- containing structural unit (a1-1) and structural unit (a1-2) is substantially free of 3) polymer.
By containing the structural unit with acidic group as other structures unit (a1-3), the adjustment transfiguration of developability is easy. In addition, being easy in the developer solution for being dissolved in alkalinity, effect of the invention can be more effectively played.So-called acidic group in the present invention is Refer to proton dissociation base of the pKa less than 7.Acidic group usually uses the monomer that can form acidic group and with the structural unit containing acidic group Form is set into polymer.By containing such structural unit containing acidic group in the polymer, has and be easy to be dissolved in alkalinity Tendency in developer solution.
Acidic group used in the present invention can illustrate: the acidic group from carboxylic acid group, the acidic group from sulfoamido, source In the acidic group of phosphonic acid base, from sulfonic acidic group, the acidic group from phenolic hydroxyl group, sulfoamido, sulfonyl acid imide Base etc., the preferably acidic group from the acidic group of carboxylic acid group and/or from phenolic hydroxyl group.
Structural unit used in the present invention containing acidic group is more preferably the structural unit for deriving from styrene or derives from The structural unit of vinyl compound derives from (methyl) acrylic acid and/or the structural unit of its ester.Such as Japan can be used specially 0029~numbered paragraphs of 0021~numbered paragraphs of numbered paragraphs 0023 and numbered paragraphs of sharp special open 2012-88459 bulletin Its content is incorporated into present specification by the compound recorded in 0044.Wherein, para hydroxybenzene second is preferably derived from Alkene, (methyl) acrylic acid, maleic acid, maleic anhydride structural unit.
It, can be with (a1-1) structural unit and/or (a1-2) structural unit about the introduction method of the structural unit containing acidic group It is directed into identical polymer, it also can be with the structure of the polymer different from (a1-1) structural unit and (a1-2) structural unit The form of unit imports.
Such polymer is preferably the resin on side chain with carboxyl.Such as it can enumerate: such as Japanese Patent Laid-Open No. Sho 59- No. 44615, Japan Patent examined patent publication 54-34327, Japan Patent examined patent publication 58-12577, Japan Patent examined patent publication 54- No. 25957, Japanese Patent Laid-Open No. Sho 59-53836, Japanese Patent Laid-Open No. Sho 59-71048 each bulletin in record as Methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymers, maleic acid, partial esterification Maleic acid etc. and in side chain with the acid cellulose derivative of carboxyl, the addition on the polymer with hydroxyl Made of acid anhydrides etc., and then the high molecular polymer on side chain with (methyl) acryloyl group can be also enumerated as preferred.
Such as it can enumerate: (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid -2- hydroxyl second It is recorded in ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer, Japanese Patent Laid-Open 7-140654 bulletin (methyl) 2-hydroxypropyl acrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer, third Olefin(e) acid -2- hydroxyl -3- phenoxy-propyl/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, methacrylic acid -2- hydroxy methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer Object, methacrylic acid -2- hydroxy methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer Deng.
In addition to this, Japanese Patent Laid-Open 7-207211 bulletin, Japanese Patent Laid-Open 8-259876 also can be used Number bulletin, Japanese Patent Laid-Open 10-300922 bulletin, Japanese Patent Laid-Open 11-140144 bulletin, Japan Patent are special Open flat 11-174224 bulletin, Japanese Patent Laid-Open 2000-56118 bulletin, Japanese Patent Laid-Open 2003-233179 public affairs The well known high-molecular compound recorded in report, Japanese Patent Laid-Open 2009-52020 bulletin etc., by these contents be incorporated to In present specification.
These polymer can also contain two or more only containing one kind.
These polymer can also be used commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA17352P, SMA 2625P, SMA 3840F (the above are the manufactures of Cray Willie (CrayValley) company), it is sub- such as wind (ARUFON) UC-3000, sub- such as wind (ARUFON) UC-3510, sub- such as wind (ARUFON) UC-3900, Asia such as wind (ARUFON) UC- 3910, sub- such as wind (ARUFON) UC-3920, Asia such as wind (ARUFON) UC-3080 (the above are East Asia synthesis (stock) manufactures), Zhuan Ke Beautiful (Joncryl) 690, Zhuan Keli (Joncryl) 678, Zhuan Keli (Joncryl) 67, Zhuan Keli (Joncryl) 586 (the above are BASF (BASF) manufacture) etc..
In the present invention, especially for the viewpoint of sensitivity, preferably contain carboxylic structural unit.Such as day can be used 0021~the numbered paragraphs of numbered paragraphs 0023 and 0029~paragraph of numbered paragraphs of this patent special open 2012-88459 bulletin are compiled The compound recorded in number 0044, its content is incorporated into present specification.
Structural unit containing acidic group is preferably 1mol%~80mol% of the structural unit of all component of polymer, more excellent It is selected as 1mol%~50mol%, and then preferably 5mol%~40mol%, especially preferably 5mol%~30mol%, especially Preferably 5mol%~25mol%.
There is no particular restriction for the monomer of structural unit (a1-3) other than structural unit containing acidic group described in being formed, such as can It enumerates: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, no Saturated dicarboxylic acid diester, bicyclic unsaturated compound class, maleimide compound class, unsaturated aromatic compound, conjugation Diene compound, unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.Form it The monomer of his structural unit (a1-3) may be used alone or in combination using two or more.
It is specific enumerable: from styrene, methyl styrene, hydroxy styrenes, α-methylstyrene, Alpha-Methyl to hydroxyl Base styrene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, Vinyl benzoic acid ethyl ester, 4-HBA (3- methacryloxypropyl) ester, (methyl) acrylic acid, (methyl) propylene Sour methyl esters, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2- Hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) Acryloyl morpholine, N- N-cyclohexylmaleimide, acrylonitrile, ethylene glycol single acetyl acetic acid esters list (methyl) acrylate etc. Structural unit.In addition to this, 0021~numbered paragraphs of numbered paragraphs of Japanese Patent Laid-Open 2004-264623 bulletin can be enumerated The compound recorded in 0024.
In addition, other structures unit (a1-3) is preferably phenylethylene, has aliphatic for the viewpoint of electrical characteristic The group of ring type skeleton.It is specific enumerable: styrene, methyl styrene, hydroxy styrenes, α-methylstyrene, (methyl) third Two ring pentyl ester of olefin(e) acid, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate etc..
In turn, in addition for the viewpoint of adherence, other structures unit (a1-3) is preferably (methyl) acrylic acid alkyl Ester.It is specific enumerable: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid N-butyl etc., more preferably (methyl) methyl acrylate.
In addition, component of polymer can also also contain the structural unit with oxazoline group as other structures unit (a1- 3)。
It is exemplified below the preferred implementation form of component of polymer of the invention, but the present invention is not limited to these to implement shape State.
(the 1st implementation form)
Polymer (1) also contains the form of one kind or two or more other structures unit (a1-3).
(the 2nd implementation form)
The polymerization of the structural unit of the group that containing (a1-1) there is acidic group to protect through sour decomposability base in polymer (2) Object also contains the form of one kind or two or more other structures unit (a1-3).
(the 3rd implementation form)
In polymer (2) containing (a1-2) have bridging property base structural unit polymer also contain a kind or 2 kinds with On other structures unit (a1-3) form.
(the 4th implementation form)
It is different from the polymer (1) or polymer (2) and also contains and be substantially free of structural unit (a1-1) and structure The form of unit (a1-2) and the polymer containing other structures unit (a1-3).
(the 5th implementation form)
More than two combined forms comprising the 1st implementation form~the 4th implementation form.
Containing the form for being substantially free of (a1-1) and (a1-2) and the polymer containing other structures unit (a1-3) In, containing (a1-1) and/or (a1-2) polymer total amount, be substantially free of (a1-1) and (a1-2) and contain other The weight ratio of the total amount of the polymer of structural unit (a1-3) is preferably 99: 1~5: 95, and more preferably 97: 3~30: 70, And then preferably 95: 5~50: 50.
Composition of the invention preferably contains (A-1) with the ratio of the 70 mass % or more of the solid component of composition Component of polymer.
<<molecular weight of (A-1) polymer>>
(A-1) molecular weight of polymer is with polystyrene converted weight average molecular weight, and preferably 1,000~200, 000, more preferably 2,000~50,000 range.In the range of the numerical value, then various characteristics are good.Quantity is average Molecular weight and the ratio (point spacious degree) of weight average molecular weight are preferably 1.0~5.0, and more preferably 1.5~3.5.
(A-1) weight average molecular weight of component of polymer and dispersion degree are defined as by gel permeation chromatography (Gel Permeation Chromatography, GPC) the resulting polystyrene scaled value of measurement.In this specification, component of polymer Weight average molecular weight (Mw) and number average molecular weight (Mn) for example can by using HLC-8120 (Tosoh (stock) manufacture), It uses the porous HXL-M of tsk gel (TSK gel Multipore HXL-M) (Tosoh (stock) manufactures, 7.8mm ID × 30.0cm) It is found out as tubing string, and using tetrahydrofuran (Tetrahydrofuran, THF) as eluent.
<<manufacturing method of (A-1) polymer>>
In addition, the synthetic method about (A-1) component of polymer, it is also known that various methods, if enumerating an example, can by with Under type is synthesized: in organic solvent, using radical polymerization initiator, being made at least containing being used to form (the a1- 1) and the free radical polymerization monomer mixture of the free radical polymerization monomer of structural unit represented by (a1-3) carries out Polymerization.In addition, can also be synthesized using so-called high molecular weight reactive.
In addition, pentaerythrite four (3-thiopropionate), trimethylolpropane tris (3- mercaptopropionic acid for example can also be used Ester), α-methylstyrenedimer equimolecular quantity regulator.
(A-1) polymer is preferably to derive from (methyl) third relative to all structural units and containing 50mol% or more The structural unit of olefin(e) acid and/or its ester more preferably derives from (methyl) acrylic acid and/or its ester containing 80mol% or more Structural unit.
<(B-1) photoacid generator>
Photosensitive polymer combination of the invention contains (B-1) photoacid generator.Photoacid generator used in the present invention The compound for preferably incuding wavelength 300nm or more, being preferably the actinic ray of wavelength 300nm~450nm and generating acid is changed Learning structure, there is no restriction.In addition, about the photoactinic photoacid generator for not incuding wavelength 300nm or more directly, as long as being The actinic ray of wavelength 300nm or more is incuded and being used in combination with sensitizer, generates the compound of acid, then can be combined with sensitizer And it is preferably used.Photoacid generator used in the present invention is preferably to generate the photoacid generator that pKa is 4 acid below, more The photoacid generator that pKa is 3 acid below is preferably generated, the photoacid generator of 2 acid below is most preferably generated.
The example of photoacid generator can be enumerated: trichloromethyl s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazonium first Hydride compounds, acid imide sulfonate compound and oxime sulfonate compounds etc..In these, for the viewpoint of insulating properties, preferably To use oxime sulfonate compounds.These photoacid generators, which can be used alone, one kind or to be applied in combination two or more.Trichloromethyl S-triazine, two virtue base Iodonium salts, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative concrete example can illustrate day The compound recorded in 0083~numbered paragraphs of numbered paragraphs 0088 of this patent special open 2011-221494 bulletin, by these Content is incorporated into present specification.
Oxime sulfonate compounds, the i.e. compound with oxime sulfonates structure, which preferably illustrate, contains the following general formula (B1- 1) compound of the oxime sulfonates structure represented by.
General formula (B1-1)
[changing 16]
(in general formula (B1-1), R21Indicate alkyl or aryl.Swash indicates the key with other groups.)
In general formula (B1-1), any group can be substituted, R21Alkyl can be straight-chain be also that branch-like can also be It is cyclic annular.The substituent group allowed will be illustrated below.
R21Alkyl be preferably carbon number 1~10 straight-chain or branch-like alkyl.R21Alkyl can be through halogen atom, carbon The aryl of number 6~11, the alkoxy of carbon number 1~10 or naphthenic base (including 7, the bridgings such as 7- dimethyl -2- oxo norborny Formula alcyl, preferably bicyclic alkyl etc.) replace.
R21Aryl be preferably carbon number 6~11 aryl, more preferably phenyl or naphthyl.R21Aryl can be through lower alkyl Base, alkoxy or halogen atom replace.
The compound containing oxime sulfonates structure represented by the general formula (B1-1) is also preferably the following general formula (B1-2) oxime sulfonate compounds represented by.
General formula (B1-2)
[changing 17]
(in formula (B1-2), 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 be may be the same or different.)
R42Preferred scope and the R21Preferred scope it is identical.
Alkyl as X is preferably the straight-chain or branch-like alkyl of carbon number 1~4.In addition, the alkoxy as X is preferred For the straight-chain or branch-like alkoxy of carbon number 1~4.In addition, the halogen atom as X is preferably chlorine atom or fluorine atom.
M4 is preferably 0 or 1.In the general formula (B-2), especially preferably m4 is that 1, X is methyl, and the position of substitution of X is neighbour Position, and R42For the straight-chain alkyl of carbon number 1~10,7,7- dimethyl -2- oxo norbornylmethyl or to toluyl groups Compound.
Compound containing oxime sulfonates structure represented by the general formula (B1-1) is also preferably the following general formula (B1-3) Represented oxime sulfonate compounds.
General formula (B1-3)
[changing 18]
(in formula (B1-3), R43With the R in formula (B1-2)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 (B1-3)43Preferably methyl, ethyl, n-propyl, normal-butyl, n-octyl, trifluoromethyl, five Fluoro ethyl, perfluor n-propyl, perfluoro-n-butyl group, p-methylphenyl, 4- chlorphenyl or pentafluorophenyl group, especially preferably n-octyl.
X1The preferably alkoxy of carbon number 1~5, more preferably methoxyl group.
N4 is preferably 0~2, and especially preferably 0~1.
The concrete example of compound represented by the general formula (B1-3) and the concrete example of preferred oxime sulfonate compounds can Referring to the record of 0080~numbered paragraphs of numbered paragraphs 0082 of Japanese Patent Laid-Open 2012-163937 bulletin, by its content It is incorporated into present specification.
Compound containing oxime sulfonates structure represented by the general formula (B1-1) is also preferably the following general formula (OS-1) Represented compound.
[changing 19]
In the general formula (OS-1), R101Indicate hydrogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl, acyl group, ammonia first Acyl group, sulfamoyl, sulfo group, cyano, aryl or heteroaryl.R102Indicate alkyl or aryl.
X101Expression-O- ,-S- ,-NH- ,-NR105-、-CH2-、-CR106H- or-CR105R107, R105~R107Indicate 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 mutually be bonded respectively and Form ring.
R121~R124Preferably hydrogen atom, halogen atom and alkyl, in addition, also in addition preferably enumerating R121~R124In At least two mutually bond and form the form of aryl.Wherein, for the viewpoint of sensitivity, preferably R121~R124It is hydrogen The form of atom.
The functional group can further have substituent group.
Compound represented by the general formula (OS-1) is for example preferably Japanese Patent Laid-Open 2012-163937 bulletin Compound represented by the general formula (OS-2) recorded in 0087~numbered paragraphs of numbered paragraphs 0089, its content is incorporated to this Shen It please be in specification.
The concrete example that can be preferably used as compound represented by the general formula (OS-1) of the invention can enumerate Japan specially Compound (the exemplary compounds recorded in 0128~numbered paragraphs of numbered paragraphs 0132 of sharp special open 2011-221494 bulletin B-1~exemplary compounds b-34), but the present invention is not limited thereto.
In the present invention, the compound containing oxime sulfonates structure represented by the general formula (B1-1) is preferably the following general formula (OS-3), oxime sulfonate compounds represented by the following general formula (OS-4) or the following general formula (OS-5).
[changing 20]
(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.)
About the general formula (OS-3)~general formula (OS-5), such as it can refer to Japanese Patent Laid-Open 2012-163937 public affairs The record of 0098~numbered paragraphs of numbered paragraphs 0115 of report, its content is incorporated into present specification.
In addition, the compound containing oxime sulfonates structure represented by the general formula (B1-1) is for example especially preferably Japanese The general formula (OS-6) recorded in the numbered paragraphs 0117 of open patent 2012-163937 bulletin~general formula (OS-11) any A represented compound, its content is incorporated into present specification.
The general formula (OS-6)~general formula (OS-11) preferred scope and Japanese Patent Laid-Open 2011-221494 bulletin Numbered paragraphs 0110~0112 in the preferred scope of (OS-6)~(OS-11) recorded it is identical, its content is incorporated to this Shen It please be in specification.
The concrete example of oxime sulfonate compounds represented by the general formula (OS-3)~general formula (OS-5) can be enumerated day The compound recorded in 0114~numbered paragraphs of numbered paragraphs 0120 of this patent special open 2011-221494 bulletin, will be in it Appearance is incorporated into present specification.The present invention is not limited to these compounds.
Compound containing oxime sulfonates structure represented by the general formula (B1-1) is also preferably the following general formula (B1-4) Represented oxime sulfonate compounds.
General formula (B1-4)
[changing 21]
(in general formula (B1-4), R1Indicate alkyl or aryl, R2Indicate alkyl, aryl or heteroaryl.R3~R6It respectively indicates Hydrogen atom, alkyl, aryl, halogen atom.Wherein, R3With R4、R4With R5Or R5With R6It can also be bonded and form alicyclic ring or aromatic rings. X expression-O- or-S-.)
R1Indicate alkyl or aryl.Alkyl is preferably the alkyl with branched structure or the alkyl of cyclic structure.
The carbon number of alkyl is preferably 3~10.Especially when alkyl has the situation of branched structure, preferably carbon number 3~6 Alkyl, in the situation with cyclic structure, the preferably alkyl of carbon number 5~7.
Alkyl can for example be enumerated: propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, amyl, isopentyl, new Amyl, 1,1- dimethyl propyl, hexyl, 2- ethylhexyl, cyclohexyl, octyl etc., preferably isopropyl, tert-butyl, neopentyl, Cyclohexyl.
The carbon number of aryl is preferably 6~12, and more preferably 6~8, and then preferably 6~7.The aryl can enumerate phenyl, Naphthalene etc., preferably phenyl.
R1Represented alkyl and aryl can also have substituent group.Substituent group can for example be enumerated: halogen atom (fluorine atom, Chlorine atom, bromine atom, iodine atom), straight chain, branch or cricoid alkyl (such as methyl, ethyl, propyl etc.), alkenyl, alkynyl, Aryl, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, cyano, carboxyl, hydroxyl, alkoxy, aryloxy group, alkylthio group, Arylthio, heterocyclic oxy group, acyloxy, amino, nitro, diazanyl, heterocycle etc..In addition, can also be further substituted with through these groups. Preferably halogen atom, methyl.
Composition of the invention is for the viewpoint of the transparency, R1Preferably alkyl just has both storage stability and sensitivity Viewpoint for, R1Preferably the alkyl with branched structure of carbon number 3~6, the cyclic structure of carbon number 5~7 alkyl or benzene Base, the more preferably alkyl of the cyclic structure of the alkyl or carbon number 5~7 with branched structure of carbon number 3~6.By using this The group (the especially alkyl of large volume) of kind large volume is used as R1, can further improve the transparency.
In the substituent group of large volume, preferably isopropyl, tert-butyl, neopentyl, cyclohexyl, more preferably tert-butyl, ring Hexyl.
R2Indicate alkyl, aryl or heteroaryl.R2Represented alkyl is preferably straight chain, branch or the ring-type of carbon number 1~10 Alkyl.The alkyl can for example be enumerated: methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, amyl, neopentyl, oneself Base, cyclohexyl etc., preferably methyl.
Aryl is preferably the aryl of carbon number 6~10.The aryl can be enumerated: phenyl, naphthalene, to toluyl groups (to first Base phenyl) etc., preferably phenyl, to toluyl groups.
Heteroaryl can for example be enumerated: pyrrole radicals, indyl, carbazyl, furyl, thienyl etc..
R2Represented alkyl, aryl and heteroaryl can also have substituent group.Substituent group and R1Represented alkyl and aryl The substituent group that can have is synonymous.
R2Preferably alkyl or aryl, more preferably aryl, and then preferably phenyl.The substituent group of phenyl is preferably first Base.
R3~R6Respectively indicate hydrogen atom, alkyl, aryl or halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom). R3~R6Represented alkyl and R2Represented alkyl is synonymous, and preferred scope is also identical.In addition, R3~R6Represented Aryl and R1Represented aryl is synonymous, and preferred scope is also identical.
R3~R6In, R3With R4、R4With R5Or R5With R6It can also be bonded and form ring, about ring, preferably form alicyclic ring or virtue Fragrant ring, more preferably phenyl ring.
R3~R6Preferably hydrogen atom, alkyl, halogen atom (fluorine atom, chlorine atom, bromine atom) or R3With R4、R4With R5Or R5With R6It is bonded and constitutes phenyl ring, more preferably hydrogen atom, methyl, fluorine atom, chlorine atom, bromine atom or R3With R4、R4With R5Or R5With R6It is bonded and constitutes phenyl ring.
R3~R6Preferred configuration it is as follows.
(form 1) at least two is hydrogen atom.
The number of (form 2) alkyl, aryl or halogen atom is 1 or less.
(form 3) R3With R4、R4With R5Or R5With R6It is bonded and constitutes phenyl ring.
(form 4) meets the form of the form 1 and form 2 and/or meets the form of the form 1 and form 3.
X expression-O- or-S-.
The concrete example of the general formula (B1-4) can be listed below compound, but be not particularly limited in this in the present invention.Furthermore In exemplary compounds, Ts indicates tosyl (p-toluenesulfonyl), and Me indicates that methyl, Bu indicate that normal-butyl, Ph indicate benzene Base.
[changing 22]
In photosensitive polymer combination of the invention, relative to 100 matter of total solid content in photosensitive polymer combination Part is measured, the content of (B-1) photoacid generator is preferably 0.1 mass parts~20 mass parts, more preferably 0.5 mass parts~10 mass Part, and then preferably 0.5 mass parts~5 mass parts.One kind can be used only in photoacid generator, can also and with two or more.Make When with two or more situations, preferably its total amount becomes the range.
<(C-1) solvent>
Photosensitive polymer combination of the invention contains (C-1) solvent.Photosensitive polymer combination of the invention is preferably Be prepared into solution essential component of the invention and further aftermentioned any ingredient being dissolved in solvent.It is used to prepare this hair The solvent of bright composition can be used essential component and any ingredient uniform dissolution and the solvent that does not react with each ingredient.
Well known solvent can be used in solvent used in photosensitive polymer combination of the invention, can illustrate: ethylene glycol list Alkyl ether, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dioxane Base ethers, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, two Propylene-glycol monoalky lether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone, amide Class, lactone etc..In addition, the concrete example of solvent used in photosensitive polymer combination of the invention can also enumerate Japan Patent The solvent recorded in 0174~numbered paragraphs of numbered paragraphs 0178 of special open 2011-221494 bulletin, Japanese Patent Laid-Open The solvent recorded in 0167~numbered paragraphs of numbered paragraphs 0168 of 2012-194290 bulletin, these contents are incorporated to this Shen It please be in specification.
In addition, optionally can also add benzylisoeugenol, hexyl ether, ethyleneglycol monophenylether second in turn in these solvents Acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, benzylalcohol, benzene first Ether, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, propylene carbonate equal solvent.This A little solvents, which can be used alone, one kind or to be used in mixed way two or more.Workable solvent is preferably individually a kind of or simultaneously in the present invention 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, diethyl Esters of gallic acid 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 molten that solvent, which is preferably boiling point, The mixture of agent or these solvents.
Boiling point is that 130 DEG C of solvents more than and less than 160 DEG C can illustrate: propylene glycol methyl ether acetate (146 DEG C of boiling point), 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 n-propyl Ether (131 DEG C of boiling point).
Boiling point is that 160 DEG C or more of solvent can illustrate: 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 diformazan 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 Glycol dimethyl ether (175 DEG C of boiling point), 1,3-BDO diacetate esters (232 DEG C of boiling point).
Relative to 100 mass parts of all the components in photosensitive polymer combination, photosensitive polymer combination of the invention In the content of solvent be preferably 50 mass parts~95 mass parts, more preferably 60 mass parts~90 mass parts.
One kind can be used only in solvent, it is possible to use two or more.When using two or more situations, preferably it is total Amount becomes the range.
<(S) polymer>
Composition of the invention contains following polymer and is used as (S) polymer, that is, containing with the following general formula (1) institute table The structural unit (structural unit with siloxanes position) of the part-structure shown, with have it is at least one selected from by epoxy group, The polymer of the structural unit of group (X) in group composed by sulfydryl, (methyl) acryloyl group, vinyl and amino.(S) Polymer contains multiple each structural units respectively, usually contains 5 or more respectively.
General formula (1)
[changing 23]
(in general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.)
<<structural unit with part-structure represented by general formula (1)>>
In the general formula (1), R1And R2Separately indicate the alkyl of carbon number 1~4, the preferably alkyl of carbon number 1~3, More preferably methyl or ethyl.Specific alkyl can be enumerated: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl etc..R1And R2 Preferably indicate same group.
N indicates 0~2 integer, preferably 0 or 1 integer, more preferably 0.
Structural unit with part-structure represented by general formula (1) preferably by the following general formula (I) represented by.
Logical formula (I)
[changing 24]
(in logical formula (I), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.R3Indicate hydrogen Atom or methyl.L1Indicate the concatenating group that the atomicity of singly-bound or linking part is 1~6.)
R in logical formula (I)1And R2With the R in general formula (1)1And R2For synonymous, preferred scope is also identical.
N in the logical formula (I) and n in general formula (1) is synonymous, and preferred scope is also identical.
R3Indicate hydrogen atom or methyl, preferably hydrogen atom.
L1Indicate the concatenating group that the atomicity of singly-bound or linking part is 1~6, the preferably atomicity of linking part is 2~6 The bivalence linking base that bivalence linking base, the more preferably atomicity of linking part are 3~6.By the way that the atomicity of linking part is set It is 2~6, the motility at siloxanes position becomes good (siloxanes position becomes flexible), improves adherence and cone property in hole mentions It is high.
Herein, the atomicity of so-called linking part refers to what the carbon atom and silicon atom that will constitute the main chain of logical formula (I) linked The atomicity of chain, there are refer to the number for constituting the atom of shortest chain when the situation of a plurality of chain due to branch or ring-type.Tool For body, in the L as represented by following formula (A)1For propylidene situation when, by main chain and silicon atom connection chain be 3 Carbon atom, therefore the atomicity of linking part becomes 3.In addition, in L1It is the situation of cyclohexylidene as represented by following formula (B) When, the chain of main chain and silicon atom connection there are into 3 situations and 5 situations, due to indicating shortest chain, therefore the original of linking part Subnumber becomes 3.As represented by following formula (C) in L1In main chain in carbonyl situation when, the atom of linking part Number also becomes 3.
[changing 25]
L1The concrete example for the concatenating group that the atomicity of represented linking part is 1~6 can be enumerated: the alkylidene of carbon number 1~6 Arlydene (the example of (such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclohexylidene), carbon number 6~10 Such as phenylene, naphthylene).Wherein, the preferably alkylidene of carbon number 1~6.
<<structural unit at least one group (X)>>
Group (X) is selected from the group as composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino, In group composed by group represented by being preferably selected from by epoxy group, sulfydryl and (methyl) acryloyl group, more preferably ring Oxygroup and sulfydryl.
(S) group contained in polymer (X) can also be different, but preferably group (X) is identical.
Structural unit at least one group (X) preferably by the following general formula (II) represented by.
Logical formula (II)
[changing 26]
(in logical formula (II), R4Separately indicate hydrogen atom or methyl.L2The atomicity for indicating singly-bound or linking part is 1 ~6 concatenating group.R5Indicate epoxy group, sulfydryl, (methyl) acryloyl group, vinyl or amino.)
R4With the R in general formula (1-1)3For synonymous, preferred scope is also identical.
R5Indicate epoxy group, sulfydryl, (methyl) acryloyl group, vinyl or amino, preferably epoxy group, sulfydryl, (first Base) acryloyl group, more preferably epoxy group.
L2With the L in general formula (1-1)1For synonymous, preferred scope is also identical.
(S) polymer used in the present invention contains the structural unit with part-structure represented by general formula (1) (structural unit represented by preferably logical formula (I)) and structural unit (the preferably logical formula (II) at least one group (X) Represented structural unit) other than structural unit, the structural unit can illustrate structural unit described in (a1-3).
(S) polymer used in the present invention preferably contains structural unit represented by logical formula (I) and logical formula (II) institute The structural unit of expression, it is poly- that structural unit represented by structural unit and logical formula (II) represented by preferably logical formula (I) accounts for (S) The 60mol% or more for closing all structural units of object, more preferably accounts for 80mol% or more.
(S) structural unit (the preferably logical formula (I) institute table with part-structure represented by general formula (1) in polymer The structural unit shown) with the structural unit (structural unit represented by preferably logical formula (II)) at least one group (X) Containing ratio (molar ratio) be preferably 15~85: 85~15, more preferably 25~75: 75~25.By being set as such ratio Rate can further improve effect of the invention.
Hereinafter, showing the exemplary compounds of (S) polymer used in the present invention, but the present invention is not limited to these certainly Exemplary compounds.Me indicates that methyl, Et indicate ethyl.
[changing 27]
[changing 28]
(S) polymer used in the present invention can also be used commercially available product, for example, can be used X-12-981S, X-12-984S, X-12-1154, X-12-1048, X-12-972F (being the manufacture of silicone company, SHIN-ETSU HANTOTAI).
(S) weight average molecular weight of polymer is preferably 800 or more, and more preferably 800~5000, and then preferably 800~3000.By the way that the weight average molecular weight of (S) polymer is set as 800 or more, the hydroxyl at siloxanes position and substrate Bond ratio increase, adherence can be improved, do not undermine the ageing stability of resist hereinafter, can get by being set as 5000 Effect.
Weight average molecular weight can be found out using gel permeation chromatography (GPC).
Relative to total solid content, the composition of the 1st form of the invention is preferably with 0.1 mass of mass %~20 %'s Ratio contains (S) ingredient, more preferably contains (S) ingredient with the ratio of 0.1 mass of mass %~10 %, and then preferably with 1 The ratio of the mass of quality %~10 % contains (S) ingredient, especially preferably with the ratio of 2 mass of mass %~5 % contain (S) at Point.(S) ingredient can be only one kind, can also be two or more.When (S) ingredient is two or more situation, preferably it is total Amount is the range.By the way that blending amount is set as 0.1 mass % or more, adherence is further increased, by being set as 20 matter % is measured hereinafter, can further improve solution keeping quality.
(S) polymer can be only one kind, can also be two or more.When (S) polymer is two or more situation, preferably It is the range for its total amount.
<other compositions>
In photosensitive polymer combination of the invention, other than the ingredient, optionally preferably add sensitizer, Crosslinking agent, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkali compounds, surfactant, antioxidant.In turn, photonasty tree of the invention In oil/fat composition, acid proliferation generator, development accelerant, plasticiser, hot radical producing agent, thermal acid generator, ultraviolet light can be added Additive well known to antisettling agent of absorbent, thickener and organic or inorganic etc..In addition, these compounds for example can be used The compound that 0201~numbered paragraphs of numbered paragraphs 0224 of Japanese Patent Laid-Open 2012-88459 bulletin are recorded, will be in these Appearance is incorporated into present specification.One kind can be used only in these ingredients respectively, it is possible to use two or more.
<<sensitizer>>
Photosensitive polymer combination of the invention preferably contains to promote its decomposition when combining with photoacid generator Sensitizer.Sensitizer absorbs actinic ray and becomes electron excitation state.Sensitizer and light acid as electron excitation state produce Raw agent contact, generates the effects of electronics is mobile, energy is mobile, fever.Photoacid generator occurs chemical change and decomposes as a result, Generate acid.The example of preferred sensitizer can be enumerated: belong to compounds below, and in the wave-length coverage of 350nm~450nm Interior any place 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), oxa anthracenes (such as fluorescein, eosin, erythrosine, sieve Red bright B, Bengal rose red), xanthone (such as xanthone, thioxanthone, dimethyl thioxanthone, diethyl sulfide Miscellaneous anthrone), cyanine class (such as thia-carbonyl cyanine, oxa- carbocyanine), merocyanine class (such as merocyanine, carbonyl merocyanine) if, it is red Cyanines (rhodacyanine) class, oxonols class, thiazide (such as thionine, methylenum careuleum, toluidine blue), acridine (such as acridine Orange, chloroflavin, acriflavine), acridine ketone (such as acridone, 10- butyl -2- chloro-acridine ketone), Anthraquinones (such as anthraquinone), Class (such as side acid in) in side's acid, styrene base class, basicity styrene base class (such as 2- [2- [4- (dimethylamino) benzene Base] vinyl] benzoxazoles), Coumarins (such as 7- diethylamino 4- methylcoumarin, 7- hydroxyl 4- methylcoumarin, 2,3,6,7- tetrahydro -9- methyl-1 H, 5H, 11H [1] chromenes simultaneously [6,7,8-ij] quinolizine -11- ketone).
In these sensitizers, preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, perfume (or spice) Legumin class, more preferably the polynuclear aromatic same clan.In the polynuclear aromatic same clan, most preferably anthracene derivant.
When photosensitive polymer combination of the invention contains the situation of sensitizer, relative to (A-1) polymer at Point total 100 mass parts, the additive amount of sensitizer is preferably 0 mass parts~100 mass parts, more preferably 0.1 mass parts~ 50 mass parts, and then preferably 0.5 mass parts~20 mass parts.Sensitizer can also and with two or more.
<<crosslinking agent>>
Photosensitive polymer combination of the invention can also optionally contain crosslinking agent.By adding crosslinking agent, can make by this The resulting cured film of the photosensitive polymer combination of invention becomes more strong film.
As long as crosslinking agent causes cross-linking reaction by heat, there is no restriction.Such as it can add: the intramolecular that will be stated below Compound with 2 or more epoxy groups or oxetanylmethoxy, the crosslinking agent containing alkoxy methyl have at least one second Compound, blocked isocyanate compound of alkene unsaturated double-bond etc..
When photosensitive polymer combination of the invention contains the situation of crosslinking agent, relative to total in photosensitive composite 100 mass parts of solid component, the content of crosslinking agent are preferably 0.01 mass parts~50 mass parts, and more preferably 0.1 mass parts~ 30 mass parts, and then preferably 0.5 mass parts~20 mass parts.By being added in the range, can get mechanical strength and The cured film of excellent solvent resistance.Crosslinking agent can also be used together by more than one, crosslinking agent is all total when the situation and calculate content.
<<<intramolecular is with 2 or more epoxy groups or the compound of oxetanylmethoxy>>>
The concrete example of compound of the intramolecular with 2 or more epoxy groups can be enumerated: bisphenol A type epoxy resin, Bisphenol F Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc..
These can be used as commercially available product and obtain.Such as can enumerate: JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (Mitsubishi Chemical holding (Mitsubishi Chemical Holdings) (stock) manufacture) etc., Japan Patent The commercially available product etc. recorded in the numbered paragraphs 0189 of special open 2011-221494 bulletin can also be enumerated: Dai Nakao in addition to this Your (Denacol) EX-611, for that Cauer (Denacol) EX-612, for that Cauer (Denacol) EX-614, for that Cauer (Denacol) EX-614B, for that Cauer (Denacol) EX-622, for that Cauer (Denacol) EX-512, for that Cauer (Denacol) EX-521, for that Cauer (Denacol) EX-411, for that Cauer (Denacol) EX-421, for that Cauer (Denacol) EX-313, for that Cauer (Denacol) EX-314, for that Cauer (Denacol) EX-321, for that Cauer (Denacol) EX-211, for that Cauer (Denacol) EX-212, for that Cauer (Denacol) EX-810, for that Cauer (Denacol) EX-811, for that Cauer (Denacol) EX-850, for that Cauer (Denacol) EX-851, for that Cauer (Denacol) EX-821, for that Cauer (Denacol) EX-830, for that Cauer (Denacol) EX-832, for that Cauer (Denacol) EX-841, for that Cauer (Denacol) EX-911, for that Cauer (Denacol) EX-941, for that Cauer (Denacol) EX-920, for that Cauer (Denacol) EX-931, for that Cauer (Denacol) EX-212L, for that Cauer (Denacol) EX-214L, for that Cauer (Denacol) EX-216L, for that Cauer (Denacol) EX-321L, for that Cauer (Denacol) EX-850L, for that Cauer (Denacol) DLC-201, for that Cauer (Denacol) DLC-203, for that Cauer (Denacol) DLC-204, for that Cauer (Denacol) DLC-205, for that Cauer (Denacol) DLC-206, for that Cauer (Denacol) DLC-301, for that Cauer (Denacol) DLC-402, (the above are the rapids chemical conversions (Nagase Chemtex) of length to make Make), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (the above are the manufactures of Nippon Steel's chemistry) etc..These cities The product of selling, which can be used alone, one kind or to be applied in combination two or more.
In these, it may be more preferable to which ground is enumerated: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type Epoxy resin and aliphatic epoxy resin can especially preferably enumerate bisphenol A type epoxy resin.
The concrete example of compound of the intramolecular with 2 or more oxetanylmethoxies can be used: sub- dragon oxetanes (Aron Oxetane) OXT-121, sub- dragon oxetanes (Aron Oxetane) OXT-221, sub- imperial oxetanes (Aron Oxetane) OX-SQ, sub- dragon oxetanes (Aron Oxetane) PNOX (the above are East Asia synthesis (stock) manufactures).
In addition, the compound containing oxetanylmethoxy is preferably to be used alone or mix with the compound containing epoxy group to make With.
In addition, other crosslinking agents it may also be preferred to use the numbered paragraphs of Japanese Patent Laid-Open 2012-8223 bulletin The crosslinking agent containing alkoxy methyl recorded in 0107~numbered paragraphs 0108 and there is at least one ethylene unsaturated double-bond Compound etc., these contents are incorporated into present specification.Crosslinking agent containing alkoxy methyl is preferably alkoxy first Base glycoluril.
<<<blocked isocyanate compound>>>
In photosensitive polymer combination of the invention, also preferably using blocked isocyanate based compound as crosslinking Agent.There is no particular restriction for blocked isocyanate compound, for indurative viewpoint, a preferably intramolecular have 2 with On blocked isocyanate base compound.
Furthermore so-called blocked isocyanate base in the present invention, refers to the group that isocyanate group can be generated by heat, example As preferably illustrated the group for making sealer react and protect isocyanate group with isocyanate group.In addition, the closing is different Cyanic acid ester group is preferably the group that isocyanate group can be generated by 90 DEG C~250 DEG C of heat.
In addition, the skeleton of blocked isocyanate compound is not particularly limited, as long as having 2 isocyanic acids in a molecule Ester group then can be any compound, can be aliphatic, alicyclic or aromatic polyisocyanate, such as preferably use: 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI), isophorone diisocyanate, 1,6- hexa-methylene diisocyanate Ester, 1,3- trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4- tri-methyl hexamethylene diisocyanates Ester, 2,4,4- trimethyl hexamethylene diisocyanates, 1,9-, nine methylene diisocyanate, 1,10- decamethylene, two isocyanide Acid esters, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-Anaesthetie Ether diisocyanate, 4,4 '-diisocyanate of diphenyl methane-, Ortho-xylene diisocyanate, m xylene diisocyanate, paraxylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanide Acid esters), hexamethylene -1,3- dimethylene diisocyanate, hexamethylene-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5- naphthalene two it is different Cyanate, paraphenylene diisocyanate, 3,3 '-xylene -4,4 '-diisocyanate, 4,4 '-diphenyl ether diisocyanates Ester, tetrachloro phenylene diisocyanate, norbornene alkyl diisocyanate, hydrogenation 1,3- xylene diisocyanate, hydrogenation Isosorbide-5-Nitrae-diformazan The compound of the isocyanate compounds such as phenylene diisocyanate and the skeleton of prepolymer type as derived from these compounds.These In, especially preferably toluene di-isocyanate(TDI) (TDI) or methyl diphenylene diisocyanate (MDI), hexa-methylene diisocyanate Ester (HDI), isophorone diisocyanate (IPDI).
The parent structure of blocked isocyanate compound in photosensitive polymer combination of the invention can be enumerated: biuret Type, isocyanurate type, adduct type, two functional prepolymer types etc..
The sealer for forming the enclosed construction of the blocked isocyanate compound can be enumerated: oxime compound, lactamization Close object, phenolic compounds, alcoholic compound, amine compounds, activity methene compound, pyrazole compound, mercaptan compound, imidazoles system Compound, imide series compound etc..In these, especially preferably selected from oxime compound, lactam compound, phenolic compounds, Alcoholic compound, amine compounds, activity methene compound, the sealer in pyrazole compound.
The oxime compound can enumerate oxime and ketoxime, can specifically illustrate: acetoxime (acetoxime), formaldoxime (formaldoxime), hexamethylene oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diphenyl-ketoxime etc..
The lactam compound can illustrate epsilon-caprolactams, butyrolactam etc..
The phenolic compounds can illustrate: phenol, naphthols, cresols, dimethlbenzene, halogen-substituted phenol etc..
The alcoholic compound can illustrate: methanol, ethyl alcohol, propyl alcohol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol list Alkyl ether, lactic acid alkyl ester etc..
The amine compounds can enumerate level-one amine and secondary amine, can be any of aromatic amine, aliphatic amine, cycloaliphatic amines Kind, aniline, diphenylamine, ethylenimine, polyethylene imine etc. can be illustrated.
The activity methene compound can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, second Methyl acetoacetate etc..
The pyrazole compound can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc..
The mercaptan compound can illustrate: alkyl hydrosulfide, aryl mercaptan etc..
Workable blocked isocyanate compound can be used as commercially available product and obtain in photosensitive polymer combination of the invention Take, for example, preferably use: Crow Knight (Coronate) AP stablize (stable) M, Crow Knight (Coronate) 2503, Crow Knight (Coronate) 2515, Crow Knight (Coronate) 2507, Crow Knight (Coronate) 2513, Crow Knight (Coronate) 2555, rice Leo (Millionate) MS-50 (the above are Japanese polyurethane industrial (stock) manufactures), Plutarch Knight (Takenate) B-870, Plutarch Knight (Takenate) B-830, Plutarch Knight (Takenate) B-815N, Plutarch Knight (Takenate) B-820NSU, Plutarch Knight (Takenate) B-842N, Plutarch Knight (Takenate) B-846N, Plutarch Knight (Takenate) B-870N, Plutarch Knight (Takenate) B-874N, (the above are three wells by Plutarch Knight (Takenate) B-882N Chemical (stock) manufacture), Du draws Knight (Duranate) 17B-60PX, Du that Knight (Duranate) 17B-60P, Du is drawn to draw Knight (Duranate) TPA-B80X, Du draw Knight (Duranate) TPA-B80E, Du to draw Knight (Duranate) MF-B60X, Du La Knight (Duranate) MF-B60B, Du draw Knight (Duranate) MF-K60X, Du to draw Knight (Duranate) MFA-100, Du Draw Knight (Duranate) MF-K60B, Du that Knight (Duranate) E402-B80B, Du is drawn to draw Knight (Duranate) SBN- 70D, Du draw Knight (Duranate) SBB-70P, Du to draw Knight (Duranate) K6000, and (the above are Asahi Chemical Industry chemical (stock) systems Make), De Shimo all (Desmodur) BL1100, De Shimo all (Desmodur) BL1265MPA/X, De Shimo all (Desmodur) BL3575/1, De Shimo (Desmodur) BL3272MPA, De Shimo (Desmodur) BL3370MPA, De Shimo are (Desmodur) BL3475BA/SN, De Shimo all (Desmodur) BL5375MPA, De Shimo all (Desmodur) VPLS2078/ 2, De Shimo all (Desmodur) BL4265SN, De Shimo all (Desmodur) PL340, De Shimo all (Desmodur) PL350, Su meter Du (Sumidur) BL3175 (the above are live to change bayer urethane (stock) manufacture) etc..
<<alkoxysilane compound containing trialkylsilyl group in molecular structure>>
Photosensitive polymer combination of the invention can also contain alkoxy silane chemical combination other than containing (S) polymer Object is as adherence modifying agent.If can be improved using alkoxysilane compound containing trialkylsilyl group in molecular structure by photosensitive polymer combination institute of the invention The film of formation and the adherence of substrate, or adjustment are formed by the property of film by photosensitive polymer combination of the invention.This hair Workable alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably the inorganic matter for becoming substrate in bright photosensitive polymer combination, such as The compound that the adherence of the metals such as the silicon compounds such as silicon, silica, silicon nitride, gold, copper, molybdenum, titanium, aluminium and insulating film improves. Specifically, well known silane coupling agent etc. is also effective.
Silane coupling agent can for example be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl dialkoxy silicane, γ-methacryl Oxygroup propyl trialkoxy silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4- epoxycyclohexyl) ethyltrialkoxysilanes, vinyl tri-alkoxy silicon Alkane.In these, three alkane of more preferably γ-glycidyloxypropyl silane or γ-methacryloxypropyl Oxysilane, and then preferably γ-glycidyloxypropyl silane, and then more preferably 3- glycidoxypropyl Propyl trimethoxy silicane.These, which can be used alone, one kind or is applied in combination two or more.
Alkoxysilane compound containing trialkylsilyl group in molecular structure in photosensitive polymer combination of the invention is not particularly limited to these compounds, Well known compound can be used.
When photosensitive polymer combination of the invention contains the situation of alkoxysilane compound containing trialkylsilyl group in molecular structure, relative to photonasty group 100 mass parts of total solid content in object are closed, the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably 0.1 mass parts~30 mass parts, More preferably 0.5 mass parts~20 mass parts.
In addition, in the present invention, because containing (S) ingredient, even if therefore the alkoxysilane compound containing trialkylsilyl group in molecular structure by molecular weight less than 1000 Blending amount be set as less than composition of the invention solid component 0.1 mass %, high adherence can also be maintained.
<<alkali compounds>>
Photosensitive polymer combination of the invention can also contain alkali compounds.Alkali compounds can be from chemically amplified photo resist Arbitrarily selection is used in agent to use.Such as aliphatic amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic can be enumerated The quarternary ammonium salt etc. of acid.These concrete example can enumerate the numbered paragraphs 0204 of Japanese Patent Laid-Open 2011-221494 bulletin These contents are incorporated into present specification by the compound recorded in~numbered paragraphs 0207.
Specifically, aliphatic amine can for example be enumerated: trimethylamine, diethylamine, triethylamine, di-n-propylamine, Tri-n-Propylamine, two N-amylamine, tri-n-amyl amine, diethanol amine, triethanolamine, dicyclohexyl amine, dicyclohexylmethylamine etc..
Aromatic amine can for example be enumerated: aniline, benzylamine, n,N-Dimethylaniline, diphenylamines etc..
Hetero ring type amine can for example be enumerated: pyridine, 2- picoline, 4- picoline, 2- ethylpyridine, 4- ethylpyridine, 2- phenylpyridine, 4- phenylpyridine, N- methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4- methyl Imidazoles, 2-Phenylbenzimidazole, 2,4,5- triphenylimidazolyls, nicotine, niacin, niacinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrrole Azoles, pyridazine, purine, pyrrolidines, piperidines, piperazine, morpholine, 4- methyl morpholine, N- cyclohexyl-N '-[2- (4- morpholinyl) ethyl] Thiocarbamide, 1,5- diazabicyclo [4.3.0] -5- nonene, 1,8- diazabicyclo [5.3.0] -7- hendecene etc..
Hydroxide level Four ammonium can for example be enumerated: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, Hydroxide benzyltrimethylammon.um, hydroxide tetra-n-butyl ammonium, four n-hexyl ammonium of hydroxide etc..
The quarternary ammonium salt of carboxylic acid can for example be enumerated: acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid tetra-n-butyl ammonium, Benzoic acid tetra-n-butyl ammonium etc..
Workable alkali compounds can be used alone one kind in the present invention, can also and with two or more.
When photosensitive polymer combination of the invention contains the situation of alkali compounds, relative to photosensitive resin composition 100 mass parts of total solid content in object, the content of alkali compounds are preferably 0.001 mass parts~3 mass parts, more preferably 0.005 mass parts~1 mass parts.
<<surfactant>>
Photosensitive polymer combination of the invention can also contain surfactant.Surfactant can be used anionic system, Cationic system, nonionic system or both sexes it is any, but preferred surfactant is nonionic surfactant.Of the invention Surfactant used in composition for example can be used: the numbered paragraphs 0201 of Japanese Patent Laid-Open 2012-88459 bulletin 0185~paragraph of numbered paragraphs record in~numbered paragraphs 0205 or Japanese Patent Laid-Open 2011-215580 bulletin is compiled It is recorded in number 0188, these records is incorporated into present specification.
The example of nonionic surfactants can be enumerated: polyoxyethylene senior alkyl ethers, polyoxyethylene are advanced Higher aliphatic acid diesters class, the silicone-based, fluorine system surfactant of alkyl phenyl ethers, polyoxyethylene glycol.In addition, can be by following Trade name and enumerate: KP-341, X-22-822 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Pohle not Lip river (Polyflow) No.99C (common prosperity society chemistry (stock) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials are melted into company's manufacture), Mei Jiafa (Megafac) (enlightening love Raw (DIC) (stock) manufacture), Fu Lade Cécile Nowak (Florad Novec) FC-4430 (Sumitomo 3M (stock) manufacture), Sha Fulong (Surflon) S-242 (AGC beautifies clearly (AGC Seimi Chemicals) company manufacture), treasured reason Fox (PolyFox) PF- 6320 (manufactures of Europe Nova (OMNOVA) company), SH-8400 (Dong Li-DOW CORNING silicone (Toray-Dow corning Silicone)), Fu Jite (Ftergent) FTX-218G (manufacture of Ni Aosi (Neos) company) etc..
In addition, can enumerate about surfactant containing structural unit A and structure represented by the following general formula (I-1-1) Unit B and utilize measured using tetrahydrofuran (THF) as the gel permeation chromatography of the situation of solvent polystyrene conversion Weight average molecular weight (Mw) be 1,000 or more and 10,000 copolymers below as preference.
General formula (I-1-1)
[changing 29]
(in formula (I-1-1), R401And R403Separately indicate hydrogen atom or methyl, R402Indicate carbon number 1 or more and 4 with Under straight-chain alkyl-sub, R404Indicate that hydrogen atom or the alkyl below of carbon number 1 or more and 4, L indicate that carbon number 3 or more and 6 is below Alkylidene, p and q are the quality percentage for indicating polymerization ratio, and p indicates 10 mass % or more and 80 mass % numerical value below, q table Show 20 mass % or more and 90 mass % numerical value below, r indicates 1 or more and 18 integers below, s indicate 1 or more and 10 with Under integer.)
The L is preferably branched alkylene groups represented by the following general formula (I-1-2).R in general formula (I-1-2)405Indicate carbon The alkyl below of number 1 or more and 4, with regard to compatibility and for the moist aspect of rapids in the face that is applied, preferably 1 or more carbon number and 3 alkyl below, the more preferably alkyl of carbon number 2 or 3.P and q's and (p+q) be preferably p+q=100, i.e. 100 mass %.
General formula (I-1-2)
[changing 30]
The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
These surfactants, which can be used alone, one kind or to be used in mixed way two or more.
When photosensitive polymer combination of the invention contains the situation of surfactant, relative to photosensitive resin composition 100 mass parts of total solid content in object, the additive amount of surfactant are preferably 10 below the mass more preferably 0.001 Mass parts~10 mass parts, and then preferably 0.01 mass parts~3 mass parts.
<<antioxidant>>
Photosensitive polymer combination of the invention can also contain antioxidant.Antioxidant can contain well known anti-oxidant Agent.By adding antioxidant, the film thickness that has the coloring that can prevent cured film or can reduce caused by decomposing is thinned, is in addition resistance to The excellent advantage of the hot transparency.
Such antioxidant can for example be enumerated: phosphorous antioxidant, amides, hydrazides, amine antioxidant of being obstructed, sulphur Be antioxidant, phenolic antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, Hydroxy amine derivatives etc..In these, for the thinned viewpoint of the coloring of cured film, film thickness, especially preferably phenol system is anti-oxidant Agent, amine antioxidant of being obstructed, phosphorous antioxidant, acyl amine antioxidant, hydrazides system antioxidant, sulfur antioxidant, Most preferably phenolic antioxidant.These antioxidants can be used alone one kind, can also be used in mixed way two or more.
Concrete example can be enumerated: 0026~numbered paragraphs of numbered paragraphs 0031 of Japanese Patent Laid-Open 2005-29515 bulletin Remember in the compound of middle record, 0106~numbered paragraphs of numbered paragraphs 0116 of Japanese Patent Laid-Open 2011-227106 bulletin These contents are incorporated into present specification by the compound of load.
Preferred commercially available product can be enumerated: Ai Di Coase tower wave (Adekastab) AO-60, Ai Di Coase tower wave (Adekastab) AO-20, Ai Di Coase tower wave (Adekastab) AO-80, Ai Di Coase tower wave (Adekastab) LA-52, Chinese mugwort Enlightening Coase tower wave (Adekastab) LA-81, Ai Di Coase tower wave (Adekastab) AO-412S, Ai Di Coase tower wave (Adekastab) PEP-36, gorgeous Northey (Irganox) 1035, gorgeous Northey (Irganox) 1098, refined (Tinuvin) 144 of slave.
When composition of the invention contains the situation of antioxidant, relative to the total solid in photosensitive polymer combination 100 mass parts of ingredient, the content of antioxidant are preferably 0.1 mass parts~10 mass parts, more preferably 0.2 mass parts~5 matter Measure part, especially preferably 0.5 mass parts~4 mass parts.By being set as the range, it can get and be formed by the sufficient of film The transparency, and sensitivity when pattern formation also becomes good.
<<acid proliferation generator>>
In order to improve sensitivity, acid proliferation generator is can be used in photosensitive polymer combination of the invention.
Workable acid proliferation generator is that can react further generate acid, make reaction system by acid catalyst in the present invention The compound that interior acid concentration rises, and be steadily existing compound in the state of there is no acid.
The concrete example of such acid proliferation generator can enumerate 0226~paragraph of numbered paragraphs of Japanese Patent Laid-Open 2011-221494 Its content is incorporated into present specification by the acid proliferation generator recorded in number 0228.
<<development accelerant>>
Photosensitive polymer combination of the invention can contain development accelerant.
Development accelerant can refer to 0171~numbered paragraphs of numbered paragraphs of Japanese Patent Laid-Open 2012-042837 bulletin Its content is incorporated into present specification by the development accelerant recorded in 0172.
Development accelerant can be used alone one kind, can also and with two or more.
When photosensitive polymer combination of the invention contains the situation of development accelerant, with regard to sensitivity and the viewpoint of residual film ratio For, relative to 100 mass parts of total solid content of photosensitive composite, the additive amount of development accelerant is preferably 0 mass parts ~30 mass parts, more preferably 0.1 mass parts~20 mass parts, most preferably 0.5 mass parts~10 mass parts.
In addition, 0120~section of numbered paragraphs of Japanese Patent Laid-Open 2012-8223 bulletin also can be used in other additives The hot radical producing agent recorded in number 0121, the nitrogenous compound recorded in WO2011/136074A1 and hot acid is fallen to generate These contents are incorporated into present specification by agent.
[the 2nd form of the invention]
Hereinafter, the 2nd form to composition of the invention is illustrated.
Composition of the invention contains:
It (A-2) include the component of polymer for meeting the polymer of at least one of following (1) and (2),
(1) structural unit containing (a2-1) with acidic group and (a2-2) have the polymerization of the structural unit of bridging property base Object,
(2) polymer containing the structural unit of (a2-1) with acidic group and the knot containing (a2-2) with bridging property base The polymer of structure unit；
(B-2) quinone di-azido compound；
(C-2) solvent；And
(S) ring is selected from having at least one containing the structural unit with part-structure represented by the following general formula (1) The polymerization of the structural unit of group (X) in group composed by oxygroup, sulfydryl, (methyl) acryloyl group, vinyl and amino Object.
General formula (1)
[changing 31]
(in general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.)
<(A-2) component of polymer>
(A-2) component of polymer used in the present invention includes at least one of following polymer: being had containing (a2-1) The polymer of the structural unit of the structural unit of acidic group and (a2-2) with bridging property base and there is acidic group containing (a2-1) The polymer of the polymer of structural unit and the structural unit containing (a2-2) with bridging property base.In turn, (A-2) polymer at Divide and contains the polymer other than these.
<<structural unit that (a2-1) has acidic group>>
The structural unit for having acidic group by containing (a2-1) in (A-2) component of polymer, is easy to be dissolved in alkalinity In developer solution, effect of the invention can be more effectively played.Acidic group usually uses the monomer that can form acidic group and to have acid The form of the structural unit of base is set into polymer.By containing such structural unit with acidic group in polymer, Have the tendency that being easy to be dissolved in the developer solution of alkalinity.
Described in usable (A-1) component of polymer with the 1st form described above of acidic group used in the present invention (a1-3) structural unit containing acidic group in other structures unit is identical, and preferred scope is also identical other than blending amount.
<<structural unit that (a2-2) has bridging property base>>
In addition, the structural unit of (a2-2) with bridging property base, which preferably contains, to be had selected from by epoxy group, oxa- ring fourth Base ,-NH-CH2Group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1~20), composed by ethylene unsaturated group The structural unit of at least one of group.
(a2-2) (a1-2) in structural unit and (A-1) polymer described above with bridging property base has crosslinking Property base structural unit be synonymous, preferred scope is also identical other than blending amount.
<<(a2-3) other structures unit>>
It in turn, can also be with the structural unit (a2-1) and the structural unit (a2-2) one in (A-2) component of polymer It rises and contains the structural unit (a2-3) other than the structural unit (a2-1) and the structural unit (a2-2).
Form structural unit (a2-3) if monomer be other than the structural unit (a2-1) and structural unit (a2-2) Unsaturated compound, then there is no particular restriction.
Such as it can enumerate: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) Benzyl acrylate, unsaturated dicarboxylic diester, bicyclic unsaturated compound class, maleimide compound class, unsaturated virtue Fragrant compounds of group, conjugated diene based compound, other unsaturated compounds.It is specific enumerable: N- N-cyclohexylmaleimide, first Base tetrahydrofurfuryl acrylate, styrene, acryloyl morpholine, lauryl methacrylate, methacrylic acid tricyclic [5.2.1.02 , 6] decane -8- base ester, acrylic acid -2- methyl cyclohexyl, to vinyl benzyl -2,3- glycidyl ethers, (methyl) acrylic acid etc.. The monomer for forming structural unit (a2-3) may be used alone or in combination using two or more.
(A-2) in all structural units of component of polymer, preferably containing the structural unit of 3mol%~70mol% (a2-1), more preferably contain 10mol%~60mol%, and then preferably contain 15mol%~50mol%.
(A-2) in all structural units of component of polymer, preferably containing the structural unit of 3mol%~70mol% (a2-2), more preferably contain 10mol%~60mol%, and then preferably contain 15mol%~40mol%.
(A-2) in all structural units of component of polymer, preferably containing the structural unit of 1mol%~80mol% (a2-3), more preferably contain 5mol%~50mol%, and then preferably contain 8mol%~30mol%.
Composition of the invention preferably contains (A-2) with the ratio of the 70 mass % or more of the solid component of composition Component of polymer.
<(B-2) quinone di-azido compound>
Quinone di-azido compound used in composition of the invention, which can be used, generates carboxylic acid by the irradiation of radioactive ray 1,2- quinone di-azido compound.1,2- quinone di-azido compound can be used: phenoloid or alcohol compound are (hereinafter referred to as " parent nucleus ") with the condensation product of 1,2- naphthoquinones, two nitrine sulfonic acid halide.The concrete example of these compounds for example can refer to Japan Patent spy The record for opening 0075~numbered paragraphs of numbered paragraphs 0078 of 2012-088459 bulletin, its content is incorporated to the application and is said In bright book.
In the condensation reaction of phenoloid or alcohol compound (parent nucleus) and 1,2- naphthoquinones, two nitrine sulfonic acid halide, it can make Be equivalent to relative to the OH radix in phenoloid or alcohol compound preferably 30mol%~85mol%, more preferably For 1,2- naphthoquinones, the two nitrine sulfonic acid halide of 50mol%~70mol%.Condensation reaction can be implemented using well known method.
In addition, 1,2- quinone di-azido compound, which it may also be preferred to use, is changed to amide for the ester bond of the parent nucleus of the illustration 1,2- naphthoquinones, the two nitrine sulfonamides of key, such as 2,3,4- triamido benzophenone-1, two nitrine -4- sulfonamide of 2- naphthoquinones Deng.
These quinone di-azido compounds may be used alone or in combination using two or more.Relative to the photoresist group Close 100 mass parts of total solid content in object, the allotment of the quinone di-azido compound in photosensitive polymer combination of the invention Amount is preferably 1 mass parts~50 mass parts, more preferably 2 mass parts~40 mass parts, and then preferably 10 mass parts~25 matter Measure part.By the way that the blending amount of (B-2) quinone di-azido compound is set as the range, photoactinic irradiation part with not according to The difference for penetrating solubility of the part in the alkaline aqueous solution for becoming developer solution is big, and patterning performance becomes good, in addition resulting hard The solvent resistance for changing film becomes good.
<(C-2) solvent>
Photosensitive polymer combination of the invention contains solvent.Solvent used in photosensitive polymer combination of the invention (C-1) solvent of the 1st form described above can be used, preferred scope is also identical.
Relative to 100 mass parts of all the components in photosensitive polymer combination, photosensitive polymer combination of the invention In the content of solvent be preferably 50 mass parts~95 mass parts, more preferably 60 mass parts~90 mass parts.Solvent can only make With one kind, it is possible to use two or more.When using two or more situations, preferably its total amount becomes the range.
<(S) polymer>
Composition of the invention contains (S) polymer described above.(S) polymer used in 2nd form can be used (S) polymer of 1st form described above, preferred scope are also identical.
The gross mass of photosensitive polymer combination relative to the 2nd form, (S) ingredient is preferably with 0.1 mass %~20 The ratio of quality % and contain, more preferably contained with the ratio of 0.1 mass of mass %~10 %, so preferably with 1 matter It measures the ratio of the mass of %~10 % and contains, especially preferably contained with the ratio of 2 mass of mass %~5 %.(S) ingredient can It is only a kind of, it can also be two or more.When (S) ingredient is two or more situation, preferably its total amount becomes the model It encloses.
<other compositions>
Composition of the invention, can be in the range of not undermining effect of the invention, optionally other than the ingredient And preferably add crosslinking agent described above, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkali compounds, surfactant, antioxidant. In turn, in photosensitive polymer combination of the invention, development accelerant, plasticiser, hot radical producing agent, hot acid can be added and produced Give birth to additive well known to antisettling agent of agent, ultraviolet absorbing agent, thickener and organic or inorganic etc..These ingredients and above 1st homomorphosis, preferred scope are also identical.
[the 3rd form of composition of the invention]
Composition of the invention contains:
(A-3) polymerizable monomer；
(B-3) Photoepolymerizationinitiater initiater；
It (A-4) include the component of polymer for meeting the polymer of at least one of following (1) and (2),
(1) structural unit containing (a4-1) with acidic group and (a4-2) have the polymerization of the structural unit of bridging property base Object,
(2) polymer containing the structural unit of (a4-1) with acidic group and the knot containing (a4-2) with bridging property base The polymer of structure unit；
(C-3) solvent；And
(S) containing with part-structure represented by the following general formula (1) structural unit with have it is at least one be selected from by The structural unit of group (X) in group composed by epoxy group, sulfydryl, (methyl) acryloyl group, vinyl and amino gathers Close object.
General formula (1)
[changing 32]
(in general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.)
(A-3) polymerizable monomer
Polymerizable monomer used in the present invention can be selected suitably using the monomer for being suitable for such composition, wherein excellent It is selected as using ethylene unsaturated compound.
Ethylene unsaturation platform object is the polymerizable compound at least one ethylene unsaturated double-bond.Ethylene The example of unsaturated compound can be enumerated: unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, isobutyl Olefin(e) acid, maleic acid etc.) or its esters, amides, the ester, no of unsaturated carboxylic acid and aliphatic polybasic alcoholic compound preferably can be used The amides of saturated carboxylic acid and aliphatic polybasic amine compounds.
Such as the ingredient recorded in the paragraph 0011 of Japanese Patent Laid-Open 2006-23696 bulletin or Japan can be enumerated specially These records are incorporated to the application by the ingredient recorded in 0031~paragraph of paragraph 0047 of sharp special open 2006-64921 bulletin In specification.
In addition, carbamate addition polymerization compound manufactured by addition reaction using isocyanates and hydroxyl It is preferred that Japanese Patent Laid-Open No. Sho 51-37193 bulletin, Japanese Patent Laid-fair 2-32293 bulletin, Japanese Patent Laid-fair Such propenoic methyl carbamate class or Japan Patent examined patent publication 58-49860 bulletin, day are recorded in 2-16765 bulletin This patent examined patent publication 56-17654 bulletin, Japan Patent examined patent publication 62-39417 bulletin, Japan Patent examined patent publication 62- The carbamate compounds class with skeletal oxirane recorded in No. 39418 bulletins it is also preferred that, these records are incorporated to Into present specification.
Other examples can be enumerated: Japanese Patent Laid-Open No. Sho 48-64183 bulletin, Japan Patent examined patent publication 49-43191 public affairs It reports, record such polyester acrylates in each bulletin of Japan Patent examined patent publication 52-30490 bulletin, make epoxy resin The polyfunctional acrylate such as resulting Epoxy Acrylates or methacrylate are reacted with (methyl) acrylic acid, by these Record is incorporated into present specification.In turn, also can be used " Japan then association's magazine " (vol.20, No.7, page 300~ Page 308 (1984)) in the compound introduced as photo-hardening monomer and oligomer.
About these ethylene unsaturated compounds, structure, exclusive use or and the application methods such as use, additive amount it is detailed Details condition can arbitrarily be set according to the performance design of final sense material (sensitive material).Such as it can be according to as follows Viewpoint selects.
Polymerizable monomer is preferably multifunctional, more than more preferably 3 functions, and then more than preferably 4 functions.The upper limit is not Especially exist, it is more practical below 10 functions.In turn, by and with functional number is different and/or different (such as the propylene of polymerism base Acid esters, methacrylate, distyryl compound, vinyl ether compound) compound it is also effective to adjust mechanical characteristic.
In addition, with regard to adjust developability viewpoint for, carboxylic polymerizable compound it is also preferred that.In the situation, By being crosslinked for resin and (C-3) ingredient, mechanical characteristic can be improved, thus preferably.
In turn, for the adherence of substrate, the viewpoint with the compatibility of radical polymerization initiator etc., also preferably Contain ethylene oxide (EO (Ethylene Oxide)) modified body, urethane bond.
According to above viewpoint, preferably pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylic acid Ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three ((methyl) acryloxies Ethyl) isocyanuric acid ester, pentaerythrite four (methyl) acrylate EO modified body, dipentaerythritol six (methyl) acrylate EO Modified body etc., and as Ka Yala get (KAYARAD) DPHA (Japanese chemical drug (stock) manufacture) of commercially available product, NK ester (NK Ester) A-TMMT, NK ester (NK Ester) A-TMPT, NK ester (NK Ester) A-TMM-3, NK oligomerization (NK Oligo) UA- 32P, NK oligomerization (NK Oligo) UA-7200 (the above are the village Xin Zhong chemical industry (stock) manufactures), Aronix (Aronix) M- 305, Aronix (Aronix) M-306, Aronix (Aronix) M-309, Aronix (Aronix) M-450, Ya Luoni This (Aronix) M-402, TO-1382 (the above are East Asia synthesis (stock) manufactures), V#802 (Osaka Organic Chemical Industry (stock) system It makes).
The polymerizable monomer applied in the present invention is preferably compound represented by following formula (A-3-1).
Formula (A-3-1)
[changing 33]
In formula (A-3-1), L indicates the concatenating group of divalent or more.Concatenating group is not particularly limited, and can enumerate alkylidene, carbonyl Base, imino group, ether (- O-), thioether group (- S-) or these combination.The carbon number of concatenating group is not particularly limited, and preferably 2 ~24, more preferably 2~12.Wherein, the branched alkylene groups of the preferably described carbon number.
In formula (A-3-1), A indicates polymerizable functional groups.Polymerizable functional groups are preferably vinyl or the base containing vinyl Group.Group containing vinyl can be enumerated: acryloyl group, methylacryloyl, acryloxy, methacryloxy, ethylene Base phenyl etc..
In formula (A-3-1), Ra indicates substituent group.Substituent group is not particularly limited, and can be enumerated: alkyl (preferably carbon number 1~ 21), alkenyl (preferably carbon number 2~12), aryl (preferably carbon number 6~24) etc..These substituent groups, which can also further have, to be taken Dai Ji, the substituent group that can have can be enumerated: hydroxyl, alkoxy (preferably carbon number 1~6), carboxyl, acyl group (preferably carbon number 1~ 6) etc..
In formula (A-3-1), the integer of na expression 1~10, preferably 3~8.The integer of nb expression 0~9, preferably 2~7. Na+nb is 10 hereinafter, preferably 2~8.When na, nb are 2 or more, multiple structure positions of defined can also be different.
Relative to total 100 mass parts of (A-3) component of polymer, the content of polymerizable monomer is preferably 5 mass Part~60 mass parts, more preferably 10 mass parts~50 mass parts, and then preferably 15 mass parts~45 mass parts.
Relative to total solid content, photosensitive polymer combination of the invention is preferably with 5 mass of mass %~60 %'s Ratio and contain polymerizable monomer, more preferably contained with the ratio of 10 mass of mass %~50 %, so preferably with 15 matter The ratio of the amount mass of %~45 % contains.
(B-3) Photoepolymerizationinitiater initiater
Workable Photoepolymerizationinitiater initiater is photosensitive by exposure light in the present invention, causes, promotes the polymerism The compound of the polymerization of single body.
Workable Photoepolymerizationinitiater initiater is photosensitive preferably by exposure light in the present invention, causes, promotes the second The compound of the polymerization of alkene unsaturated compound.
" radioactive ray " so-called in the present invention, as long as that can assign by its irradiation initiation kind can be generated by ingredient B-3 The active energy ray of energy, then there is no particular restriction, widely comprising alpha ray, gamma-rays, X-ray, ultraviolet light (UV), visible Light, electron beam etc..
Photoepolymerizationinitiater initiater is that induction is preferably wavelength 300nm or more, is more preferably the photochemical of wavelength 300nm~450nm Ray causes, the compound of the polymerization of (A-3) polymerizable monomer described in promotion.In addition, about wavelength 300nm is not incuded directly Above photoactinic Photoepolymerizationinitiater initiater, as long as being also the light for incuding wavelength 300nm or more and being used in combination with sensitizer The compound for changing ray, then can combine with sensitizer and be preferably used.
Photoepolymerizationinitiater initiater can for example be enumerated: oxime ester compound, organic halogenation compound, oxygroup diazole compounds, carbonyl Compound, ketal compound, benzoin compound, acridine compounds, organic peroxy compound, azo-compound, cumarin Compound, azido compound, metallocene compound, six aryl united imidazoles, organic boric acid compounds, disulfonic acid chemical combination Object, α amino ketone compound, salt compound, acylphosphanes (oxide) compound.In these, for the aspect of sensitivity, preferably For oxime ester compound, α amino ketone compound, six aryl united imidazoles, more preferably oxime ester compound or α amino assimilation is closed Object.
The concrete example of these compounds for example can refer to the numbered paragraphs 0061 of Japanese Patent Laid-Open 2011-186398 bulletin Its content is incorporated into present specification by the record of~numbered paragraphs 0073.
Commercially available product can also be used in Photoepolymerizationinitiater initiater, such as gorgeous good solid (IRGACURE) OXE 01, gorgeous good solid can be used (IRGACURE) OXE 02 (BASF (BASF) manufacture) etc..
Photoepolymerizationinitiater initiater can be used a kind of or be applied in combination two or more.In addition, not having in use to exposure wavelength When the situation of the initiator of absorption, it is necessary to use sensitizer.
Relative to total 100 mass parts of (A-3) component of polymer, in photosensitive polymer combination of the invention The content of Photoepolymerizationinitiater initiater is preferably 0.5 parts by weight~30 parts by weight, more preferably 2 parts by weight~20 parts by weight.
Relative to total solid content, photosensitive polymer combination of the invention is preferably with 0.5 mass of mass %~30 % Ratio and contain Photoepolymerizationinitiater initiater, more preferably contained with the ratio of 2 mass of mass %~20 %.
(A-4) component of polymer
At least one that (A-4) component of polymer contains following polymer used in the present invention: have containing (a4-1) The polymer of the structural unit of the structural unit of acidic group and (a4-2) with bridging property base and there is acidic group containing (a4-1) The polymer of the polymer of structural unit and the structural unit containing (a4-2) with bridging property base.It in turn, can also be poly- at (A-4) In polymer component, contain the structural unit (a4- together with the structural unit (a4-1) and the structural unit (a4-2) 1) structural unit (a4-3) and other than the structural unit (a4-2).
(A-4) (a4-1) contained by polymer there is the structural unit of acidic group can be used and the 2nd form described above (A-2) (a2-1) described in component of polymer has the structural unit of acidic group identical, and preferred scope is also identical.
(A-4) (a4-2) contained by polymer there is the structural unit of bridging property base can be used and the 2nd shape described above (a2-2) described in (A-2) component of polymer of state has the structural unit of bridging property base identical, and preferred scope is also identical.
(A-4) structural unit contained by polymer (a4-3) for example can be used poly- with (A-2) of the 2nd form described above (a2-3) other structures unit described in polymer component is identical, and preferred scope is also identical.
The composition of 3rd form of the invention is preferably with the ratio of the 30 weight % or more of total solid content and containing poly- Polymer component.
<(C-3) solvent>
Photosensitive polymer combination of the invention contains solvent.Photosensitive polymer combination of the invention will be preferably to incite somebody to action this Each ingredient of invention is dissolved in the form preparation of the solution in solvent.
Well known solvent, for example described above the can be used in solvent used in photosensitive polymer combination of the invention (C-1) solvent of 1 form.
Relative to 100 mass parts of total ingredient in photosensitive polymer combination, in photosensitive polymer combination of the invention The content of solvent be preferably 50 mass parts~95 mass parts, more preferably 60 mass parts~90 mass parts.Solvent can be used only It is a kind of, it is possible to use two or more.When using two or more situations, preferably its total amount becomes the range.
<(S) polymer>
Composition of the invention contains (S) polymer described above.(S) polymer used in 3rd form can be used (S) polymer of 1st form described above, preferred scope are also identical.Relative to the gross mass of photosensitive polymer combination, (S) ingredient is preferably contained with the ratio of 0.1 mass of mass %~20 %, more preferably with 0.1 mass of mass %~10 % Ratio and contain, and then preferably contained with the ratio of 1 mass of mass %~10 %, especially preferably with 2 mass %~5 The ratio of quality % and contain.(S) ingredient can be only one kind, can also be two or more.It is two or more situations in (S) ingredient When, preferably its total amount becomes the range.
<other compositions>
Composition of the invention, can be in the range of not undermining effect of the invention, optionally other than the ingredient Preferably add crosslinking agent described above, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkali compounds, surfactant, antioxidant.Into And in photosensitive polymer combination of the invention, development accelerant, plasticiser, hot radical producing agent, hot acid can be added and produced Give birth to additive well known to antisettling agent of agent, ultraviolet absorbing agent, thickener and organic or inorganic etc..These ingredients and above 1st homomorphosis, preferred scope are also identical.
<preparation method of photosensitive polymer combination>
By each ingredient with set ratio and using arbitrary method mix, stirring and dissolving and prepare photosensitive resin composition Object.For example, these solution are mixed with set ratio after may also be fabricated which ingredient being dissolved in the solution in solvent in advance respectively And prepare resin combination.The composition solution prepared as described above can also be using such as the filter in 0.2 μm of aperture Be subject to after being filtered using.
<manufacturing method of the cured film of the 1st form of the invention>
The step of manufacturing method of the cured film of 1st form of the invention preferably comprises (1-1) below~(5-1).
The photosensitive polymer combination of 1st form of the invention is coated on the step on substrate by (1-1)；
(2-1) removes the step of solvent from the photosensitive polymer combination being coated with；
The step of (3-1) is exposed the photosensitive polymer combination for eliminating solvent using actinic ray；
The step of (4-1) develops to exposed photosensitive polymer combination using aqueous developer；
(5-1) carries out the rear baking procedure of thermmohardening to developed photosensitive polymer combination.
Sequentially each step is illustrated below.
In the application step of (1-1), preferably photosensitive polymer combination of the invention is coated on substrate and is made At the wet film containing solvent.Preferably before photosensitive polymer combination is coated on substrate, carries out alkali cleaning or wait The cleaning of the substrates such as gas ions cleaning, more preferably further utilizes hexamethyldisilazane to substrate surface after base-plate cleaning It is handled.By carrying out the processing, have the tendency that photosensitive polymer combination improves the adherence of substrate.Utilize pregnancy The method that base disilazane handles substrate surface is not particularly limited, such as can enumerate substrate being exposed to hexamethyl two Method etc. in silazane steam.
The substrate can enumerate inorganic substrate, resin, resin composite materials etc..
Inorganic substrate can for example be enumerated: glass, quartz, silicone, silicon nitride, and be vapor-deposited on the substrate of these materials The composite substrate of molybdenum, titanium, aluminium, copper etc..
It about resin, can enumerate: polybutylene terephthalate, polyethylene terephthalate, poly- naphthalenedicarboxylic acid second two Ester, poly- naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyether sulfone, polyarylate, allyl diglycol carbonates, Polyamide, polyimides, polyamidoimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, polycyclic alkene, norbornene tree The fluororesin such as rouge, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer Resin, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic ether, maleimide-alkene, cellulose, ring The synthetic resin such as sulphur compound.
These substrates are seldom directly used in the form of described, are usually regarded the form difference of final products and are formed such as TFT Multilayer laminate constructions as element.
The coating method of substrate is not particularly limited, such as can be used: slot coated method, spray-on process, roller coating method, rotation Turn the methods of rubbing method, cast coating method, slit and rotary process.
Wet film thickness when coating is not particularly limited, and can be coated with corresponding with purposes film thickness, but usually 0.5 μm~10 μm in the range of use.
It in turn, can also be before being coated with composition used in the present invention on substrate, using Japanese Patent Laid-Open 2009- Such so-called (pre-wet) method of prewetting is recorded in No. 145395 bulletins.
In the solvent removal step of (2-1), through decompression (vacuum) and/or heating etc. from the film being coated with Except solvent, dry coating is formed on substrate.The heating condition of solvent removal step is preferably 30 seconds at 70 DEG C~130 DEG C~ 300 seconds or so.When temperature and time is the situation of the range, figuratum adherence is better and can also be further Reduce the tendency of residue.
Actinic ray in the step of exposure of (3-1), to the substrate irradiation predetermined pattern for being equipped with film.In the step In, photoacid generator decomposes and generates acid.Using the catalyst action of generated acid, acid contained in film component will be applied and decomposed Property base hydrolysis, generate carboxyl or phenolic hydroxyl group.
Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemistry can be used using photoactinic exposure light source Lamp, light emitting diode (Light Emitting Diode, LED) light source, excimer laser generation device etc., it is preferable to use I ray (365nm), h ray (405nm), g ray (436nm) etc. have the photochemical of 300nm or more and 450nm wavelength below Ray.In addition, can also optionally pass through as long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter points Optical filter adjusts irradiation light.Light exposure is preferably 1mJ/cm2~500mJ/cm2。
Exposure device can be used: mirror surface projection is directed at machine (mirror projection aligner), stepper (stepper), scanner (scanner), close induction type (proximity), contact (contact), microlens array The exposure machine of the various modes such as (microlens array), lens scan device (lens scanner), laser explosure.
In the region for generating acid catalyst, in order to accelerate the hydrolysis, heat treatment (exposes after being exposed (Post Exposure Bake) is toasted after light hereinafter also referred to " PEB ").By PEB, it can promote and carboxylic is generated by sour decomposability base Base or phenolic hydroxyl group.Carry out PEB situation temperature be preferably 30 DEG C or more and 130 DEG C hereinafter, more preferably 40 DEG C or more and 110 DEG C hereinafter, especially preferably 50 DEG C or more and 100 DEG C or less.
Wherein, the activation evergy that the acid of sour decomposability base of the invention decomposes is low, is easy reason and exposes photogenic derive from The acid of acid producing agent and decompose, generate carboxyl or phenolic hydroxyl group, therefore not necessarily to carry out PEB, can also be formed by developing Eurymeric image.
In the development step of (4-1), using alkaline-based developer to the copolymer with free carboxyl or phenolic hydroxyl group Develop.It is easy to be dissolved in the exposure of the resin combination with carboxyl or phenolic hydroxyl group in alkaline-based developer by that will contain The removal of light portion region, and form eurymeric image.
In developer solution used in development step, preferably containing the aqueous solution of alkali compounds.Alkali compounds is for example It can be used: the alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium hydroxide；The alkali such as sodium carbonate, potassium carbonate, cesium carbonate Metal carbonate salt；The alkaline metal bicarbonates class such as sodium bicarbonate, potassium bicarbonate；Tetramethyl ammonium hydroxide, tetraethylammonium hydroxide base The tetraalkylammonium hydroxides class such as ammonium, tetrapropylammonium hydroxide, tetrabutylammonium, diethyldimethylammonhydroxide hydroxide；Choline Equal hydroxides (hydroxy alkyl) trialkyl ammonium class；The silicates such as sodium metasilicate, sodium metasilicate；Ethamine, propylamine, diethylamine, three second The alkyl amines such as amine；The alcamines such as dimethylethanolamine, triethanolamine；1,8- diazabicyclo-[5.4.0] -7- hendecene, 1, The ester ring types amines such as 5- diazabicyclo-[4.3.0] -5- nonene.
In these, preferably sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide four Propyl ammonium, tetrabutylammonium, choline (hydroxide -2- hydroxyethyl trimethyl ammonium).
In addition, can will also add the water-miscible organic solvents such as methanol or the ethyl alcohol of appropriate amount in the aqueous solution of the bases Or aqueous solution made of surfactant is used as developer solution.
Preferred developer solution can enumerate 0.4%~2.5% aqueous solution of tetramethyl ammonium hydroxide.
The pH value of developer solution is preferably 10.0~14.0.
Developing time is preferably 30 seconds~500 seconds, in addition, the method for development can be covering liquid method (puddle Method), spray process, infusion process etc. is any.
After development, rinsing step can also be carried out.In rinsing step, by utilizing the base after the cleanings such as pure water development Plate, and carry out accompanying developer solution removal, development residue removal.Well known method can be used in ELUTION METHOD.Such as it can enumerate Spray elution or dipping elution etc..
In the rear baking procedure of (5-1), resulting eurymeric image is heated, thermally decomposes sour decomposability base And carboxyl or phenolic hydroxyl group are generated, it is crosslinked with bridging property base, crosslinking agent etc., thus can form cured film.The heating is preferably Using heating devices such as hot plate or baking ovens, in set temperature, at such as 180 DEG C~250 DEG C carry out given time heating at Reason, such as if the heat treatment for then carrying out 5 minutes~90 minutes on hot plate, then carried out if baking oven 30 minutes~120 minutes Heat treatment.By so carrying out cross-linking reaction, the superior protective film such as heat resistance, hardness can be formed or interlayer is exhausted Velum.In addition, by carrying out in a nitrogen environment, also can further improve the transparency when being heated.
Before rear baking, baking (is dried in additional after can also carrying out after being toasted at relatively low temperature Roasting step).When the situation of underway baking, heated preferably at 90 DEG C~150 DEG C 1 minute~after sixty minutes, at 200 DEG C It is toasted after being carried out at a high temperature of above.In addition, also middle baking, rear baking can be divided into for three the multistages more than stage to be added Heat.By the way that such middle baking, rear baking is arranged, the cone angle of pattern can adjust.These baking heating can be used hot plate, baking oven, Heating means well known to infrared heater etc..
Furthermore (rear exposure can be exposed again comprehensively to figuratum substrate progress is formed using actinic ray before rear baking Light) after, it is toasted after progress, acid is thus generated by the photoacid generator being present in unexposed portion, as promotion cross-linking step Catalyst and function, to can promote the sclerous reaction of film.The preferred light exposure of situation including post-exposure step is excellent It is selected as 100mJ/cm2~3,000mJ/cm2, especially preferably 100mJ/cm2~500mJ/cm2。
In turn, also dry-etching resist can will be used as by the resulting cured film of photosensitive polymer combination of the invention. When situation of the resulting cured film of thermmohardening as dry-etching resist will be carried out by rear baking procedure, at etching Reason, can be ashed, plasma etching, ozone etching etc. dry-etchings processing.
<manufacturing method of the cured film of the 2nd form of the invention>
The step of manufacturing method of the cured film of 2nd form of the invention preferably comprises (1-2) below~(5-2).
The photosensitive polymer combination of 2nd form of the invention is coated on the step on substrate by (1-2)；
(2-2) removes the step of solvent from the photosensitive polymer combination being coated with；
The step of (3-2) is exposed the photosensitive polymer combination for eliminating solvent using actinic ray；
The step of (4-2) develops to exposed photosensitive polymer combination using aqueous developer；
(5-2) carries out the rear baking procedure of thermmohardening to developed photosensitive polymer combination.
Each step (1-2) of the manufacturing method of cured film of the invention~step (5-2) can be respectively with the described above the 1st The step of (1-1) of the manufacturing method of the cured film of form~(5-1), is carried out similarly, and optimum condition is also identical.
Etching resist is also acted as by the resulting cured film of composition of the invention.
[manufacturing method of the cured film of the 3rd form of the invention]
The step of manufacturing method of the cured film of 3rd form of the invention preferably comprises (1-3) below~(5-3).
The photosensitive polymer combination of 3rd form of the invention is coated on the step on substrate by (1-3)；
(2-3) removes the step of solvent from the photosensitive polymer combination being coated with；
The step of (3-3) is exposed the photosensitive polymer combination for eliminating solvent using actinic ray；
The step of (4-3) develops to exposed photosensitive polymer combination using aqueous developer etc.；
(5-3) carries out the rear baking procedure of thermmohardening to developed photosensitive polymer combination.
Sequentially each step is illustrated below.
In the application step of (1-3), photosensitive polymer combination is coated on substrate.
About the preparation of photosensitive polymer combination, such as may be made as being dissolved in described in advance respectively containing ingredient molten After solution in agent, by these solution with set ratio mixes and prepares resin combination.The combination prepared as described above Object solution can also using after being filtered such as the filter in 0.2 μm of aperture for using.
In the application step of (1-3), the substrate recorded in (1-1) step described above can be used, in addition, can be used The coating method recorded in (1-1) step described above.
In the solvent removal step of (2-3), preferably by decompression and/or heat from the photoresist group being coated with It closes in object and removes solvent, form dry coating on substrate.The heating condition of (2-3) solvent removal step also regards the kind of each ingredient Class or allotment ratio and it is different, 30 seconds~120 seconds or so at preferably 80 DEG C~130 DEG C.
In the step of exposure of (3-3), preferably to resulting film with set pattern-like illumination wavelength 300nm or more And 450nm actinic ray below.In the step, work that polymerizable monomer (polymerizable compound) passes through polymerization initiator With and polymerize hardening.
About the photoactinic exposure of utilization, in the manufacturing method that the cured film of the 1st form described above can be used The actinic ray enumerated in the explanation of step of exposure.In addition, optionally can also be ended by long wavelength cutoff filter, short wavelength Filter is divided as filter, bandpass filter to adjust irradiation light.
In the development step of (4-3), it is preferable to use alkaline-based developer develops.By that will contain with acidic group Resin combination the removal of unexposed portion region, and form minus image.
In developer solution used in development step, preferably contain alkali compounds.On alkali compounds for example can be used The alkali compounds enumerated in the explanation of development step in the manufacturing method of the cured film of 1st form described in text.
The pH value of developer solution is preferably 10.0~14.0.Developing time is preferably 30 seconds~180 seconds, in addition, development Method can be any of covering liquid method, infusion process etc..After development, flowing water cleaning in 30 seconds~90 seconds can be carried out and formed Required pattern.After development, elution step can also be carried out similarly with the manufacturing method of the cured film of the 1st form described above Suddenly.
In the rear baking procedure of (5-3), resulting minus image is heated, thus removes the solvent composition of remaining It removes, optionally promotes the crosslinking of resin, thus can form cured film.The heating is preferably heated to 150 DEG C or more of high temperature, 180 DEG C~250 DEG C are more preferably heated to, is especially preferably heated to 200 DEG C~240 DEG C.Heating time can be according to heating temperature Degree etc. and suitably set, be preferably set as in the range of 10 minutes~120 minutes.It can also be with the 1st form described above The manufacturing method of cured film is toasted in similarly implementing.
If the step of increasing before rear baking procedure to developing pattern entire surface irradiation actinic ray, preferably ultraviolet light (post-exposure step) can then be irradiated by actinic ray and promote cross-linking reaction.In turn, by photosensitive resin composition of the invention The resulting cured film of object also acts as dry-etching resist.
The feelings that the resulting cured film of thermmohardening is used as dry-etching resist will carried out by the rear baking procedure of (5-3) When shape, about etching process, can be ashed, plasma etching, ozone etching etc. dry-etchings processing.
[cured film]
Cured film of the invention is to make the 1st form of invention discussed above~the 3rd form photosensitive resin composition Object hardens resulting cured film.
Cured film of the invention is preferably used as interlayer dielectric.In addition, cured film of the invention is preferably by above The resulting cured film of forming method of 1st form~the 3rd form cured film of the invention.
Using photosensitive polymer combination of the invention, even if it is excellent and toasted at high temperature to can get insulating properties Also there is the interlayer dielectric of the high transparency when situation.Use layer insulation made of photosensitive polymer combination of the invention Film has a high transparency, and cured film physical properties excellent, therefore in liquid crystal display device or organic EL display device with having on the way With.
[liquid crystal display device]
Liquid crystal display device of the invention has cured film of the invention.
Liquid crystal display device of the invention is formed by addition to having using the photosensitive polymer combination of the invention Other than planarization film or interlayer dielectric, there is no particular restriction, can enumerate the well known liquid crystal display device using various structures.
For example, the thin film transistor (TFT) (Thin-Film Transistor, TFT) that liquid crystal display device of the invention has Concrete example can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention due to Excellent electrical characteristic, therefore can combine and be preferably used with these TFT.
In addition, the liquid crystal drive mode that liquid crystal display device of the invention can use can be enumerated: twisted nematic (Twisted Nematic, TN) mode, vertical orientation (Vertical Alignment, VA) mode, coplanar switching (In-Plane- Switching, IPS) mode, fringing field switching (Fringe Field Switching, FFS) mode, optical compensation curved (Optical Compensated Bend, OCB) mode etc..
It is constituted about panel, in the liquid crystal of colorful optical filter array (Color Filter on Array, COA) mode Cured film of the invention can also be used in showing device, for example, can be used as the organic insulating film of Japanese Patent Laid-Open 2005-284291 (115) or the organic insulating film of Japanese Patent Laid-Open 2005-346054 (212).In addition, liquid crystal display device of the invention is desirable The specific of liquid crystal orientation film aligned enumerate friction orientation method, optical alignment method etc..In addition, also using Japan Patent spy Open the polymer stabilizing orientation recorded in 2003-149647 bulletin or Japanese Patent Laid-Open 2011-257734 bulletin (Polymer Sustained Alignment, PSA) technology carries out polymer orientation support.
In addition, photosensitive polymer combination of the invention and cured film of the invention are not limited to the purposes, can be used for In various uses.For example, also can be preferably used as the protection of colored filter other than planarization film or interlayer dielectric Film or to by the liquid crystal layer in liquid crystal display device be held in certain thickness spacer (spacer) or solid-state image pickup member The lenticule etc. of colorized optical filtering on piece is set in part.
Fig. 2 is the conceptual sectional view for indicating an example of liquid crystal display device 10 of active matrix mode.The colour liquid Crystal device 10 is liquid crystal display panel on the back side with back light unit 12, and in liquid crystal display panel, configured with be pasted with The element of the corresponding TFT16 of all pixels configured between 2 sheet glass substrates 14 of light polarizing film, glass substrate 15.It is formed in Each element on glass substrate is by the contact hole 18 that is formed in cured film 17, and the indium oxide of the tangible pixel electrode of wiring Tin (Indium Tin Oxide, ITO) transparent electrode 19.On ito transparent electrode 19, layer equipped with liquid crystal 20 and configured with black RGB (Red Green Blue, RGB) colored filter 22 of colour moment battle array.
The light source of backlight is not particularly limited, and well known light source can be used.Such as can enumerate White LED, blue it is red The multi-colored led of color green etc., fluorescent lamp (cold-cathode tube), organic EL etc..
In addition, liquid crystal display device may be set to three-dimensional (Three Dimensions, 3D) (stereopsis) type, can also set For touch screen type.And then may also be set to flexible type, can be used as recording in Japanese Patent Laid-Open 2011-145686 bulletin the The interlayer dielectric (520) recorded in 2 interlayer dielectrics (48) or Japanese Patent Laid-Open 2009-258758 bulletin.
[organic EL display device]
Organic EL display device of the invention has cured film of the invention.
Organic EL display device of the invention is formed in addition to having using the photosensitive polymer combination of the invention Planarization film or interlayer dielectric other than, there is no particular restriction, can enumerate well known various organic EL using various structures Display device or liquid crystal display device.
For example, thin film transistor (TFT) that organic EL display device of the invention has (Thin-Film Transistor, TFT concrete example) can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention Due to excellent electrical characteristic, therefore it can combine and be preferably used with these TFT.
Fig. 1 is the composition concept map of an example of organic EL display device.It indicates that organic EL of bottom emission type shows dress The schematic cross sectional view of substrate in setting has planarization film 4.
The TFT1 of bottom gate type is formed on glass substrate 6, is formed with covering the state of the TFT1 comprising Si3N4's Insulating film 3.After forming the contact hole of illustration omitted herein in insulating film 3, it will be connected to TFT1's via the contact hole Wiring 2 (1.0 μm of height) is formed on insulating film 3.Wiring 2 is to have by connection between TFT1 or by what is formed in subsequent step The wiring that machine EL element is connect with TFT1.
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.
On planarization film 4, the organic EL element of bottom emission type is formed.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 its subsequent step.
In turn, in Fig. 1 although not shown, but it is situated between setting hole transmission layer, organic is sequentially deposited every required pattern mask Luminescent layer, electron transfer layer then form the second electrode comprising A1 in the entire surface above substrate, hard using ultraviolet light Change type epoxy resin is bonded with glass for sealing plate, is thus sealed, and is obtained and is connected each organic EL element to drive Move the organic EL display device of active array type made of the TFT1 of the organic EL element.
Photosensitive polymer combination of the invention is pretended due to hardenability and cured film excellent as MEMS (Microelectromechanical Systems, MEMS) uses the structural elements of element, will use photonasty tree of the invention Oil/fat composition is formed by resist pattern as dividing wall, or enters as a part of group of Mechanical Driven part and use.This Kind MEMS element can for example be enumerated: surface acoustic wave (Surface Acoustic Wave, SAW) filter, bulk acoustic wave (Bulk Acoustic Wave, BAW) filter, gyrosensor (gyro sensor), the micro- shutter of display (microshutter), the parts such as imaging sensor, Electronic Paper, ink gun, biochip (biochip), sealant.More specifically Example be illustrated in Japanese patent special table 2007-522531, Japanese Patent Laid-Open 2008-250200, Japanese Patent Laid-Open 2009- In 263544 etc..
Photosensitive polymer combination of the invention for example can also be used to form Japan since flatness or the transparency are excellent The stack layer (16) and planarization film (57), Japanese Patent Laid-Open recorded in Fig. 2 of open patent 2011-107476 bulletin The dividing wall (12) and planarization film (102), Japanese Patent Laid-Open 2010- recorded in Fig. 4 (a) of 2010-9793 bulletin The stack layer (221) and the 3rd interlayer dielectric (216b), Japanese Patent Laid-Open 2009- recorded in Figure 10 of No. 27591 bulletins The 2nd interlayer dielectric (125) and the 3rd interlayer dielectric (126), the Japan Patent recorded in Fig. 4 (a) of No. 128577 bulletins are special Open the planarization film (12) recorded in Fig. 3 of 2010-182638 bulletin and pixel separation insulating film (14) etc..In addition to this, It also can be preferably used as the liquid crystal layer in liquid crystal display device is held in certain thickness spacer or facsimile machine (facsimile), the brilliant imaging optical system for carrying colored filter of electronic reprographic machine, solid-state imager etc. or optical fiber connection The lenticule of device.
[embodiment]
Embodiment is exemplified below to be more particularly described the present invention.Material shown in embodiment below, usage amount, Ratio, process content, processing sequence etc. can then be suitably changed without departing from purport of the invention.Therefore, the scope of the present invention It is not limited to concrete example as shown below.Furthermore as long as no special instructions, then " part ", " % " are quality criteria.
In synthesis example below, symbol below respectively indicates compound below.
MATHF: methacrylic acid -2- tetrahydrofuran ester (composite)
MAEVE: methacrylic acid -1- ethoxy ethyl ester (and the manufacture of Wako Pure Chemical Industries company)
OXE-30: methacrylic acid -3- ethyl -3- oxetanylmethoxy methyl esters (manufacture of Osaka Organic Chemical Industry company)
GMA: glycidyl methacrylate (and the manufacture of Wako Pure Chemical Industries company)
NBMA: n-butoxy methyl acrylamide (Tokyo chemical conversion manufacture)
HEMA: hydroxyethyl methacrylate (manufacture of He Guangchun medicine company)
MAA: methacrylic acid (and the manufacture of Wako Pure Chemical Industries company)
MMA: methyl methacrylate (and the manufacture of Wako Pure Chemical Industries company)
St: styrene (and the manufacture of Wako Pure Chemical Industries company)
DCPM: two ring pentyl ester of methacrylic acid
V-601: 2,2 '-azo of dimethyl-bis- (2 Methylpropionic acid esters) (and the manufacture of Wako Pure Chemical Industries company)
V-65:2,2 '-azos bis- (2,4- methyl pentane nitriles) (and the manufacture of Wako Pure Chemical Industries company)
PGMEA (propylene glycol monomethyl ether): (manufacture of Showa electrician company)
MEDG (diethylene glycol ethyl methyl ether): Hai Suofu (Hisolve) EDM (manufacture of Dong Bang chemical industrial company)
<synthesis of MATHF>
Methacrylic acid (86g, 1mol) is cooled to 15 DEG C, is added camphorsulfonic acid (4.6g, 0.02mol).Described molten 2- dihydrofuran (71g, 1mol, 1.0 equivalent) is added dropwise in liquid.It after stirring 1 hour, adds saturated sodium bicarbonate (500mL), utilizes Ethyl acetate (500mL) is extracted, and is depressurized after being dried using magnesium sulfate, after insoluble matter is filtered 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/3.5mmHg~ Methacrylic acid tetrahydro -2H- furans -2- base ester (MATHF) 125g (yield 80%) of 56 DEG C/3.5mmHg fraction.
<synthesis example of polymer A-1>
PGMEA (89g) is added in three-necked flask, is warming up to 90 DEG C in a nitrogen environment.With 2 hours in the solution Dropwise addition makes MAA (amount as the 9.5mol% in all monomer components), MATHF (as the 43mol% in all monomer components Amount), GMA (being equivalent to the 47.5mol% in all monomer components), the V-65 (total amount relative to all monomer components 100mol% and be equivalent to 4mol%) be dissolved in the solution in PGMEA (89g) at room temperature.It is stirred at 70 DEG C after completion of dropwise addition It mixes 2 hours, terminates reaction.Thus to obtain polymer A-1.Furthermore with the dense of the ingredient (referred to as solid component) other than solvent Degree is adjusted as 40% mode.
Monomeric species etc. are changed as shown in following tables, synthesize other polymers.
In the table, the numerical value of especially mark unit is not as unit of mol% in table.Polymerization initiator and additive Numerical value is the mol% that monomer component is set as to the situation of 100mol%.Solid component concentration is with monomer mass/(monomer matter Amount+solvent quality) × 100 (unit mass %) indicate.
<synthesis example of polymer P -1>
In the flask for having condenser pipe and blender, addition 2,2 '-azos pair-(2,4- methyl pentane nitrile) 7 mass parts And 200 mass parts of diethylene glycol ethyl methyl ether.Then, 12 mass parts of methacrylic acid, methyl propenoic acid glycidyl are added 50 mass parts of ester, 8 mass parts of 3- (2- methacryloxyethyl) oxetanes, 10 mass of N- N-cyclohexylmaleimide Part, 15 mass parts of tetrahydrofurfuryl methacrylate, 5 mass parts of acryloyl morpholine and pentaerythrite four (3-thiopropionate) 2 Mass parts and after carrying out nitrogen displacement, slowly start to stir.So that the temperature of solution is risen to 70 DEG C, reaches in reaction solution temperature Start to polymerize at the time of 70 DEG C.Thereafter, after auto polymerization begins to pass through 30 minutes, N- cyclohexyl Malaysia acyl is added dropwise in reaction solution 3 mass parts of N- N-cyclohexylmaleimide are added dropwise in 3 mass parts of imines in reaction solution after 1 hour.Thereafter it is kept for 3 hours, by This obtains the polymer solution comprising copolymer (P-1).The polystyrene converted weight average molecular weight (Mw) of copolymer p -1 is 9,000, molecular weight distribution (Mw/Mn) is 2.0.
About other polymers, also using the monomer (monomer component (raw material of (a1)~(a3))) recorded in following tables, Polymerization initiator, molecular weight regulator, solvent synthesize in the same manner as P-1.
In the table, the numerical value of especially mark unit is not as unit of mol% in table.Polymerization initiator and additive Numerical value is the mol% that monomer component is set as to the situation of 100mol%.Solid component concentration is with monomer mass/(monomer matter Amount+solvent quality) × 100 (unit mass %) indicate.
<preparation of photosensitive polymer combination>
In a manner of becoming the solid component ratio recorded in following tables, autohemagglutination polymer component, polymerizable monomer, (S) polymerization Object, photoacid generator, quinone di-azido compound, Photoepolymerizationinitiater initiater, sensitizer, alkali compounds, alkoxysilane compound containing trialkylsilyl group in molecular structure, In surfactant and other compositions, ingredient shown in each each comparative example of embodiment shown in following tables is used respectively, Dissolution mixing utilizes 0.2 μm of the polytetrafluoroethylene (PTFE) system in aperture until solid component concentration becomes 25% in solvent (PGMEA) Filter is filtered, and obtains the photosensitive polymer combination of various Examples and Comparative Examples.
Indicate that the details of the abbreviation of each compound used in Examples and Comparative Examples is as follows.
(photoacid generator)
B-1: structure shown in following (synthesis example will be aftermentioned)
[changing 34]
B-2: structure shown in following (is recorded in the paragraph 0108 according to Japanese patent special table 2002-528451 bulletin Method synthesize)
[changing 35]
B-3:PAG-103 (structure shown in following, the manufacture of BASF (BASF) company)
[changing 36]
((S) polymer)
S-1:X-12-981S (epoxy-modified, the manufacture of silicone company, SHIN-ETSU HANTOTAI), weight average molecular weight 870
S-2:X-12-984S (epoxy-modified, the manufacture of silicone company, SHIN-ETSU HANTOTAI), weight average molecular weight 1540
S-3:X-12-1154 (sulfhydryl modified, the manufacture of silicone company, SHIN-ETSU HANTOTAI), weight average molecular weight 2510
S-4:X-12-1048 (acryl-modified, the manufacture of silicone company, SHIN-ETSU HANTOTAI), weight average molecular weight 3180
S-5:X-12-972F (amino modified, the manufacture of silicone company, SHIN-ETSU HANTOTAI), weight average molecular weight 1650
S-6: structure shown in following (vinyl modified, composite), weight average molecular weight 2230
[changing 37]
S ' -1:3- glycidoxypropyltrimewasxysilane (KBM-403, the manufacture of silicone company, SHIN-ETSU HANTOTAI)
S ' -2:3- mercaptopropyi trimethoxy silane (KBM-803, the manufacture of silicone company, SHIN-ETSU HANTOTAI)
S ' -3:3- acryloyloxypropyltrimethoxysilane (KBM-5103, the manufacture of silicone company, SHIN-ETSU HANTOTAI)
S ' -4:3- TSL 8330 (KBM-903, the manufacture of silicone company, SHIN-ETSU HANTOTAI)
S ' -5:(KBE-3026, the manufacture of silicone company, SHIN-ETSU HANTOTAI)
S ' -6:(KBM-9659, the manufacture of silicone company, SHIN-ETSU HANTOTAI)
S ' -7:(JER157S65, Mitsubishi Chemical Ind's manufacture)
S ' -8:(Ka Yala get (KAYARAD) DPHA, Japanese chemical drug (stock) manufacture)
(alkali compounds)
H-1: the compound of following structures
[changing 38]
(surfactant)
W-1: nonionic surfactant (F-554, DIC (DIC) shown in following structural formula containing perfluoroalkyl Manufacture)
[changing 39]
W-2: silicone-based the surfactant (" SH of Dong Li-DOW CORNING (Toray-Dow corning) (stock) manufacture 8400FLUID”)
W-3: fluorine system surfactant (FTX-218, Ni Aosi (Neos) (stock) manufacture)
(sensitizer)
DBA:9,10- dibutoxy anthracene (Kawasaki is melted into company's manufacture)
(crosslinking agent)
F-1:JER828 (manufacture of Daicel (Daicel) company)
F-2:EX-321L (long rapids chemical conversion (Nagase Chemtex) company manufacture)
F-3: Plutarch Knight (Takenate) B870N (Mitsui Chemicals, Inc.'s system is made)
F-4: Du draws Knight (Duranate) MF-K60X (manufacture of chemical company, Asahi Chemical Industry)
F-5: Du draws Knight (Duranate) MFA-100 (manufacture of chemical company, Asahi Chemical Industry)
(antioxidant)
F-6: gorgeous Northey (Irganox) 1035 (manufacture of BASF (BASF) company)
F-7: gorgeous Northey (Irganox) 1098 (manufacture of BASF (BASF) company)
(quinone di-azido compound)
Q-1:(4,4 '-[1- [4- [1- [4- hydroxy phenyl] -1- Methylethyl] phenyl] ethylidene] bis-phenols (1.0 moles) With the condensation product of 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride (3.0 moles))
Q-2:(1, (2.0 rub 1,1- tri- (p-hydroxybenzene) ethane (1.0 moles) with 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride You) condensation product)
(polymerizable monomer)
M-1: Ka Yala get (KAYARAD) DPHA (Japanese chemical drug (stock) manufacture)
(Photoepolymerizationinitiater initiater)
I-1: gorgeous good solid (IRGACURE) OXE 02 (BASF (BASF) manufacture)
<synthesis of B-1>
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, the HCl/water that 4N is added dropwise in reaction solution is molten Liquid (60mL), addition ethyl acetate (50mL) carry out liquid separation.Potassium carbonate (19.2g) is added in organic layer, reacts 1 at 40 DEG C After hour, the HCL aqueous solution (60mL) for adding 2N carries out liquid separation, after organic layer is concentrated, will be tied using diisopropyl ether (10mL) Brilliant repulping is filtered, dries and obtain ketone compound (6.5g).
Resulting ketone compound (3.0g), methanol (30mL) suspension solution in add acetic acid (7.3g), 50 mass % Aqueous hydroxylamine (8.0g), is heated to reflux.It after placing cooling, adds water (50mL), the crystallization of precipitation is filtered, carry out It is subject to drying after cold first ferment cleaning, obtains oxime compound (2.4g).
It is dissolved in resulting oxime compound (1.8g) in acetone (20mL), adds triethylamine under ice cooling, 4 (1.5g), paratoluensulfonyl chloride (2.4g) is warming up to room temperature and reacts 1 hour.Water (50mL) is added in reaction solution, will be precipitated Crystallization filtering after, using methanol (20mL) carry out repulping, the compound (knot for being filtered, drying and obtaining B-1 Structure) (2.3g).
Furthermore B-1's1H- nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectrum (300MHz, CDCl3) it is δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
[table 4]
[table 5]
<evaluation of adherence after baking>
On the glass substrate for being formed with Mo (molybdenum) film after each photosensitive polymer combination of spin application, at 90 DEG C 120 seconds kind prebake conditions are carried out on hot plate and solvent is made to volatilize, and form 3.0 μm of film thickness of photosensitive polymer combination layer.Then, make 300mJ/cm is become with accumulative exposure with extra-high-pressure mercury vapour lamp2(energy intensity: 20mW/cm2, i ray) mode exposed Light thereafter heats the substrate 30 minutes at 230 DEG C in an oven, obtains cured film.
Then, cutter (cutter) is used to cured film, notch is cut in length and breadth with the interval of 1mm, uses adhesive tape (scotch tape) carries out belt stripping test (100 lattice cross-cut methods: according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) 5600).Cured film is evaluated according to the area for the cured film being transferred on the adhesive tape back side Adherence between substrate.It the results are shown in following tables.Numerical value is smaller then higher with the adherence of basal substrate, 3 with Upper is realistic scale.
5: the area of transfer is less than 1%
4: the area of transfer is 1% more than and less than 5%
3: the area of transfer is 5% more than and less than 10%
2: the area of transfer is 10% more than and less than 50%
1: the area of transfer is 50% or more
<evaluation of the adherence after high temperature and humidity test>
On the glass substrate for being formed with Mo (molybdenum) film after each photosensitive polymer combination of spin application, at 90 DEG C 120 seconds prebake conditions are carried out on hot plate and solvent is made to volatilize, and form the photosensitive polymer combination layer that film thickness is 3.0 μm.Then, make 300mJ/cm is become with accumulative exposure with extra-high-pressure mercury vapour lamp2(energy intensity: 20mW/cm2, i ray) mode exposed The substrate is heated 30 minutes at 230 DEG C in an oven thereafter and obtains cured film by light.Substrate after baking is being passed through It is adjusted to 100 DEG C, stands 24 hours in the environment of RH100%.
Then, cutter are used to cured film, notch is cut in length and breadth with the interval of 1mm, carry out adhesive tape using adhesive tape Disbonded test (100 lattice cross-cut methods: according to JIS5600).It is commented according to the area for the cured film being transferred on the adhesive tape back side Adherence between valence cured film and substrate.It the results are shown in following tables.Numerical value is smaller, gets over the adherence of basal substrate Height, 3 the above are realistic scales.
5: the area of transfer is less than 1%
4: the area of transfer is 1% more than and less than 5%
3: the area of transfer is 5% more than and less than 10%
2: the area of transfer is 10% more than and less than 50%
1: the area of transfer is 50% or more
<evaluation of sensitivity>
By glass substrate (Iger (EAGLE) XG, 0.7mm thick (healthy and free from worry (Corning) company manufacture)) in hexamethyl two It is exposed 30 seconds under silazane (HMDS) steam, it is enterprising in hot plate at 90 DEG C after each photosensitive polymer combination of spin application 120 seconds prebake conditions of row and so that solvent is volatilized, forming film thickness is 3.0 μm of photosensitive polymer combination layer.
Then, the MPA 5500CF (height resulting photosensitive polymer combination layer manufactured using Canon (Canon) (stock) Medium pressure mercury lamp), Jie is exposed every set mask.Then, using alkaline developer, (0.4% tetramethyl ammonium hydroxide is water-soluble Liquid) the photosensitive polymer combination layer after exposure is carried out 60 seconds after developing at 23 DEG C, utilize ultrapure water to elute 20 seconds. It regard the most suitable i x ray exposure x amount (Eopt) when parsing 5 μm of hole by these operations as sensitivity.
5: less than 20mJ/cm2
4:20mJ/cm2More than and less than 40mJ/cm2
3:40mJ/cm2More than and less than 80mJ/cm2
2:80mJ/cm2More than and less than 160mJ/cm2
1:160mJ/cm2More than
<evaluation of hole cone-shaped>
By glass substrate (Iger (EAGLE) XG, 0.7mm thick (healthy and free from worry (Corning) company manufacture)) in hexamethyl two It is exposed 30 seconds under silazane (HMDS) steam, it is enterprising in hot plate at 90 DEG C after each photosensitive polymer combination of spin application 120 seconds prebake conditions of row and so that solvent is volatilized, forming film thickness is 3.0 μm of photosensitive polymer combination layer.
Then, the MPA 5500CF (height resulting photosensitive polymer combination layer manufactured using Canon (Canon) (stock) Medium pressure mercury lamp) being situated between is exposed every set mask.Then, using alkaline developer, (0.4% tetramethyl ammonium hydroxide is water-soluble Liquid) the photosensitive polymer combination layer after exposure is carried out 60 seconds after developing at 23 DEG C, utilize ultrapure water to carry out 20 seconds Elution.Thereafter, it carries out toasting for 30 minutes at 230 DEG C using baking oven.
Resulting substrate is cut off, beamship is scanned formula electron microscope (Scanning to the hole shape Electron Microscope, SEM) observation, substrate interface portion and angle formed by wall surface of the hole are measured as cone angle. It the results are shown in following tables.For the viewpoint of high analyticity, preferably 3 points or more.
5: cone angle is 60 degree or more
4:40 degree is more than and less than 60 degree
3:30 degree is more than and less than 40 degree
2:20 degree is more than and less than 30 degree
1: less than 20 degree
<evaluation of ease gas>
By glass substrate (Iger (EAGLE) XG, 0.7mm thick (healthy and free from worry (Corning) company manufacture)) in hexamethyl two It is exposed 30 seconds under silazane (HMDS) steam, it is enterprising in hot plate at 90 DEG C after each photosensitive polymer combination of spin application 120 seconds prebake conditions of row and so that solvent is volatilized, forming film thickness is 3.0 μm of photosensitive polymer combination layer.
Then, the MPA 5500CF (height resulting photosensitive polymer combination layer manufactured using Canon (Canon) (stock) Medium pressure mercury lamp) being situated between is exposed every set mask.Then, using alkaline developer, (0.4% tetramethyl ammonium hydroxide is water-soluble Liquid) the photosensitive polymer combination layer after exposure is carried out 60 seconds after developing at 23 DEG C, utilize ultrapure water to carry out 20 seconds Elution.Thereafter, it carries out toasting for 30 minutes at 230 DEG C using baking oven.
Resulting cured film is scraped, is analyzed using thermogravimetric analyzer (Thermo Gravimetric Analyzer, TGA) Device (manufacture of Q-5000SA, TA instrument (TAInstruments) company) 10 DEG C/min of heating rate, keep 230 DEG C of temperature, Weight reduction amount is analyzed under conditions of under 60 minutes retention times, nitrogen environment.
5: weight is reduced less than 1%
4: weight is reduced to 1% more than and less than 3%
3: weight is reduced to 3% more than and less than 5%
2: weight is reduced to 5% more than and less than 10%
1: weight is reduced to 10% or more
<evaluation of solution keeping quality>
The photosensitive polymer combination deployed is taken care of at -20 DEG C, evaluation is until solution starts the time become cloudy.
5:6 months or more
4:3 months more than and less than 6 months
3:1 months more than and less than 3 months
2:2 weeks more than and less than 1 month
1: less than 2 week
[table 6]
[table 7]
[table 8]
Learnt by the table, containing (S) polymer 1~embodiment of embodiment 57 in, adherence, sensitivity, hole cone-shaped, Ease gas and solution keeping quality all become good result.It is learnt relative to this, is free of the comparative example 1 of (S) polymer, compares Not only adherence is poor for example 10, comparative example 15, but also hole cone-shaped and ease gas are also poor.And learn, use alkoxy and group (X) Respectively 2~comparative example of comparative example 5 of S ' -1~S ' -4 of simple function, 11~comparative example of comparative example 14, comparative example 16~compare Also not only adherence is poor for example 19, but also hole cone-shaped and ease gas are also poor.And learn, using there is no group (X) and with more The S ' -5 of functional alkoxy, the comparative example 6 of S ' -6, the adherence of comparative example 7 are poor.In addition learn, using there is no alkoxy and Group (X) is that polyfunctional S ' -7, the comparative example 8 of S ' -8, the adherence of comparative example 9 and hole cone-shaped are poor.
It is obtained according to embodiment 11, embodiment 12, embodiment 13, embodiment 48, embodiment 49, embodiment 56 and embodiment 57 Know, by the way that the group (X) in (S) polymer is set as epoxy group or sulfydryl, adherence is further increased.In addition, according to reality It applies example 10, embodiment 12, embodiment 47, embodiment 49, embodiment 55 and embodiment 57 to learn, by will be in (S) polymer Group (X) is set as the group other than sulfydryl or amino, and solution keeping quality further increases.
In addition, learnt according to embodiment 24, embodiment 25, embodiment 27 and embodiment 28, by by the tune of (S) polymer Dosage is set as in given area, and effect of the invention further increases.It is learnt by these situations, about group (X), with epoxy The double bonds bases such as base, sulfydryl, (methyl) acryloyl group, the sequence of amino and it is excellent.
<production of display device>
(embodiment 101)
The organic EL display device (referring to Fig.1) using thin film transistor (TFT) (TFT) 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 Si3N4's Insulating film 3.Then, it after forming the contact hole of illustration omitted herein in the insulating film 3, will be connected via the contact hole It is formed on insulating film 3 in the wiring 2 (being highly 1.0 μm) of TFT1.The wiring 2 be to will between TFT1 connection or will after The wiring that the organic EL element formed in continuous step is connect with TFT1.
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 the photoresist of embodiment 1 After carrying out prebake conditions (90 DEG C, 2 minutes) on hot plate, high pressure water is used from above mask on substrate for composition slot coated Silver-colored light irradiation 45mJ/cm2(illumination 20mW/cm2) i ray (365nm) after, developed using alkaline aqueous solution and formed Pattern carries out heat treatment in 60 minutes at 230 DEG C.
Coating when photosensitive resin coating composition is good, after exposure, development, calcining in resulting cured film, The generation of gauffer or cracking is not confirmed.In turn, the average scale of wiring 2 is 500nm, the film thickness of made planarization film 4 For 2,000nm.
Then, the organic EL element of bottom emission type is formed on resulting planarization film 4.Firstly, in planarization film 4 On, wiring 2 is connected to via contact hole 7 and forms the first electrode 5 comprising ITO.Thereafter, it is coated with commercially available resist and carries out Prebake conditions, Jie is exposed every the mask of required pattern, and develops.Using the resist pattern as mask, by making Pattern processing is carried out with the wet etching of ITO etchant.Thereafter, using anticorrosive additive stripping liquid controlling (removal liquid (Remover) 100, AZ Electronic Materials Corp's manufacture) resist pattern is removed at 50 DEG C.Such resulting first electrode 5 is equivalent to organic EL The anode of element.
Then, the insulating film 8 of the shape at the edge of covering first electrode 5 is formed.About insulating film 8, embodiment 1 is used Photosensitive polymer combination forms insulating film 8 using method same as above.It, can by the way that the insulating film 8 is arranged Prevent the short circuit between the second electrode formed in first electrode 5 and its subsequent step.
In turn, in vacuum deposition apparatus, it is situated between and setting hole transmission layer, You Jifa is sequentially deposited every required pattern mask Photosphere, electron transfer layer.Then, the second electrode comprising A1 is formed in the entire surface above substrate.By the resulting base Plate takes out from evaporator, is bonded using glass for sealing plate and ultraviolet ray hardening type epoxy resin, is thus sealed.
Obtaining as described above has made of the TFT1 to the connection of each organic EL element to drive the organic EL element The organic EL display device of source matrix type.Apply voltage via driving circuit, good display characteristic out, learns it as the result is shown For the organic EL display device of high reliablity.
(embodiment 102)
In embodiment 101 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 16 Object makes organic EL display device in the same manner as embodiment 101 in addition to this.Resulting organic EL display device is applied and is driven Dynamic voltage, good display characteristic out, learns the organic EL display device that it is high reliablity as the result is shown.
(embodiment 103)
In embodiment 101 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 23 Object makes organic EL display device in the same manner as embodiment 101 in addition to this.Resulting organic EL display device is applied and is driven Dynamic voltage, good display characteristic out, learns the organic EL display device that it is high reliablity as the result is shown.
(embodiment 104)
In embodiment 101 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 30 Object makes organic EL display device in the same manner as embodiment 101 in addition to this.Resulting organic EL display device is applied and is driven Dynamic voltage, good display characteristic out, learns the organic EL display device that it is high reliablity as the result is shown.
(embodiment 105)
In embodiment 101 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 34 Object makes organic EL display device in the same manner as embodiment 101 in addition to this.Resulting organic EL display device is applied and is driven Dynamic voltage, good display characteristic out, learns the organic EL display device that it is high reliablity as the result is shown.
(embodiment 106)
It is such as following in the active array type LCD recorded in Fig. 1 of No. 3321003 bulletins of Japanese Patent No. Cured film 17 is formed like that as interlayer dielectric, obtains the liquid crystal display device of embodiment 106.That is, using the sense of embodiment 1 Photosensitive resin composition, using identical as the forming method of planarization film 4 of organic EL display device in the embodiment 101 Method, formed cured film 17 be used as interlayer dielectric.
Driving voltage is applied to resulting liquid crystal display device, as the result is shown good display characteristic out, learns it as can The liquid crystal display device high by property.
(embodiment 107)
In embodiment 106 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 16 Object makes liquid crystal display device in the same manner as embodiment 106 in addition to this.Driving electricity is applied to resulting liquid crystal display device Pressure, good display characteristic out, learns the liquid crystal display device that it is high reliablity as the result is shown.
(embodiment 108)
In embodiment 106 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 23 Object makes liquid crystal display device in the same manner as embodiment 106 in addition to this.Driving electricity is applied to resulting liquid crystal display device Pressure, good display characteristic out, learns the liquid crystal display device that it is high reliablity as the result is shown.
(embodiment 109)
In embodiment 106 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 30 Object makes liquid crystal display device in the same manner as embodiment 106 in addition to this.Driving electricity is applied to resulting liquid crystal display device Pressure, good display characteristic out, learns the liquid crystal display device that it is high reliablity as the result is shown.
(embodiment 112)
In embodiment 106 into, the photosensitive polymer combination of embodiment 1 is changed to the photosensitive resin composition of embodiment 34 Object makes liquid crystal display device in the same manner as embodiment 106 in addition to this.Driving electricity is applied to resulting liquid crystal display device Pressure, good display characteristic out, learns the liquid crystal display device that it is high reliablity as the result is shown.

Claims (13)

1. a kind of photosensitive polymer combination, contains:
Component of polymer A-1 comprising meeting following 1 and 2 polymer of at least one,
1: the structural unit a1-1 containing the group protected with acidic group through sour decomposability base and the structure list with bridging property base The polymer of first a1-2,
2: the polymer of the structural unit a1-1 containing the group protected with acidic group through sour decomposability base and containing have crosslinking The polymer of the structural unit a1-2 of property base；
Photoacid generator B-1；
Solvent C -1；And
Containing with part-structure represented by the following general formula (1) structural unit with have it is at least one selected from by epoxy group, The polymer S of the structural unit of group X in group composed by sulfydryl, (methyl) acryloyl group, vinyl and amino；Wherein
Relative to total solid content, the blending amount of polymer S is 0.1 mass of mass %~10 %；
General formula (1)
In general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.
2. a kind of photosensitive polymer combination, contains:
Component of polymer A-2 comprising meeting following 1 and 2 polymer of at least one,
1: the polymer containing the structural unit a2-1 with the acidic group and structural unit a2-2 with bridging property base,
2: the polymer containing the structural unit a2-1 with acidic group and gathering containing the structural unit a2-2 with bridging property base Close object；
Quinone di-azido compound B-2；
Solvent C -2；And
Containing with part-structure represented by the following general formula (1) structural unit with have it is at least one selected from by epoxy group, The polymer S of the structural unit of group X in group composed by sulfydryl, (methyl) acryloyl group, vinyl and amino；Wherein
Relative to total solid content, the blending amount of polymer S is 0.1 mass of mass %~10 %；
General formula (1)
In general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.
3. a kind of photosensitive polymer combination, contains:
Polymerizable monomer A-3；
Photoepolymerizationinitiater initiater B-3；
Component of polymer comprising meeting following 1 and 2 polymer of at least one,
1: the polymer A-4 containing the structural unit a4-1 with the acidic group and structural unit a4-2 with bridging property base,
2: the polymer containing the structural unit a4-1 with acidic group and gathering containing the structural unit a4-2 with bridging property base Close object；
Solvent C -3；And
Containing with part-structure represented by the following general formula (1) structural unit with have it is at least one selected from by epoxy group, The polymer S of the structural unit of group X in group composed by sulfydryl, (methyl) acryloyl group, vinyl and amino；Wherein
Relative to total solid content, the blending amount of polymer S is 0.1 mass of mass %~10 %；
General formula (1)
In general formula (1), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer.
4. photosensitive polymer combination according to any one of claim 1 to 3, wherein polymer S contains the following general formula (I) structural unit represented by the structural unit and the following general formula (II) represented by；
In logical formula (I), R1And R2Separately indicate that the alkyl of carbon number 1~4, n indicate 0~2 integer；R3And R4Independently Ground indicates hydrogen atom or methyl；
In logical formula (II), R5Indicate epoxy group, sulfydryl, (methyl) acryloyl group, vinyl or amino, L1And L2Separately Indicate the concatenating group that the atomicity of singly-bound or linking part is 1~6.
L 5. photosensitive polymer combination according to claim 4, in formula of (I)1And L2Separately indicate The concatenating group that the atomicity of linking part is 2~6.
6. photosensitive polymer combination according to any one of claim 1 to 3, wherein the weight average of polymer S divides Son amount is 800 or more.
7. photosensitive polymer combination according to any one of claim 1 to 3, wherein the knot with bridging property base Bridging property base in structure unit is selected from by epoxy group, oxetanylmethoxy and-NH-CH2Composed by group represented by-O-R At least one of group；Wherein, R indicates the alkyl of hydrogen atom or carbon number 1~20.
8. photosensitive polymer combination according to claim 1, wherein photoacid generator B-1 is selected from oxime sulfonates chemical combination At least one of object and salt compound.
9. a kind of manufacturing method of cured film, comprising:
Step photosensitive polymer combination according to any one of claim 1 to 3 being coated on substrate；
The step of solvent is removed from the photosensitive polymer combination being coated with；
The step of resin combination for eliminating solvent is exposed using active radioactive ray；
The step of being developed using aqueous developer to the exposed resin combination；And
The rear baking procedure of thermmohardening is carried out to the developed resin combination.
10. a kind of cured film, be make photosensitive polymer combination according to any one of claim 1 to 3 harden and At.
11. cured film according to claim 10 is interlayer dielectric.
12. a kind of liquid crystal display device has cured film according to claim 10.
13. a kind of organic electroluminescent display device has cured film according to claim 10.
CN201480049945.0A 2013-09-13 2014-09-12 Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device Active CN105531627B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013-190575 2013-09-13
JP2013190575 2013-09-13
PCT/JP2014/074171 WO2015037695A1 (en) 2013-09-13 2014-09-12 Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device

Publications (2)

Publication Number Publication Date
CN105531627A CN105531627A (en) 2016-04-27
CN105531627B true CN105531627B (en) 2019-10-11

Family

ID=52665793

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480049945.0A Active CN105531627B (en) 2013-09-13 2014-09-12 Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device

Country Status (4)

Country Link
JP (1) JP6182612B2 (en)
CN (1) CN105531627B (en)
TW (1) TW201518862A (en)
WO (1) WO2015037695A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6461695B2 (en) * 2015-03-31 2019-01-30 株式会社松風 Polymer silane coupling agent and medical / dental curable composition containing the same
TWI704416B (en) * 2015-08-05 2020-09-11 日商住友化學股份有限公司 Photosensitive resin composition, pattern, partition wall for inkjet, and display device
JP6694685B2 (en) * 2015-09-25 2020-05-20 株式会社日本触媒 Acrylic polymer and method for producing the same
JP6795753B2 (en) * 2015-10-30 2020-12-02 Jsr株式会社 Resin material for forming a cured film, method for forming a cured film, cured film, semiconductor element and display element
JP6573545B2 (en) * 2015-12-21 2019-09-11 富士フイルム株式会社 Positive photosensitive transfer material and method of manufacturing circuit wiring
JP6588354B2 (en) * 2016-01-29 2019-10-09 富士フイルム株式会社 Photosensitive resin composition, cured film, liquid crystal display device, organic electroluminescence display device, and method for producing cured film
JP2017173741A (en) * 2016-03-25 2017-09-28 アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ Photosensitive siloxane composition
KR101805305B1 (en) * 2016-06-03 2017-12-05 주식회사 아이에스엠 Photo-sensitive resin composition for an insulating layer pattern
WO2018096616A1 (en) * 2016-11-24 2018-05-31 日立化成株式会社 Photosensitive resin composition, photosensitive element, protective film, and touch panel
TWI681253B (en) * 2016-12-27 2020-01-01 奇美實業股份有限公司 Chemically-amplified type positive photo sensitive resin composition, method for manufacturing substrate with casting mold, and method for manufacturing plating molded article
TWI685714B (en) * 2016-12-27 2020-02-21 奇美實業股份有限公司 Chemically-amplified type positive photo sensitive resin composition, method for manufacturing substrate with casting mold, and method for manufacturing plating molded article
KR102517695B1 (en) * 2017-01-20 2023-04-03 제이에스알 가부시끼가이샤 Photosensitive composition, cured film and method for producing same, display device, light emitting element, and light receiving element
JP6853057B2 (en) * 2017-01-31 2021-03-31 東京応化工業株式会社 Polymerizable composition, method for producing cured film, and cured film
JP7069557B2 (en) * 2017-03-31 2022-05-18 Ｈｄマイクロシステムズ株式会社 Photosensitive resin composition, manufacturing method of pattern cured product, cured product, interlayer insulating film, cover coat layer, surface protective film, and electronic components.
JP6984539B2 (en) * 2018-05-21 2021-12-22 信越化学工業株式会社 Photosensitive resin composition, pattern forming method, and manufacturing method of optical semiconductor device
JP7447605B2 (en) 2020-03-25 2024-03-12 日油株式会社 Color filter comprising thermosetting resin composition and cured film thereof
JP7397419B1 (en) * 2023-06-02 2023-12-13 Jsr株式会社 Radiation sensitive composition, cured film and method for producing the same, semiconductor element and display element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101226329A (en) * 2007-01-18 2008-07-23 Jsr株式会社 Radiation sensitive resin composition, laminated insulating film, micro lens and preparation method thereof
JP2012083387A (en) * 2010-10-06 2012-04-26 Fujifilm Corp Photosensitive composition, pattern forming material, as well as photosensitive film using the same, pattern forming method, pattern film, low refractive index film, antireflection film, optical device and solid state imaging element
JP2012159830A (en) * 2011-01-12 2012-08-23 Fujifilm Corp Positive photosensitive resin composition, method for forming cured film, cured film, organic el display device and liquid crystal display device
US8513350B2 (en) * 2007-02-28 2013-08-20 Jnc Corporation Positive type photosensitive resin composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006337567A (en) * 2005-05-31 2006-12-14 Sekisui Chem Co Ltd Photocuring resin composition for photoresist, column spacer, and liquid crystal display element
JP5115205B2 (en) * 2008-01-15 2013-01-09 Ｊｎｃ株式会社 Positive photosensitive polymer composition
JP2009169343A (en) * 2008-01-21 2009-07-30 Toray Ind Inc Photosensitive composition, cured film formed thereof, and element having cured film
JP5538039B2 (en) * 2009-05-01 2014-07-02 富士フイルム株式会社 Positive photosensitive resin composition and cured film forming method using the same
WO2011136073A1 (en) * 2010-04-28 2011-11-03 Jsr株式会社 Positive radiation-sensitive composition, interlayer insulating film for display element, and formation method for same
JP2013064973A (en) * 2011-08-26 2013-04-11 Toppan Printing Co Ltd Photosensitive resin composition, material for touch panel, touch panel protective film, touch panel insulating film, and touch panel
JP2013160825A (en) * 2012-02-02 2013-08-19 Sumitomo Chemical Co Ltd Photosensitive resin composition
JP2013210558A (en) * 2012-03-30 2013-10-10 Fujifilm Corp Chemically amplified positive photosensitive resin composition, method for producing cured film, cured film, organic el display device, and liquid crystal display device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101226329A (en) * 2007-01-18 2008-07-23 Jsr株式会社 Radiation sensitive resin composition, laminated insulating film, micro lens and preparation method thereof
US8513350B2 (en) * 2007-02-28 2013-08-20 Jnc Corporation Positive type photosensitive resin composition
JP2012083387A (en) * 2010-10-06 2012-04-26 Fujifilm Corp Photosensitive composition, pattern forming material, as well as photosensitive film using the same, pattern forming method, pattern film, low refractive index film, antireflection film, optical device and solid state imaging element
JP2012159830A (en) * 2011-01-12 2012-08-23 Fujifilm Corp Positive photosensitive resin composition, method for forming cured film, cured film, organic el display device and liquid crystal display device

Also Published As

Publication number Publication date
JPWO2015037695A1 (en) 2017-03-02
TW201518862A (en) 2015-05-16
CN105531627A (en) 2016-04-27
JP6182612B2 (en) 2017-08-16
WO2015037695A1 (en) 2015-03-19

Similar Documents

Publication Publication Date Title
CN105531627B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN105579908B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN105324718B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN104254805B (en) Chemical amplification positive photosensitive polymer combination, cured film and its manufacture method, organic EL display and liquid crystal display device
CN105683838B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN105895661B (en) The manufacturing method and its application of thin film transistor base plate
CN106324986A (en) A photosensitive resin composition, a method for producing a cured film, a cured film, and a liquid crystal display device
CN104395826B (en) Photosensitive polymer combination, cured film and its manufacturing method, organic EL display device, liquid crystal display device and composition
JP6082473B2 (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, and organic EL display device
CN104541202B (en) Resin combination, cured film, object and its preparation method and display device with pattern
WO2014080838A1 (en) Photosensitive resin composition, method for producing cured film, cured film, organic el display device, and liquid crystal display device
CN104995560A (en) Photosensitive resin composition, production method for cured film using same, cured film, liquid crystal display device, and organic EL display device
CN104508554B (en) Photosensitive polymer combination, cured film and its manufacturing method, organic EL display device, liquid crystal display device and compound
CN103293858A (en) Photo-curable resin composition, method for manufacturing cured film, cured film, organic el device and liquid crystal display
JP2014197155A (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic electroluminescence (el) display device
CN104662474B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, organic EL display device and liquid crystal display device
CN104272188A (en) Photosensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid-crystal display device
CN104756010B (en) Photosensitive polymer combination, hardening thing and its manufacturing method, resin pattern manufacturing method, cured film and its application
CN106200263A (en) Photosensitive polymer combination, cured film and its manufacture method, liquid crystal indicator, organic electroluminescence display device and method of manufacturing same and touch screen
CN105917274B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
KR101747771B1 (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device
WO2015033880A1 (en) Resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device
CN106687865A (en) Method for manufacturing TFT substrate, organic EL display device, method for manufacturing organic EL display device, liquid crystal display device, and method for manufacturing liquid crystal display device
WO2013191155A1 (en) Photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device, and liquid crystal display device
CN105051608A (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230407

Address after: Tokyo, Japan

Patentee after: JSR Corp.

Address before: Japan Tokyo port West linen 2, Ding Mu 26, No. 30

Patentee before: FUJIFILM Corp.