CN105531627A - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device - Google Patents

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

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Publication number
CN105531627A
CN105531627A CN201480049945.0A CN201480049945A CN105531627A CN 105531627 A CN105531627 A CN 105531627A CN 201480049945 A CN201480049945 A CN 201480049945A CN 105531627 A CN105531627 A CN 105531627A
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structural unit
group
polymkeric substance
photosensitive polymer
polymer combination
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CN201480049945.0A
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CN105531627B (en
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米泽裕之
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JSR Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—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

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided are: a photosensitive resin composition which exhibits good adhesion; a method for producing a cured film; a cured film; a liquid crystal display device; and an organic EL display device. A photosensitive resin composition which contains (A-1) a polymer component containing a polymer that falls under the category of (1) and/or (2) described below, (B-1) a photoacid generator, (C-1) a solvent and (S) a polymer containing a constituent unit having a partial structure represented by general formula (1) and a constituent unit having at least one group (X) that is selected from the group consisting of an epoxy group, a mercapto group, a (meth)acryloyl group, a vinyl group and an amino group. (1) a polymer having (a1-1) a constituent unit having a group wherein an acid group is protected by an acid-decomposable group and (a1-2) a constituent unit having a crosslinkable group (2) a polymer having (a1-1) a constituent unit having a group wherein an acid group is protected by an acid-decomposable group and a polymer having (a1-2) a constituent unit having a crosslinkable group

Description

The manufacture method of photosensitive polymer combination, cured film, cured film, liquid crystal indicator and organic EL display
Technical field
The present invention relates to a kind of photosensitive polymer combination (below sometimes referred to as " composition of the present invention ").In addition, the present invention relates to a kind of various image display devices using the manufacture method of the cured film of described photosensitive polymer combination, the cured film that photosensitive composite is hardened, use described cured film.
More specifically, the present invention relates to one be suitable for being formed the photosensitive polymer combination of the planarization film of the electronic component such as liquid crystal indicator, organic electroluminescent (organic EL (Electroluminescence)) display device, integrated circuit component, solid-state imager, diaphragm or interlayer dielectric and use its manufacture method of cured film.
Background technology
In thin film transistor (TFT) (being denoted as below " TFT (ThinFilmTransistor) ") electronic component such as type liquid crystal display cells or magnetic head element, integrated circuit component, solid-state imager, generally for insulation between the distribution that makes to configure with stratiform and be provided with interlayer dielectric.The material that forms interlayer dielectric is preferably few in order to the number of steps that obtains necessary pattern form and has sufficient flatness, therefore widely uses photosensitive polymer combination (such as with reference to patent documentation 1 and patent documentation 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2011-221494 publication
Patent documentation 2: Japanese Patent Laid-Open 2008-286936 publication
Summary of the invention
The problem that invention will solve
Moreover, in order to ensure the coating of photosensitive polymer combination, suppress to infiltrate the stripping to film caused between substrate and photosensitive polymer combination layer (resist) when developing by developer solution, sometimes hexamethyldisilazane (Hexamethyldisilazane is implemented to substrate, HMDS) process waits hydrophobization process, if but carry out described HMDS process, then the hydroxyl of substrate surface tails off, the function of the silane coupling agent (adhesive agent) using siloxane as abutment reduces, and the adherence of substrate and resist reduces sometimes.
On the other hand, in recent years, in flexible element (flexibledevice) purposes, require to improve adherence further.Therefore, present situation is the good photosensitive polymer combination of demand adherence.
The present invention solves described problem, and its object is to provide a kind of photosensitive polymer combination good with the adherence of substrate.
The technological means of dealing with problems
The present inventor has carried out making great efforts research according to described situation, found that, by allocating following polymkeric substance in photosensitive polymer combination, described problem can be solved, thus complete the present invention, described polymkeric substance contains the structural unit with siloxane position and the structural unit with the group (X) crosslinked with resist, and containing multiple each structural unit.
Specifically, described problem is solved by following solution <1>, preferably solution <2> ~ solution <15>.
<1> photosensitive polymer combination, contains:
(A-1) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a1-1), there is the polymkeric substance that the structural unit of the group that acidic group is protected through sour decomposability base and (a1-2) have the structural unit of bridging property base,
(2) containing (a1-1), there is the polymkeric substance of the structural unit of the group that acidic group is protected through sour decomposability base and there is containing (a1-2) polymkeric substance of the structural unit of bridging property base;
(B-1) light acid producing agent;
(C-1) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino;
General formula (1)
[changing 1]
In general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.
<2> photosensitive polymer combination, contains:
(A-2) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a2-1), there is the polymkeric substance that the structural unit of acidic group and (a2-2) have the structural unit of bridging property base,
(2) containing (a2-1), there is the polymkeric substance of the structural unit of acidic group and there is containing (a2-2) polymkeric substance of the structural unit of bridging property base;
(B-2) quinone di-azido compound;
(C-2) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino;
General formula (1)
[changing 2]
In general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.
<3> photosensitive polymer combination, contains:
(A-3) polymerizable monomer;
(B-3) Photoepolymerizationinitiater initiater;
(A-4) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a4-1), there is the polymkeric substance that the structural unit of acidic group and (a4-2) have the structural unit of bridging property base,
(2) containing (a4-1), there is the polymkeric substance of the structural unit of acidic group and there is containing (a4-2) polymkeric substance of the structural unit of bridging property base;
(C-3) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino;
General formula (1)
[changing 3]
In general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.
The photosensitive polymer combination that <4> is described any one of <1> to <3>, wherein group (X) is for being selected from least one in the cohort that is made up of epoxy radicals, sulfydryl and (methyl) acryloyl group.
The photosensitive polymer combination that <5> is described any one of <1> to <3>, wherein group (X) is epoxy radicals.
The photosensitive polymer combination that <6> is described any one of <1> to <5>, wherein (S) polymkeric substance contains the structural unit represented by following general formula (I) and the structural unit represented by following general formula (II);
General formula (I) general formula (II)
[changing 4]
In general formula (I), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2; R 3and R 4separately represent hydrogen atom or methyl;
In general formula (II), R 5represent epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl or amino, L 1and L 2separately the atomicity of expression singly-bound or linking part is the concatenating group of 1 ~ 6.
The photosensitive polymer combination of <7> described in <6>, the L in its formula of (I) 1and L 2separately represent that the atomicity of linking part is the concatenating group of 2 ~ 6.
The photosensitive polymer combination that <8> is described any one of <1> to <7>, wherein relative to total solid composition, the allotment amount of (S) polymkeric substance is 0.1 quality % ~ 10 quality %.
The photosensitive polymer combination that <9> is described any one of <1> to <8>, wherein the weight average molecular weight of (S) polymkeric substance is more than 800.
The photosensitive polymer combination that <10> is described any one of <1> to <9>, wherein has bridging property base in the structural unit of bridging property base for being selected from by epoxy radicals, oxetanylmethoxy and-NH-CH 2at least one in the cohort that group represented by-O-R forms; Wherein, R represents the alkyl of hydrogen atom or carbon number 1 ~ 20.
The photosensitive polymer combination that <11> is described any one of <1>, <4> ~ <10>, wherein (B-1) light acid producing agent is oxime sulfonate compounds and/or salt compound.
The manufacture method of a <12> cured film, is characterized in that comprising:
(1) photosensitive polymer combination described any one of <1> to <11> is coated the step on substrate;
(2) in the photosensitive polymer combination be coated with, remove the step of solvent;
(3) step utilizing active radioactive ray to expose the resin combination eliminating solvent;
(4) step that aqueous developer solution is developed to the resin combination through exposure is utilized; And
(5) baking procedure after thermmohardening is carried out to the resin combination through development.
<13> cured film, it is that photosensitive polymer combination sclerosis described any one of <1> to <11> is formed.
The cured film of <14> described in <13>, it is interlayer dielectric.
<15> liquid crystal indicator or organic EL display, have the cured film described in <13> or <14>.
The effect of invention
According to the present invention, the photosensitive polymer combination that a kind of adherence is good can be provided.
Accompanying drawing explanation
Fig. 1 represents the formation concept map of an example of organic EL display.It represents the schematic cross sectional view of the substrate in the organic EL display of bottom-emission (bottomemission) type, has planarization film 4.
Fig. 2 represents the formation concept map of an example of liquid crystal indicator.It represents the schematic cross sectional view of the active-matrix substrate in liquid crystal indicator, has the cured film 17 as interlayer dielectric.
Embodiment
Below, content of the present invention is described in detail.The explanation of the constitutive requirements below recorded is carry out according to representative example of the present invention sometimes, but the present invention is not limited to this kind of example.In addition, in present specification, " ~ " to comprise before and after it described numerical value to use as the connotation of lower limit and higher limit.
In the statement of group (atomic group) in this manual, do not record the statement being substituted and being unsubstituted and comprise not there is substituent group (atomic group), and comprise yet there is substituent group (atomic group).Such as so-called " alkyl ", not only comprises and does not have substituent alkyl (alkyl be unsubstituted), and comprises and have substituent alkyl (alkyl be substituted).
Moreover; in this instructions; " (methyl) acrylate " represents acrylate and methacrylate, and " (methyl) acrylic acid " represents acrylic acid and methacrylic acid, and " (methyl) acryloyl group " represents acryloyl group and methacryl.
Composition of the present invention contains component of polymer, solvent and (S) described later polymkeric substance, such as by photosensitive polymer combination is coated on substrate, by removal of solvents, actinic ray is utilized to expose, aqueous developer solution (being preferably alkaline developer) is utilized to develop, and carry out thermmohardening, and make cured film.
Composition of the present invention contains (S) polymkeric substance, and (S) polymkeric substance contains the structural unit with siloxane position and the structural unit with set group (X).Can think, (S) at least one group (X) in polymkeric substance is tied with the bridging property base key in component of polymer (A-1), component of polymer (A-2) and component of polymer (A-4), and the hydroxyl bond of a siloxane position in (S) polymkeric substance and substrate, the adherence of substrate and resist improves thus.Namely, can think, (S) polymkeric substance has multiple siloxane position, even if therefore the number of the hydroxyl of substrate surface is few, (S) siloxane in polymkeric substance and the hydroxyl of substrate be easy bond also, similarly, group (X) and the easy bond of bridging property base in component of polymer (A-1), component of polymer (A-2) and component of polymer (A-4), can improve adherence thus.
And then, because (S) polymkeric substance has siloxane position, therefore there is the effect promoting baking.As a result, cross-linking density when photosensitive polymer combination is hardened improves, and also has the effect that ease gas (outgas) property improves and cone angle improves.In addition, because siloxane bond is heat-resisting, therefore also has the effect that bond power improves.
Below, with the order of the 1st form ~ the 3rd form, composition of the present invention is illustrated.1st form of composition of the present invention and the 2nd form preferably can be used as the photosensitive polymer combination of eurymeric.3rd form of composition of the present invention preferably can be used as the photosensitive polymer combination of minus.
[the 1st form of the present invention]
The feature of composition of the present invention is to contain:
(A-1) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a1-1), there is the polymkeric substance that the structural unit of the group that acidic group is protected through sour decomposability base and (a1-2) have the structural unit of bridging property base,
(2) containing (a1-1), there is the polymkeric substance of the structural unit of the group that acidic group is protected through sour decomposability base and there is containing (a1-2) polymkeric substance of the structural unit of bridging property base;
(B-1) light acid producing agent;
(C-1) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino.
General formula (1)
[changing 5]
(in general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.)
Below, the 1st form of composition of the present invention is described in detail.
< (A-1) component of polymer >
Composition of the present invention contains at least one of following polymkeric substance as component of polymer: have the structural unit of the group that acidic group protect through sour decomposability base containing (a1-1) and (a1-2) has the polymkeric substance (1) of the structural unit of bridging property base and have the polymkeric substance of the structural unit of the group that acidic group is protected through sour decomposability base containing (a1-1) and contain the polymkeric substance (2) that (a1-2) has the structural unit of bridging property base.And then, also can containing the polymkeric substance beyond these.(A-1) of the present invention component of polymer as long as no special instructions, then refers to except described polymkeric substance (1) and/or described polymkeric substance (2), contains optionally and other polymkeric substance of interpolation.
Comprise (2) containing (a1-1) have the structural unit of the group that acidic group protect through sour decomposability base polymkeric substance and contain (a1-2) there is the situation of the polymkeric substance of the structural unit of bridging property base time; the polymkeric substance containing (a1-1) with the structural unit of the group that acidic group is protected through sour decomposability base is preferably 95: 5 ~ 5: 95 with the ratio containing (a1-2) with the polymkeric substance of the structural unit of bridging property base; be more preferably 80: 20 ~ 20: 80, and then be preferably 70: 30 ~ 30: 70.
(A-1) component of polymer is preferably the resin of addition polymerization type, is more preferably the polymkeric substance containing the structural unit deriving from (methyl) acrylic acid and/or its ester.Moreover, also can derive from cinnamic structural unit containing the structural unit beyond the structural unit deriving from (methyl) acrylic acid and/or its ester, such as or derive from the structural unit etc. of vinyl compound.Moreover, " structural unit of (methyl) acrylic acid and/or its ester will be derived from " also referred to as " acrylic acid series structural unit ".
<< (a1-1) has the structural unit >> of the group that acidic group is protected through sour decomposability base
(A-1) component of polymer is at least containing the structural unit (a1-1) with the group that acidic group is protected through sour decomposability base.Contain structural unit (a1-1) by (A-1) component of polymer, can be made into the photosensitive polymer combination that sensitivity is high.
" group that acidic group is protected through sour decomposability base " in the present invention can be used as acidic group and sour decomposability base and known group, is not particularly limited.
Concrete acidic group can preferably enumerate carboxyl and phenolic hydroxyl group.
In addition, concrete sour decomposability base can use: relatively held labile group acetal system functional groups such as () such as ester structure described later, oxinane ester group or tetrahydrofuran ester groups or relative difficult is decomposed by acid group carbonic acid three grades of alkyl ester groups such as () such as three grades of alkyl such as tert-butyl ester base, t-butyl carbonate bases by acid.
Structural unit (a1-1) preferably has the structural unit of the protection carboxyl protected through sour decomposability base or has the structural unit of the protection phenolic hydroxyl group through sour decomposability base protection.
Below, sequentially the structural unit (a1-1-1) and the structural unit (a1-1-2) had through the protection phenolic hydroxyl group of sour decomposability base protection with the protection carboxyl protected through sour decomposability base are illustrated respectively.
<<< (a1-1-1) has the structural unit >>> of the protection carboxyl through sour decomposability base protection
The sour decomposability base described in detail will be had the structural unit of the protection carboxyl of the carboxy protective of the structural unit of carboxyl for having by following by structural unit (a1-1-1).
There is no particular restriction to can be used for having described in described structural unit (a1-1-1) structural unit of carboxyl, can use known structural unit.Include, for example: derive from the structural unit (a1-1-1-1) in unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular with the unsaturated carboxylic acid of at least one carboxyl etc.
Below, the structural unit (a1-1-1-1) described in being used as with the structural unit of carboxyl is illustrated.
<<<< (a1-1-1-1) derives from molecule the structural unit >>>GreatT.Grea T.GT of the unsaturated carboxylic acid with at least one carboxyl etc.
Unsaturated carboxylic acid used in the present invention can use following cited such unsaturated carboxylic acid.
That is, unsaturated monocarboxylic include, for example: 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) acryloyl-oxyethyl-phthalic acid etc.
In addition, unsaturated dicarboxylic include, for example: 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 also can be its acid anhydrides.Specifically can enumerate: maleic anhydride, itaconic anhydride, citraconic anhydride etc.In addition, unsaturated polybasic carboxylic acid also can be list (2-methacryloxyalkyl) ester of polybasic carboxylic acid, include, for example: mono succinate (2-acryloyl-oxyethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloyl-oxyethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.And then unsaturated polybasic carboxylic acid also can be list (methyl) acrylate of its two ends dicarboxyl polymkeric substance, include, for example: ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc.In addition, unsaturated carboxylic acid also can use: acrylic acid-2-carboxyethyl, methacrylic acid-2-carboxyethyl, maleic acid mono alkyl ester, monoalkyl esters, 4-carboxyl styrene etc.
Wherein, with regard to the viewpoint of developability, in order to form described structural unit (a1-1-1-1), preferably use the acid anhydrides etc. of acrylic acid, methacrylic acid, 2-(methyl) acryloyl-oxyethyl-succinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl-phthalic acid or unsaturated polybasic carboxylic acid, be more preferably and use acrylic acid, methacrylic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid.
Structural unit (a1-1-1-1) can be made up of a kind of separately, also can be made up of two or more.
<<<< can be used for the sour decomposability base >>>GreatT.Grea T.GT of structural unit (a1-1-1)
The described sour decomposability base that can be used for structural unit (a1-1-1) can use sour decomposability base mentioned above.
In these sour decomposability bases, preferably there is the group of the structure protecting sour decomposability base with the form of acetal.Such as, with regard to the viewpoint of the basic physical properties of photosensitive polymer combination, particularly sensitivity or pattern form, the formative of contact hole, the storage stability of photosensitive polymer combination, be preferably with the protection carboxyl of the form of acetal protection carboxyl.And then, with regard to the viewpoint of sensitivity, be more preferably the protection carboxyl protecting carboxyl with the form of acetal represented by following general formula (a1-10).Moreover, represented by following general formula (a1-10) with the situation of protection carboxyl of the form of acetal protection carboxyl time, protection carboxyl totally becomes-(C=O)-O-CR 101r 102(OR 103) structure.
General formula (a1-10)
[changing 6]
(in formula (a1-10), R 101and R 102separately represent hydrogen atom or alkyl, wherein, by R 101with R 102except the situation being hydrogen atom.R 103represent alkyl.R 101or R 102with R 103also can link and form cyclic ether.)
In described general formula (a1-10), R 101~ R 103separately represent hydrogen atom or alkyl, described alkyl can be straight-chain, branch's chain, ring-type any one.Herein, R 101and R 102two represent that the situation of hydrogen atom does not exist, R 101and R 102at least one represent alkyl.
The alkyl of described straight-chain or branch's chain is preferably carbon number 1 ~ 12, is more preferably carbon number 1 ~ 6, and then is preferably carbon number 1 ~ 4.Specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.
In described general formula (a1-10), R 101~ R 103separately represent hydrogen atom or alkyl.Described alkyl can be straight-chain, branch's chain, ring-type any one.Herein, R 101and R 102two represent that the situation of hydrogen atom does not exist, R 101and R 102at least one represent alkyl.
The alkyl of described straight-chain or branch's chain is preferably carbon number 1 ~ 12, is more preferably carbon number 1 ~ 6, and then is preferably carbon number 1 ~ 4.Specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.
Described cyclic alkyl is preferably carbon number 3 ~ 12, is more preferably carbon number 4 ~ 8, and then is preferably carbon number 4 ~ 6.Described cyclic alkyl include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc.
Described alkyl also can have substituting group, and substituting group can illustrate halogen atom, aryl, alkoxy.When having the situation of halogen atom alternatively base, R 101, R 102, R 103become haloalkyl, when having the situation of aryl alternatively base, R 101, R 102, R 103become aralkyl.
Described halogen atom can illustrate: fluorine atom, chlorine atom, bromine atoms, atomic iodine, in these, is preferably fluorine atom or chlorine atom.
In addition, described aryl is preferably the aryl of carbon number 6 ~ 20, be more preferably carbon number 6 ~ 12, specifically can illustrate phenyl, Alpha-Methyl phenyl, naphthyl etc., through aryl replace alkyl totally, namely aralkyl can illustrate: benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc.
Described alkoxy is preferably the alkoxy of carbon number 1 ~ 6, is more preferably carbon number 1 ~ 4, and then is preferably methoxy or ethoxy.
In addition, when described alkyl is the situation of naphthenic base, described naphthenic base also can have the straight-chain of carbon number 1 ~ 10 or the alkyl alternatively base of branch's chain, when alkyl is the situation of the alkyl of straight-chain or branch's chain, also can have the naphthenic base alternatively base of carbon number 3 ~ 12.
These substituting groups also can replace through described substituting group further.
In described general formula (a1-10), at R 101, R 102and R 103when representing the situation of aryl, described aryl is preferably carbon number 6 ~ 12, is more preferably carbon number 6 ~ 10.Described aryl also can have substituting group, and described substituting group preferably can illustrate the alkyl of carbon number 1 ~ 6.Aryl such as can illustrate: phenyl, tolyl, xylyl, cumenyl, 1-naphthyl etc.
In addition, R 101, R 102and R 103can bond form ring together with the carbon atom of these bonds mutually.R 101with R 102, R 101with R 103or R 102with R 103the ring structure of the situation of bond include, for example: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.
Moreover, in described general formula (a1-10), be preferably R 101and R 102any one be hydrogen atom or methyl.
Free radical polymerization monomer for the formation of the structural unit containing the protection carboxyl represented by described general formula (a1-10) can use commercially available product, also can use and utilize known method to synthesize.The synthetic method etc. recorded in the numbered paragraphs 0037 ~ numbered paragraphs 0040 of Japanese Patent Laid-Open 2011-221494 publication such as can be utilized to synthesize, its content is incorporated in present specification.
The structural unit of the first preferred configuration represented by following general formula (A2 ') of described structural unit (a1-1-1).
[changing 7]
(in formula (A2 '), R 1and R 2represent hydrogen atom, alkyl or aryl respectively, at least R 1and R 2any one represent alkyl or aryl, R 3represent alkyl or aryl, R 1or R 2with R 3also can link and form cyclic ether, R 4represent hydrogen atom or methyl, X represents singly-bound or arlydene.)
At R 1and R 2during situation for alkyl, being preferably carbon number is the alkyl of 1 ~ 10.At R 1and R 2during situation for aryl, be preferably phenyl.R 1and R 2be preferably the alkyl of hydrogen atom or carbon number 1 ~ 4 respectively.
R 3represent alkyl or aryl, be preferably the alkyl of carbon number 1 ~ 10, be more preferably the alkyl of 1 ~ 6.
X represents singly-bound or arlydene, is preferably singly-bound.
The structural unit of the second preferred configuration represented by following general formula (1-12) of described structural unit (a1-1-1).
General formula (1-12)
[changing 8]
(in formula (1-12), R 121represent the alkyl of hydrogen atom or carbon number 1 ~ 4, L 1represent carbonyl or phenylene, R 122~ R 128separately represent the alkyl of hydrogen atom or carbon number 1 ~ 4.)
R 121be preferably hydrogen atom or methyl.
L 1be preferably carbonyl.
R 122~ R 128be preferably hydrogen atom.
The preferred concrete example of described structural unit (a1-1-1) can illustrate following structural unit.Moreover in following structural unit, R represents hydrogen atom or methyl.
[changing 9]
<<< (a1-1-2) has the structural unit >>> of the protection phenolic hydroxyl group through sour decomposability base protection
Structural unit (a1-1-2) is for having by the structural unit (a1-1-2-1) of the following protection phenolic hydroxyl group protected by the structural unit with phenolic hydroxyl group by the sour decomposability base described in detail.
<<<< (a1-1-2-1) has the structural unit >>>GreatT.Grea T.GT of phenolic hydroxyl group
The described structural unit with phenolic hydroxyl group can enumerate the structural unit in hydroxy styrenes architecture unit or novolaks system resin, in these, with regard to the viewpoint of sensitivity, preferably derives from the structural unit of hydroxy styrenes or Alpha-Methyl hydroxy styrenes.In addition, with regard to the viewpoint of sensitivity, there is the structural unit of structural unit also preferably represented by following general formula (a1-20) of phenolic hydroxyl group.
General formula (a1-20)
[changing 10]
(in general formula (a1-20), R 220represent hydrogen atom or methyl, R 221represent singly-bound or bivalence linking base, R 222represent halogen atom or the straight chain of carbon number 1 ~ 5 or the alkyl of branch's chain, a represents the integer of 1 ~ 5, and b represents the integer of 0 ~ 4, and a+b is less than 5.Moreover, at the R of existence more than 2 222situation time, these R 222can different also can be identical.)
In described general formula (a1-20), R 220represent hydrogen atom or methyl, be preferably methyl.
In addition, R 221represent singly-bound or bivalence linking base.When the situation for singly-bound, can sensitivity be improved, and then the transparency of cured film can be improved, therefore preferably.R 221bivalence linking base can illustrate alkylidene, R 221for the concrete example of alkylidene can be enumerated: methylene, ethylidene, propylidene, isopropylidene, sub-normal-butyl, isobutylidene, the sub-tert-butyl group, pentylidene, isoamylidene, sub-neopentyl, hexylidene etc.Wherein, R 221be preferably singly-bound, methylene, ethylidene.In addition, described bivalence linking base also can have substituting group, and substituting group can enumerate halogen atom, hydroxyl, alkoxy etc.In addition, a represents the integer of 1 ~ 5, and with regard to the viewpoint of effect of the present invention or aspect easy to manufacture, a is preferably 1 or 2, and being more preferably a is 1.
In addition, about the binding site of the hydroxyl on phenyl ring, with R 221when the carbon atom of bond is benchmark (1), be preferably binding on 4.
R 222for halogen atom or the straight chain of carbon number 1 ~ 5 or the alkyl of branch's chain.Specifically can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl etc.Wherein, with regard to aspect easy to manufacture, be preferably chlorine atom, bromine atoms, methyl or ethyl.
In addition, b represents the integer of 0 or 1 ~ 4.
<<<< can be used for the sour decomposability base >>>GreatT.Grea T.GT of structural unit (a1-1-2)
The described sour decomposability base that can be used for described structural unit (a1-1-2) can use known group in the same manner as the sour decomposability base that can be used for described structural unit (a1-1-1), is not particularly limited.In acid decomposability base; with regard to the viewpoint of the basic physical properties of photosensitive polymer combination, particularly sensitivity or pattern form, the storage stability of photosensitive polymer combination, the formative of contact hole, preferably there is the structural unit of the protection phenolic hydroxyl group through acetal protection.And then, in sour decomposability base, with regard to the viewpoint of sensitivity, be more preferably the protection phenolic hydroxyl group protecting phenolic hydroxyl group with the form of acetal represented by described general formula (a1-10).Moreover, represented by described general formula (a1-10) with the situation of protection phenolic hydroxyl group of the form of acetal protection phenolic hydroxyl group time, protection phenolic hydroxyl group totally becomes-Ar-O-CR 101r 102(OR 103) structure.Moreover Ar represents arlydene.
The preference of the acetal ester structure of phenolic hydroxyl group can illustrate: R 101=R 102=R 103=methyl or R 101=R 102=methyl and R 103the combination of=benzyl.
In addition, record in the numbered paragraphs 0042 of Japanese Patent Laid-Open 2011-215590 publication for the formation of having to include, for example with the free radical polymerization monomer of structural unit of the protection phenolic hydroxyl group of the form of acetal protection phenolic hydroxyl group.
In these, with regard to the viewpoint of the transparency, be preferably the 1-alkoxyalkyl protective of methacrylic acid-4-hydroxylphenyl ester, the THP trtrahydropyranyl protective of methacrylic acid-4-hydroxylphenyl ester.
The concrete example of the acetal protecting group of phenolic hydroxyl group can enumerate 1-alkoxyalkyl; include, for example: 1-ethoxyethyl group, 1-methoxy ethyl, 1-n-butoxyethyl, 1-isobutoxyethy, 1-(2-chloroethoxy) ethyl, 1-(2-ethyl hexyl oxy) ethyl, 1-positive propoxy ethyl, 1-cyclohexyloxy ethyl, 1-(2-cyclohexylethoxy radical) ethyl, 1-Benzyloxyethyl etc., these can be used alone or combinationally use two or more.
Free radical polymerization monomer for the formation of described structural unit (a1-1-2) can use commercially available product, also can use and utilize synthesized by known method.Such as, by making the compound with phenolic hydroxyl group react to synthesize with vinyl ether in the presence of acid catalyst.Described synthesis also can make to have the monomer of phenolic hydroxyl group and other monomers carry out copolymerization in advance, reacts in the presence of acid catalyst thereafter with vinyl ether.
The preferred concrete example of described structural unit (a1-1-2) can illustrate following structural unit, but the present invention is not limited to these structural units.
[changing 11]
[changing 12]
[changing 13]
The preferred configuration >>> of <<< structural unit (a1-1)
When the polymkeric substance containing described structural unit (a1-1) does not contain in fact the situation of structural unit (a1-2), in the polymer, the content of structural unit (a1-1) is preferably 20mol% (molar percentage) ~ 100mol%, is more preferably 30mol% ~ 90mol%.
When the polymkeric substance containing described structural unit (a1-1) contains the situation of structural unit (a1-2), in the polymer, with regard to the viewpoint of sensitivity, the content of single structure unit (a1-1) is preferably 3mol% ~ 70mol%, is more preferably 10mol% ~ 60mol%.In addition, especially the described sour decomposability base that can be used for described structural unit (a1-1) be have with the situation of structural unit of the protection carboxyl of the form of acetal protection carboxyl time, be preferably 20mol% ~ 50mol%.
Described structural unit (a1-1-1), compared with described structural unit (a1-1-2), has feature fast of developing.Therefore, when the situation for rapid development, structural unit (a1-1-1) is preferably.Otherwise make development slowly situation time, preferably use structural unit (a1-1-2).
<< (a1-2) has the structural unit >> of bridging property base
(A-1) component of polymer contains the structural unit (a1-2) with bridging property base.As long as described bridging property base for causing the group of sclerous reaction by heating, is then not particularly limited.The form preferably with the structural unit of bridging property base can be enumerated: containing being selected from by epoxy radicals, oxetanylmethoxy ,-NH-CH 2the structural unit of at least one in the cohort that the group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1 ~ 20) and ethene unsaturated group form, is preferably selected from epoxy radicals, oxetanylmethoxy and-NH-CH 2at least one in group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1 ~ 20).Wherein, photosensitive polymer combination of the present invention is preferably the structural unit that (A-1) component of polymer contains at least one had in epoxy radicals and oxetanylmethoxy.More specifically, following structural unit can be enumerated.
<<< (a1-2-1) has the structural unit >>> of epoxy radicals and/or oxetanylmethoxy
Described (A-1) component of polymer is preferably containing the structural unit (hereinafter also referred to structural unit (a1-2-1)) with epoxy radicals and/or oxetanylmethoxy.
Described structural unit (a1-2-1) as long as have at least one of epoxy radicals or oxetanylmethoxy in a structural unit, the oxetanylmethoxy of the epoxy radicals of more than 1 and the oxetanylmethoxy of more than 1, the epoxy radicals of more than 2 or more than 2 can be had, be not particularly limited, preferably there is epoxy radicals and/or the oxetanylmethoxy of total 1 ~ 3, be more preferably the epoxy radicals and/or oxetanylmethoxy with total 1 or 2, and then preferably there is 1 epoxy radicals or oxetanylmethoxy.
The concrete example of free radical polymerization monomer for the formation of the structural unit with epoxy radicals include, for example: glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3, 4-epoxy butyl ester, methacrylic acid-3, 4-epoxy butyl ester, acrylic acid-3, 4-epoxycyclohexanecarboxylate, methacrylic acid-3, 4-epoxycyclohexanecarboxylate, α-ethylacrylate-3, 4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl ether, between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, the compound etc. containing ester ring type epoxy skeleton recorded in the numbered paragraphs 0031 ~ numbered paragraphs 0035 of Jap.P. No. 4168443 publication, these contents are incorporated in present specification.
The concrete example of free radical polymerization monomer for the formation of the structural unit with oxetanylmethoxy include, for example: that records in the numbered paragraphs 0011 ~ numbered paragraphs 0016 of Japanese Patent Laid-Open 2001-330953 publication has the compound etc. recorded in (methyl) acrylate of oxetanylmethoxy or the numbered paragraphs 0027 of Japanese Patent Laid-Open 2012-088459 publication, these contents is incorporated in present specification.
Be preferably containing the monomer of metacrylic acid ester structure, the monomer containing acrylate structural for the formation of the described concrete example with the free radical polymerization monomer of the structural unit (a1-2-1) of epoxy radicals and/or oxetanylmethoxy.
In these, with regard to improving the viewpoint of the various characteristics of copolymerization and cured film, be preferably glycidyl methacrylate, acrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, acrylic acid (3-Ethyloxetane-3-base) methyl esters and methacrylic acid (3-Ethyloxetane-3-base) methyl esters.These structural units can be used alone one or combinationally use two or more.
The preferred concrete example of described structural unit (a1-2-1) can illustrate following structural unit.Moreover in following structural unit, R represents hydrogen atom or methyl.
[changing 14]
<<< (a1-2-2) has the structural unit >>> of ethene unsaturated group
Described have a kind of of the structural unit (a1-2) of bridging property base and enumerate the structural unit (a1-2-2) with ethene unsaturated group.Described structural unit (a1-2-2) preferably has the structural unit of ethene unsaturated group on side chain, is more preferably and has ethene unsaturated group at end and have the structural unit of the side chain of carbon number 3 ~ 16.
In addition, about structural unit (a1-2-2), the conducts such as the compound recorded in the record of the numbered paragraphs 0072 ~ numbered paragraphs 0090 of Japanese Patent Laid-Open 2011-215580 publication and the numbered paragraphs 0013 ~ numbered paragraphs 0031 of Japanese Patent Laid-Open 2008-256974 can be enumerated preferred, these contents are incorporated in present specification.
<<< (a1-2-3) has-NH-CH 2the structural unit >>> of the group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1 ~ 20)
(A-1) component of polymer used in the present invention also preferably has-NH-CH 2the structural unit (a1-2-3) of the group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1 ~ 20).By containing structural unit (a1-2-3), causing sclerous reaction by heating slowly, the cured film of various excellent can be obtained.Herein, R is preferably the alkyl of carbon number 1 ~ 9, is more preferably the alkyl of carbon number 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, is preferably the alkyl of straight chain or branch.Structural unit (a1-2-3) is more preferably the structural unit of the group had represented by following general formula (a2-30).
General formula (a2-30)
[changing 15]
(in general formula (a2-30), R 1represent hydrogen atom or methyl, R 2represent the alkyl of hydrogen atom or carbon number 1 ~ 20.)
R 2be preferably the alkyl of carbon number 1 ~ 9, be more preferably the alkyl of carbon number 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, is preferably the alkyl of straight chain or branch.
R 2concrete example can enumerate: methyl, ethyl, normal-butyl, isobutyl, cyclohexyl and n-hexyl.Wherein, isobutyl, normal-butyl, methyl is preferably.
<<< has the preferred configuration >>> of the structural unit (a1-2) of bridging property base
When the polymkeric substance containing described structural unit (a1-2) does not contain in fact the situation of structural unit (a1-1), in the polymer, the content of structural unit (a1-2) is preferably 5mol% ~ 90mol%, is more preferably 20mol% ~ 80mol%.
When the polymkeric substance containing described structural unit (a1-2) contains the situation of described structural unit (a1-1), in the polymer, with regard to the viewpoint of chemical-resistant, the content of structural unit (a1-2) is preferably 3mol% ~ 70mol%, is more preferably 10mol% ~ 60mol%.
In the present invention, and then no matter be which form, in all structural units of (A-1) component of polymer, the content of structural unit (a1-2) is all preferably 3mol% ~ 70mol%, is more preferably 10mol% ~ 60mol%.
By being set as, in the scope of described numerical value, the cured film of various excellent can being formed.
<< (a1-3) other structural units >>
In the present invention, (A-1) component of polymer is preferably except containing except described structural unit (a1-1) and/or structural unit (a1-2), at least containing having the structural unit of acidic group as other structural units (a1-3) in addition.Described polymkeric substance (1) and/or polymkeric substance (2) also can contain structural unit (a1-3).In addition, described polymkeric substance (1) or polymkeric substance (2) and another containing the polymkeric substance in fact containing structural unit (a1-1) and structural unit (a1-2) containing other structural units (a1-3) can be also different from.
By containing having the structural unit of acidic group as other structural units (a1-3), the adjustment transfiguration of developability is easy.In addition, be easily dissolved in the developer solution of alkalescence, can more effectively play effect of the present invention.So-called acidic group in the present invention, refers to the proton dissociation base that pKa is less than 7.Acidic group typically uses the monomer that can form acidic group and is set in polymkeric substance with the form of the structural unit containing acidic group.By in the polymer containing the structural unit of this kind containing acidic group, there is the tendency in the developer solution being easily dissolved in alkalescence.
Acidic group used in the present invention can illustrate: the acidic group deriving from carboxylic acid group, the acidic group deriving from sulfoamido, derive from phosphonate group acidic group, derive from sulfonic acidic group, derive from the acidic group of phenolic hydroxyl group, sulfoamido, sulfonyl imide etc., preferably derive from the acidic group of carboxylic acid group and/or derive from the acidic group of phenolic hydroxyl group.
Structural unit containing acidic group used in the present invention is more preferably the structural unit deriving from cinnamic structural unit or derive from vinyl compound, the structural unit deriving from (methyl) acrylic acid and/or its ester.Such as can use the compound recorded in the numbered paragraphs 0021 ~ numbered paragraphs 0023 of Japanese Patent Laid-Open 2012-88459 publication and numbered paragraphs 0029 ~ numbered paragraphs 0044, its content is incorporated in present specification.Wherein, the structural unit of 4-Vinyl phenol, (methyl) acrylic acid, maleic acid, maleic anhydride is preferably derived from.
About the introduction method of the structural unit containing acidic group, can be directed in identical polymkeric substance with (a1-1) structural unit and/or (a1-2) structural unit, also can import with the form of the structural unit of the polymkeric substance different from (a1-1) structural unit and (a1-2) structural unit.
This kind of polymkeric substance preferably has the resin of carboxyl on side chain.Include, for example: as No. 59-44615, Japanese Patent Laid-Open No. Sho, No. 54-34327, Jap.P. examined patent publication, No. 58-12577, Jap.P. examined patent publication, No. 54-25957, Jap.P. examined patent publication, No. 59-53836, Japanese Patent Laid-Open No. Sho, such methacrylic acid copolymer is recorded in each publication of No. 59-71048, Japanese Patent Laid-Open No. Sho, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymers, maleic acid, partial esterification maleic acid etc., and there is at side chain the acid cellulose derivant of carboxyl, on the polymkeric substance with hydroxyl addition acid anhydrides etc., and then also can be set forth on side chain the high molecular polymer with (methyl) acryloyl group as preferably.
Include, for example: (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) 2-hydroxypropyl acrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer recorded in Japanese Patent Laid-Open 7-140654 publication, acrylic acid-2-hydroxyl-3-phenoxy-propyl/polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, methacrylic acid-2-hydroxy methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer, methacrylic acid-2-hydroxy methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc.
In addition, also can use the known macromolecular compound recorded in Japanese Patent Laid-Open 7-207211 publication, Japanese Patent Laid-Open 8-259876 publication, Japanese Patent Laid-Open 10-300922 publication, Japanese Patent Laid-Open 11-140144 publication, Japanese Patent Laid-Open 11-174224 publication, Japanese Patent Laid-Open 2000-56118 publication, Japanese Patent Laid-Open 2003-233179 publication, Japanese Patent Laid-Open 2009-52020 publication etc., these contents are incorporated in present specification.
These polymkeric substance can, only containing a kind of, also can contain two or more.
These polymkeric substance also can use commercially available SMA1000P, SMA2000P, SMA3000P, SMA1440F, SMA17352P, SMA2625P, SMA3840F (being that Cray Willie (CrayValley) company manufactures above), sub-to wind (ARUFON) UC-3000, sub-to wind (ARUFON) UC-3510, sub-to wind (ARUFON) UC-3900, sub-to wind (ARUFON) UC-3910, sub-to wind (ARUFON) UC-3920, sub-to wind (ARUFON) UC-3080 (above for East Asia synthesis (stock) manufactures), Zhuan Keli (Joncryl) 690, Zhuan Keli (Joncryl) 678, Zhuan Keli (Joncryl) 67, Zhuan Keli (Joncryl) 586 (being BASF (BASF) manufacture above) etc.
In the present invention, especially with regard to the viewpoint of sensitivity, be preferably containing carboxylic structural unit.Such as can use the compound recorded in the numbered paragraphs 0021 ~ numbered paragraphs 0023 of Japanese Patent Laid-Open 2012-88459 publication and numbered paragraphs 0029 ~ numbered paragraphs 0044, its content is incorporated in present specification.
Structural unit containing acidic group is preferably the 1mol% ~ 80mol% of the structural unit of all component of polymer, be more preferably 1mol% ~ 50mol%, and then be preferably 5mol% ~ 40mol%, be especially preferably 5mol% ~ 30mol%, be particularly preferably 5mol% ~ 25mol%.
There is no particular restriction to form the described monomer containing the structural unit (a1-3) beyond the structural unit of acidic group, include, for example: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, dicyclo unsaturated compound class, maleimide compound class, unsaturated aromatics, conjugated diolefine based compound, unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.The monomer forming other structural units (a1-3) can be used alone or combinationally use two or more.
Specifically can enumerate: derive from styrene, methyl styrene, hydroxy styrenes, α-methyl styrene, Alpha-Methyl 4-Vinyl phenol, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, vinyl benzoic acid ethyl ester, 4-HBA (3-methacryloxypropyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (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, vinyl cyanide, the structural unit of ethylene glycol single acetyl acetic acid esters list (methyl) acrylate etc.In addition, the compound recorded in the numbered paragraphs 0021 ~ numbered paragraphs 0024 of Japanese Patent Laid-Open 2004-264623 publication can be enumerated.
In addition, with regard to the viewpoint of electrical specification, other structural units (a1-3) are preferably phenylethylene, have the group of aliphatics ring type skeleton.Specifically can enumerate: styrene, methyl styrene, hydroxy styrenes, α-methyl styrene, (methyl) acrylic acid two ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate etc.
And then in addition with regard to the viewpoint of adherence, other structural units (a1-3) are preferably (methyl) alkyl acrylate.Specifically can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate etc., be more preferably (methyl) methyl acrylate.
In addition, component of polymer also can also contain the structural unit of Ju You oxazolinyl as other structural units (a1-3).
Below enumerate the preferred example of component of polymer of the present invention, but the present invention is not limited to these examples.
(the 1st example)
The form of polymkeric substance (1) also containing one kind or two or more other structural units (a1-3).
(the 2nd example)
The form of polymkeric substance also containing one kind or two or more other structural units (a1-3) containing (a1-1) with the structural unit of the group that acidic group is protected through sour decomposability base in polymkeric substance (2).
(the 3rd example)
The form of polymkeric substance also containing one kind or two or more other structural units (a1-3) containing (a1-2) with the structural unit of bridging property base in polymkeric substance (2).
(the 4th example)
Be different from described polymkeric substance (1) or polymkeric substance (2) and form also containing the polymkeric substance in fact containing structural unit (a1-1) and structural unit (a1-2) containing other structural units (a1-3).
(the 5th example)
Comprise the form of the plural combination of described 1st example ~ the 4th example.
In the form containing the polymkeric substance in fact not containing (a1-1) and (a1-2) containing other structural units (a1-3), contain the total amount of the polymkeric substance of (a1-1) and/or (a1-2), be preferably 99: 1 ~ 5: 95 with the part by weight of the total amount of the polymkeric substance in fact containing (a1-1) and (a1-2) containing other structural units (a1-3), be more preferably 97: 3 ~ 30: 70, and then be preferably 95: 5 ~ 50: 50.
Composition of the present invention preferably contains (A-1) component of polymer with the ratio of more than the 70 quality % of the solid constituent of composition.
The molecular weight >> of << (A-1) polymkeric substance
(A-1) molecular weight of polymkeric substance is with polystyrene conversion weight average molecular weight, is preferably 1,000 ~ 200,000, is more preferably 2,000 ~ 50, the scope of 000.If in the scope of described numerical value, then various characteristic is good.The ratio (dispersion degree) of number average molecular weight and weight average molecular weight is preferably 1.0 ~ 5.0 and is more preferably 1.5 ~ 3.5.
(A-1) weight average molecular weight of component of polymer and dispersion degree are defined as the polystyrene conversion value being measured gained by gel permeation chromatography (GelPermeationChromatography, GPC).In this instructions, the weight average molecular weight (Mw) of component of polymer and number average molecular weight (Mn) are such as by using HLC-8120 (eastern Cao (stock) manufacture), (eastern Cao (stock) manufactures to use tsk gel porous HXL-M (TSKgelMultiporeHXL-M), 7.8mmID × 30.0cm is as tubing string, and use tetrahydrofuran (Tetrahydrofuran, THF) to obtain as eluent.
The manufacture method >> of << (A-1) polymkeric substance
In addition, about the synthetic method of (A-1) component of polymer, also known various method, if enumerate an example, then by synthesizing with under type: in organic solvent, use radical polymerization initiator, make at least to be polymerized containing the free radical polymerization monomer potpourri for the formation of the free radical polymerization monomer of the structural unit represented by described (a1-1) and described (a1-3).In addition, also can utilize so-called high molecular weight reactive to synthesize.
In addition, pentaerythrite four (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), α-methylstyrenedimer equimolecular quantity adjusting agent can such as also be used.
(A-1) polymkeric substance is preferably the structural unit deriving from (methyl) acrylic acid and/or its ester relative to all structural units containing more than 50mol%, is more preferably the structural unit deriving from (methyl) acrylic acid and/or its ester containing more than 80mol%.
< (B-1) light acid producing agent >
Photosensitive polymer combination of the present invention contains (B-1) light acid producing agent.The light acid producing agent used in the present invention is preferably the actinic ray and acidic compound of responding to more than wavelength 300nm, preferably wavelength 300nm ~ 450nm, and its chemical constitution is also unrestricted.In addition, about the photoactinic smooth acid producing agent directly not responding to more than wavelength 300nm, as long as responding to the actinic ray of more than wavelength 300nm, acidic compound by also using with sensitizer, then can combine with sensitizer and preferably use.The light acid producing agent used in the present invention is preferably and produces the light acid producing agent that pKa is the acid of less than 4, is more preferably and produces the light acid producing agent that pKa is the acid of less than 3, most preferably be the light acid producing agent of the acid of generation less than 2.
The example of light acid producing agent can be enumerated: trichloromethyl s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc.In these, with regard to the viewpoint of insulativity, preferably use oxime sulfonate compounds.These light acid producing agents can be used alone one or combinationally use two or more.The concrete example of trichloromethyl s-triazine, two fragrant base Iodonium salts, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative can illustrate the compound recorded in the numbered paragraphs 0083 ~ numbered paragraphs 0088 of Japanese Patent Laid-Open 2011-221494 publication, these contents is incorporated in present specification.
Oxime sulfonate compounds, the compound namely with oxime sulfonates structure preferably can illustrate the compound containing the oxime sulfonates structure represented by following general formula (B1-1).
General formula (B1-1)
[changing 16]
(in general formula (B1-1), R 21represent alkyl or aryl.Swash represents the key with other groups.)
In general formula (B1-1), arbitrary group all can be substituted, R 21alkyl can be straight-chain and also can be branch-like and also can be ring-type.Be illustrated to the substituting group of allowing below.
R 21alkyl be preferably straight-chain or the branch-like alkyl of carbon number 1 ~ 10.R 21alkyl can replace through the alkoxy of the aryl of halogen atom, carbon number 6 ~ 11, carbon number 1 ~ 10 or naphthenic base (comprise the bridge linking type alicyclic groups such as 7,7-dimethyl-2-oxo norborny, be preferably bicyclic alkyl etc.).
R 21aryl be preferably the aryl of carbon number 6 ~ 11, be more preferably phenyl or naphthyl.R 21aryl can through low alkyl group, alkoxy or halogen atom replace.
Described compound containing the oxime sulfonates structure represented by described general formula (B1-1) is also preferably the oxime sulfonate compounds represented by following general formula (B1-2).
General formula (B1-2)
[changing 17]
(in formula (B1-2), R 42the alkyl or aryl that expression can be substituted, X represents alkyl, alkoxy or halogen atom, and m4 represents the integer of 0 ~ 3, when m4 is 2 or 3, multiple X can identical also can be different.)
R 42preferable range and described R 21preferable range identical.
Alkyl as X is preferably straight-chain or the branch-like alkyl of carbon number 1 ~ 4.In addition, straight-chain or the branch-like alkoxy of carbon number 1 ~ 4 is preferably as the alkoxy of X.In addition, the halogen atom as X is preferably chlorine atom or fluorine atom.
M4 is preferably 0 or 1.In described general formula (B2), especially preferably m4 is 1, X is methyl, and the position of substitution of X is ortho position, and R 42for straight-chain alkyl, 7,7-dimethyl-2-oxo norborny methyl or the compounds to toluyl groups of carbon number 1 ~ 10.
Compound containing the oxime sulfonates structure represented by described general formula (B1-1) is also preferably the oxime sulfonate compounds represented by following general formula (B1-3).
General formula (B1-3)
[changing 18]
(in formula (B1-3), R 43with the R in formula (B1-2) 42for synonymous, X 1represent the alkoxy of the alkyl of halogen atom, hydroxyl, carbon number 1 ~ 4, carbon number 1 ~ 4, cyano group or nitro, n4 represents the integer of 0 ~ 5.)
R in described general formula (B1-3) 43be preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor n-pro-pyl, perfluoro-n-butyl group, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, be especially preferably n-octyl.
X 1be preferably the alkoxy of carbon number 1 ~ 5, be more preferably methoxyl.
N4 is preferably 0 ~ 2, is especially preferably 0 ~ 1.
The concrete example of the compound represented by described general formula (B1-3) and the concrete example of preferred oxime sulfonate compounds can refer to the record of the numbered paragraphs 0080 ~ numbered paragraphs 0082 of Japanese Patent Laid-Open 2012-163937 publication, its content are incorporated in present specification.
Compound containing the oxime sulfonates structure represented by described general formula (B1-1) is also preferably the compound represented by following general formula (OS-1).
[changing 19]
In described general formula (OS-1), R 101represent hydrogen atom, alkyl, thiazolinyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl, sulfamoyl, sulfo group, cyano group, aryl or heteroaryl.R 102represent alkyl or aryl.
X 101represent-O-,-S-,-NH-,-NR 105-,-CH 2-,-CR 106h-or-CR 1O5r 107-, R 105~ R 107represent alkyl or aryl.
R 121~ R 124separately represent hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxy, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide group, sulfo group, cyano group or aryl.R 121~ R 124in 2 also can mutual bond and form ring respectively.
R 121~ R 124be preferably hydrogen atom, halogen atom and alkyl, in addition, also preferably can enumerate R in addition 121~ R 124in at least two mutual bonds and form the form of aryl.Wherein, with regard to the viewpoint of sensitivity, be preferably R 121~ R 124be the form of hydrogen atom.
Described functional group all can have substituting group further.
Compound represented by described general formula (OS-1) is such as preferably the compound represented by general formula (OS-2) recorded in the numbered paragraphs 0087 ~ numbered paragraphs 0089 of Japanese Patent Laid-Open 2012-163937 publication, its content is incorporated in present specification.
The concrete example that can be preferably used for the compound represented by described general formula (OS-1) of the present invention can enumerate the compound (exemplary compounds b-1 ~ exemplary compounds b-34) recorded in the numbered paragraphs 0128 ~ numbered paragraphs 0132 of Japanese Patent Laid-Open 2011-221494 publication, but the present invention is not limited to this.
In the present invention, the compound containing the oxime sulfonates structure represented by described general formula (B1-1) is preferably the oxime sulfonate compounds represented by following general formula (OS-3), following general formula (OS-4) or following general formula (OS-5).
[changing 20]
(in general formula (OS-3) ~ general formula (OS-5), R 22, R 25and R 28separately represent alkyl, aryl or heteroaryl, R 23, R 26and R 29separately represent hydrogen atom, alkyl, aryl or halogen atom, R 24, R 27and R 30separately represent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X 1~ X 3separately represent oxygen atom or sulphur atom, n 1~ n 3separately represent 1 or 2, m 1~ m 3separately represent the integer of 0 ~ 6.)
About described general formula (OS-3) ~ general formula (OS-5), such as, can refer to the record of the numbered paragraphs 0098 ~ numbered paragraphs 0115 of Japanese Patent Laid-Open 2012-163937 publication, its content is incorporated in present specification.
In addition, compound containing the oxime sulfonates structure represented by described general formula (B1-1) such as be especially preferably Japanese Patent Laid-Open 2012-163937 publication numbered paragraphs 0117 in record general formula (OS-6) ~ general formula (OS-11) any one represented by compound, its content is incorporated in present specification.
The preferable range of (OS-6) ~ (OS-11) recorded in described general formula (the OS-6) ~ preferable range of general formula (OS-11) and the numbered paragraphs 0110 ~ 0112 of Japanese Patent Laid-Open 2011-221494 publication is identical, its content is incorporated in present specification.
The concrete example of the oxime sulfonate compounds represented by described general formula (OS-3) ~ described general formula (OS-5) can enumerate the compound recorded in the numbered paragraphs 0114 ~ numbered paragraphs 0120 of Japanese Patent Laid-Open 2011-221494 publication, its content is incorporated in present specification.The present invention is not limited to these compounds.
Compound containing the oxime sulfonates structure represented by described general formula (B1-1) is also preferably the oxime sulfonate compounds represented by following general formula (B1-4).
General formula (B1-4)
[changing 21]
(in general formula (B1-4), R 1represent alkyl or aryl, R 2represent alkyl, aryl or heteroaryl.R 3~ R 6represent hydrogen atom, alkyl, aryl, halogen atom respectively.Wherein, R 3with R 4, R 4with R 5or R 5with R 6also can bond and form alicyclic ring or aromatic rings.X represents-O-or S-.)
R 1represent alkyl or aryl.Alkyl preferably has the alkyl of branched structure or the alkyl of ring texture.
The carbon number of alkyl is preferably 3 ~ 10.Especially when alkyl has the situation of branched structure, being preferably the alkyl of carbon number 3 ~ 6, when having the situation of ring texture, being preferably the alkyl of carbon number 5 ~ 7.
Alkyl include, for example: propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl, 1,1-dimethyl propyl, hexyl, 2-ethylhexyl, cyclohexyl, octyl group etc., be preferably isopropyl, the tert-butyl group, neopentyl, cyclohexyl.
The carbon number of aryl is preferably 6 ~ 12, is more preferably 6 ~ 8, and then is preferably 6 ~ 7.Described aryl can enumerate phenyl, naphthyl etc., is preferably phenyl.
R 1represented alkyl and aryl also can have substituting group.Substituting group include, for example: the alkyl (such as methyl, ethyl, propyl group etc.) of halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine), straight chain, branch or ring-type, thiazolinyl, alkynyl, aryl, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, cyano group, carboxyl, hydroxyl, alkoxy, aryloxy group, alkylthio group, arylthio, heterocyclic oxy group, acyloxy, amino, nitro, diazanyl, heterocyclic radical etc.In addition, also can replace further through these groups.Be preferably halogen atom, methyl.
Composition of the present invention with regard to the transparency viewpoint with regard to, R 1be preferably alkyl, with regard to having the viewpoint of storage stability and sensitivity concurrently, R 1be preferably the alkyl with branched structure of carbon number 3 ~ 6, the alkyl of the ring texture of carbon number 5 ~ 7 or phenyl, be more preferably the alkyl of the alkyl with branched structure of carbon number 3 ~ 6 or the ring texture of carbon number 5 ~ 7.By adopting the group (particularly the alkyl of large volume) of this kind of large volume as R 1, can further improve the transparency.
In the substituting group of large volume, be preferably isopropyl, the tert-butyl group, neopentyl, cyclohexyl, be more preferably the tert-butyl group, cyclohexyl.
R 2represent alkyl, aryl or heteroaryl.R 2represented alkyl is preferably the alkyl of the straight chain of carbon number 1 ~ 10, branch or ring-type.Described alkyl include, for example: methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, amyl group, neopentyl, hexyl, cyclohexyl etc., is preferably methyl.
Aryl is preferably the aryl of carbon number 6 ~ 10.Described aryl can be enumerated: phenyl, naphthyl, to toluyl groups (p-methylphenyl) etc., is preferably phenyl, to toluyl groups.
Heteroaryl include, for example: pyrrole radicals, indyl, carbazyl, furyl, thienyl etc.
R 2represented alkyl, aryl and heteroaryl also can have substituting group.Substituting group and R 1the substituting group that represented alkyl and aryl can have is synonymous.
R 2be preferably alkyl or aryl, be more preferably aryl, and then be preferably phenyl.The substituting group of phenyl is preferably methyl.
R 3~ R 6represent hydrogen atom, alkyl, aryl or halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine) respectively.R 3~ R 6represented alkyl and R 2represented alkyl is synonymous, and preferable range is also identical.In addition, R 3~ R 6represented aryl and R 1represented aryl is synonymous, and preferable range is also identical.
R 3~ R 6in, R 3with R 4, R 4with R 5or R 5with R 6also can bond and form ring, about ring, be preferably and form alicyclic ring or aromatic rings, be more preferably phenyl ring.
R 3~ R 6be preferably hydrogen atom, alkyl, halogen atom (fluorine atom, chlorine atom, bromine atoms) or R 3with R 4, R 4with R 5or R 5with R 6bond and form phenyl ring, is more preferably hydrogen atom, methyl, fluorine atom, chlorine atom, bromine atoms or R 3with R 4, R 4with R 5or R 5with R 6bond and form phenyl ring.
R 3~ R 6preferred configuration as follows.
(form 1) at least two is hydrogen atom.
The number of (form 2) alkyl, aryl or halogen atom is less than 1.
(form 3) R 3with R 4, R 4with R 5or R 5with R 6bond and form phenyl ring.
(form 4) meets the form of described form 1 and form 2 and/or meets the form of described form 1 and form 3.
X represents-O-or S-.
The concrete example of described general formula (B1-4) can be listed below compound, but is not particularly limited in this in the present invention.Moreover in exemplary compounds, Ts represents tosyl (p-toluenesulfonyl), and Me represents methyl, and Bu represents normal-butyl, and Ph represents phenyl.
[changing 22]
In photosensitive polymer combination of the present invention, relative to total solid composition 100 mass parts in photosensitive polymer combination, (B-1) content of light acid producing agent is preferably 0.1 mass parts ~ 20 mass parts, be more preferably 0.5 mass parts ~ 10 mass parts, and then be preferably 0.5 mass parts ~ 5 mass parts.Light acid producing agent only can use one, also can and with two or more.When using two or more situations, being preferably its total amount becomes described scope.
< (C-1) solvent >
Photosensitive polymer combination of the present invention contains (C-1) solvent.Photosensitive polymer combination of the present invention is preferably prepared into required composition of the present invention and the solution of further aftermentioned any component dissolves in solvent.Solvent for the preparation of composition of the present invention can use by must composition and arbitrarily uniform composition dissolve and the solvent do not reacted with each composition.
The solvent used in photosensitive polymer combination of the present invention can use known solvent, can illustrate: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, ester class, ketone, amide-type, lactone etc.In addition, the concrete example of the solvent used in photosensitive polymer combination of the present invention also can enumerate record in the numbered paragraphs 0174 ~ numbered paragraphs 0178 of Japanese Patent Laid-Open 2011-221494 publication solvent, Japanese Patent Laid-Open 2012-194290 publication numbered paragraphs 0167 ~ numbered paragraphs 0168 in the solvent recorded, these contents are incorporated in present specification.
In addition, in these solvents, optionally also and then benzylisoeugenol, hexyl ether, ethyleneglycol monophenylether acetic acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, methyl phenyl ethers anisole, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, propylene carbonate equal solvent can be added.These solvents can be used alone a kind of or used in combination two or more.In the present invention spendable solvent be preferably separately a kind of or and with two kinds, be more preferably and use two kinds, and then be preferably and use propylene-glycol monoalky lether acetate esters or dialkyl ether, diacetate esters class and diethylene glycol dialkyl ether class, or ester class and butylene glycol alkylether acetates class.
In addition, solvent be preferably boiling point be more than 130 DEG C and be less than the solvent of 160 DEG C, boiling point is the solvent of more than 160 DEG C or the potpourri of these solvents.
Boiling point is more than 130 DEG C and the solvent being less than 160 DEG C can illustrate: propylene glycol methyl ether acetate (boiling point 146 DEG C), propylene glycol monoethyl ether acetate (boiling point 158 DEG C), propylene glycol methyl n-butyl ether (boiling point 155 DEG C), propylene glycol methyl n-propyl ether (boiling point 131 DEG C).
Boiling point is that the solvent of more than 160 DEG C can illustrate: 3-ethoxyl ethyl propionate (boiling point 170 DEG C), diethylene glycol methyl ethyl ether (boiling point 176 DEG C), propylene glycol monomethyl ether propionate (boiling point 160 DEG C), dipropylene glycol methyl ether acetic acid esters (boiling point 213 DEG C), 3-methoxybutyl ether acetic acid ester (boiling point 171 DEG C), diethylene glycol diethyl ether (boiling point 189 DEG C), diethylene glycol dimethyl ether (boiling point 162 DEG C), propylene-glycol diacetate (boiling point 190 DEG C), diethylene glycol monoethyl ether acetic acid esters (boiling point 220 DEG C), dimethyl ether (boiling point 175 DEG C), 1, 3-butylene glycol diacetate esters (boiling point 232 DEG C).
Relative to all the components 100 mass parts in photosensitive polymer combination, the content of the solvent in photosensitive polymer combination of the present invention is preferably 50 mass parts ~ 95 mass parts, is more preferably 60 mass parts ~ 90 mass parts.
Solvent only can use one, also can use two or more.When using two or more situations, being preferably its total amount becomes described scope.
< (S) polymkeric substance >
Composition of the present invention contains following polymkeric substance as (S) polymkeric substance; namely; structural unit (having the structural unit at siloxane position) containing the part-structure had represented by following general formula (1), with the polymkeric substance having at least one and be selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino.(S) polymkeric substance is respectively containing multiple each structural unit, usually respectively containing more than 5.
General formula (1)
[changing 23]
(in general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.)
<< has the structural unit >> of the part-structure represented by general formula (1)
In described general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, be preferably the alkyl of carbon number 1 ~ 3, be more preferably methyl or ethyl.Concrete alkyl can be enumerated: methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group etc.R 1and R 2preferably represent same group.
N represents the integer of 0 ~ 2, is preferably the integer of 0 or 1, is more preferably 0.
The structural unit with the part-structure represented by general formula (1) is preferably represented by following general formula (I).
General formula (I)
[changing 24]
(in general formula (I), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.R 3represent hydrogen atom or methyl.L 1the atomicity of expression singly-bound or linking part is the concatenating group of 1 ~ 6.)
R in general formula (I) 1and R 2with the R in general formula (1) 1and R 2for synonymous, preferable range is also identical.
N in n in general formula (I) and general formula (1) is synonymous, and preferable range is also identical.
R 3represent hydrogen atom or methyl, be preferably hydrogen atom.
L 1the atomicity of expression singly-bound or linking part is the concatenating group of 1 ~ 6, and the atomicity being preferably linking part is the bivalence linking base of 2 ~ 6, and the atomicity being more preferably linking part is the bivalence linking base of 3 ~ 6.By the atomicity of linking part is set as 2 ~ 6, the motility at siloxane position becomes good (siloxane position becomes pliability), improves adherence and hole cone property raising.
Herein, the atomicity of so-called linking part, refers to the number of the chain carbon atom of the main chain of formation general formula (I) and silicon atom linked, refers to the number of the atom of the chain that formation is the shortest when there is the situation of many chains because of branch or ring-type.Specifically, at L as following formula (A) is represented 1during situation for propylidene, be 3 carbon atoms by the chain that main chain and silicon atom link, therefore the atomicity of linking part become 3.In addition, at L 1when being the situation of cyclohexylidene as following formula (B) is represented, the chain that main chain and silicon atom link is had the situation of 3 and the situation of 5, owing to representing the shortest chain, therefore the atomicity of linking part becomes 3.As following formula (C) is represented at L 1in main chain in when there is the situation of carbonyl, the atomicity of linking part also becomes 3.
[changing 25]
L 1the atomicity of represented linking part is that the concrete example of the concatenating group of 1 ~ 6 can be enumerated: the alkylidene (such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclohexylidene) of carbon number 1 ~ 6, the arlydene (such as phenylene, naphthylene) etc. of carbon number 6 ~ 10.Wherein, the alkylidene of carbon number 1 ~ 6 is preferably.
<< has the structural unit >> of at least one group (X)
Group (X) is selected from the cohort that is made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino; preferably be selected from the cohort that the group represented by epoxy radicals, sulfydryl and (methyl) acryloyl group forms, be more preferably epoxy radicals and sulfydryl.
(S) contained in polymkeric substance group (X) also can be different, but it is identical to be preferably group (X).
The structural unit with at least one group (X) is preferably represented by following general formula (II).
General formula (II)
[changing 26]
(in general formula (II), R 4separately represent hydrogen atom or methyl.L 2the atomicity of expression singly-bound or linking part is the concatenating group of 1 ~ 6.R 5represent epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl or amino.)
R 4with the R in general formula (1-1) 3for synonymous, preferable range is also identical.
R 5represent epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl or amino, be preferably epoxy radicals, sulfydryl, (methyl) acryloyl group, be more preferably epoxy radicals.
L 2with the L in general formula (1-1) 1for synonymous, preferable range is also identical.
(S) polymkeric substance used in the present invention also can structural unit beyond structural unit containing the part-structure had represented by general formula (1) (being preferably the structural unit represented by general formula (I)) and the structural unit (being preferably the structural unit represented by general formula (II)) with at least one group (X), and described structural unit can illustrate described structural unit described in (a1-3).
(S) polymkeric substance used in the present invention is preferably containing the structural unit represented by general formula (I) and the structural unit represented by general formula (II), preferably the structural unit represented by general formula (I) and the structural unit represented by general formula (II) account for more than the 60mol% of all structural units of (S) polymkeric substance, are more preferably and account for more than 80mol%.
(S) structural unit (being preferably the structural unit represented by general formula (I)) with the part-structure represented by general formula (1) in polymkeric substance is preferably 15 ~ 85: 85 ~ 15 with the ratio (mol ratio) that contains of the structural unit (being preferably the structural unit represented by general formula (II)) with at least one group (X), is more preferably 25 ~ 75: 75 ~ 25.By setting as this kind of ratio, can further improve effect of the present invention.
Below, the exemplary compounds of (S) polymkeric substance used in the present invention is shown, but the present invention is not limited to these exemplary compounds certainly.Me represents methyl, and Et represents ethyl.
[changing 27]
[changing 28]
(S) polymkeric substance used in the present invention also can use commercially available product, such as, can use X-12-981S, X-12-984S, X-12-1154, X-12-1048, X-12-972F (being silicone company of SHIN-ETSU HANTOTAI to manufacture).
(S) weight average molecular weight of polymkeric substance is preferably more than 800, is more preferably 800 ~ 5000, and then is preferably 800 ~ 3000.By the weight average molecular weight of (S) polymkeric substance is set as more than 800, the bond ratio of the hydroxyl of siloxane position and substrate increases, can adherence being improved, by being set as less than 5000, the effect of the ageing stability not undermining resist can be obtained.
Weight average molecular weight can utilize gel permeation chromatography (GPC) to obtain.
Relative to total solid composition, the composition of the 1st form of the present invention preferably contains (S) composition with the ratio of 0.1 quality % ~ 20 quality %, be more preferably and contain (S) composition with the ratio of 0.1 quality % ~ 10 quality %, and then preferably contain (S) composition with the ratio of 1 quality % ~ 10 quality %, especially preferably contain (S) composition with the ratio of 2 quality % ~ 5 quality %.(S) composition can be only one, also can be two or more.When (S) composition is two or more situation, being preferably its total amount is described scope.By allotment amount is set as more than 0.1 quality %, adherence improves further, by being set as below 20 quality %, can further improve solution keeping quality.
(S) polymkeric substance can be only one, also can be two or more.When (S) polymkeric substance is two or more situation, being preferably its total amount is described scope.
Other compositions of < >
In photosensitive polymer combination of the present invention, except described composition, optionally can preferably add sensitizer, crosslinking chemical, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkali compounds, surfactant, antioxidant.And then, in photosensitive polymer combination of the present invention, acid proliferation generator can be added, development accelerant, plasticiser, hot radical produce agent, thermal acid generator, ultraviolet light absorber, thickening agent and organic or inorganic the known adjuvant such as antisettling agent.In addition, these contents are incorporated in present specification by the compound that these compounds such as can use the numbered paragraphs 0201 ~ numbered paragraphs 0224 of Japanese Patent Laid-Open 2012-88459 publication to record.These compositions only can use one respectively, also can use two or more.
<< sensitizer >>
Photosensitive polymer combination of the present invention, in order to promote that when combining with light acid producing agent it decomposes, is preferably containing sensitizer.Sensitizer absorbs actinic ray and becomes electron excitation state.The sensitizer becoming electron excitation state contacts with light acid producing agent, produces the effects such as electronics moves, energy moves, heating.Thus, light acid producing agent generation chemical change and decomposing, generates acid.The example of preferred sensitizer can be enumerated: belong to following compounds, and the arbitrary place in the wavelength coverage of 350nm ~ 450nm has the compound of absorbing wavelength.
The polynuclear aromatic same clan (such as pyrene, perylene, 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, rhodamine B, rose bengal), xanthone (such as xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class (such as thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (such as merocyanine, carbonyl merocyanine), if 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 in side's acid) in side's acid, styrene base class, basicity styrene base class (such as 2-[2-[4-(dimethylamino) phenyl] vinyl] benzoxazole), Coumarins (such as 7-diethylamino 4-methylcoumarin, 7-hydroxyl 4-methylcoumarin, 2,3,6,7-tetrahydrochysene-9-methyl isophthalic acid H, 5H, 11H [1] chromene is [6,7,8-ij] quinolizine-11-ketone also).
In these sensitizers, be preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, Coumarins, be more preferably the polynuclear aromatic same clan.In the polynuclear aromatic same clan, most preferably be anthracene derivant.
When photosensitive polymer combination of the present invention contains the situation of sensitizer, relative to total 100 mass parts of described (A-1) component of polymer, the addition of sensitizer is preferably 0 mass parts ~ 100 mass parts, be more preferably 0.1 mass parts ~ 50 mass parts, and then be preferably 0.5 mass parts ~ 20 mass parts.Sensitizer also can and with two or more.
<< crosslinking chemical >>
Photosensitive polymer combination of the present invention optionally also can contain crosslinking chemical.By adding crosslinking chemical, can make to become more strong film by the cured film of photosensitive polymer combination gained of the present invention.
As long as crosslinking chemical causes cross-linking reaction by heat, then also unrestricted.Such as can add: below by the compound of the epoxy radicals or oxetanylmethoxy in the molecule stated with more than 2, containing alkoxy methyl crosslinking chemical or there is the compound, blocked isocyanate compound etc. of at least one ethene unsaturated double-bond.
When photosensitive polymer combination of the present invention contains the situation of crosslinking chemical, relative to total solid composition 100 mass parts in photosensitive composite, the content of crosslinking chemical is preferably 0.01 mass parts ~ 50 mass parts, be more preferably 0.1 mass parts ~ 30 mass parts, and then be preferably 0.5 mass parts ~ 20 mass parts.By adding in described scope, the cured film of physical strength and excellent solvent resistance can be obtained.Crosslinking chemical also can and with multiple, during described situation, crosslinking chemical all added up to and calculate content.
There is in <<< molecule the epoxy radicals of more than 2 or the compound >>> of oxetanylmethoxy
The concrete example in molecule with the compound of the epoxy radicals of more than 2 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.Include, for example: JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (holding (MitsubishiChemicalHoldings) (stock) of Mitsubishi Chemical manufactures) etc., the commercially available product etc. recorded in the numbered paragraphs 0189 of Japanese Patent Laid-Open 2011-221494 publication, in addition, also can enumerate: for that Cauer (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 (above is that long rapids change into (NagaseChemtex) manufactures), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (being that Nippon Steel's chemistry manufactures above) etc.These commercially available products can be used alone one or combinationally use two or more.
In these, more preferably can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin and aliphatic epoxy resin, especially preferably can enumerate bisphenol A type epoxy resin.
The concrete example in molecule with the compound of the oxetanylmethoxy of more than 2 can use: sub-imperial oxetanes (AronOxetane) OXT-121, sub-imperial oxetanes (AronOxetane) OXT-221, sub-imperial oxetanes (AronOxetane) OX-SQ, sub-imperial oxetanes (AronOxetane) PNOX (above for East Asia synthesis (stock) manufactures).
In addition, the compound containing oxetanylmethoxy is preferably used alone or used in combination with the compound containing epoxy radicals.
In addition, other crosslinking chemicals also preferably can use the crosslinking chemical containing alkoxy methyl recorded in the numbered paragraphs 0107 ~ numbered paragraphs 0108 of Japanese Patent Laid-Open 2012-8223 publication and the compound etc. with at least one ethene unsaturated double-bond, these contents are incorporated in present specification.Crosslinking chemical containing alkoxy methyl is preferably aikoxymethytated glycolurils.
<<< blocked isocyanate compound >>>
In photosensitive polymer combination of the present invention, also can preferably adopt blocked isocyanate based compound as crosslinking chemical.There is no particular restriction for blocked isocyanate compound, with regard to indurative viewpoint, is preferably the compound in a part with the blocked isocyanate base of more than 2.
Moreover so-called blocked isocyanate base in the present invention, refers to by heat and generate the group of isocyanate group, such as, preferably can illustrate and make sealer and isocyanates radical reaction and the group of protecting isocyanate group.In addition, described blocked isocyanate base is preferably the heat by 90 DEG C ~ 250 DEG C and generates the group of isocyanate group.
In addition, the skeleton of blocked isocyanate compound is not particularly limited, as long as have 2 isocyanate group in a part, then can be any compound, can be aliphatics, alicyclic or aromatic polyisocyanate, such as, can preferably use: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-nine methylene diisocyanate, 1,10-decamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-Anaesthetie Ether diisocyanate, diphenyl methane-4,4 '-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate, P-xylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, 3,3 '-xylene-4,4 '-diisocyanate, 4,4 '-diphenyl ether diisocyanate, tetrachlorobenzene diisocyanate, norbornene alkyl diisocyanate, hydrogenation 1,3-Xylene Diisocyanate, the compound of the isocyanate compounds such as hydrogenation Isosorbide-5-Nitrae-Xylene Diisocyanate and the skeleton by the prepolymer type of these compound derivings.In these, be especially preferably toluene diisocyanate (TDI) or methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).
The parent structure of the blocked isocyanate compound in photosensitive polymer combination of the present invention can be enumerated: biuret form, isocyanuric acid ester type, adduct type, two functional prepolymer types etc.
The sealer forming the enclosed construction of described blocked isocyanate compound can be enumerated: oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazole compound, imide series compound etc.In these, be especially preferably selected from the sealer in oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound.
Described oxime compound can enumerate oxime and ketoxime, specifically can illustrate: acetoxime (acetoxime), formaldoxime (formaldoxime), cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone-oxime, diphenyl-ketoxime, acetoxime etc.
Described lactam compound can illustrate epsilon-caprolactams, butyrolactam etc.
Described phenolic compounds can illustrate: phenol, naphthols, cresols, xylenols, halogen substiuted phenol etc.
Described alcoholic compound can illustrate: methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, lactic acid alkyl ester etc.
Described amines can lift primary amine and secondary amine, can be aromatic amine, fatty amine, cycloaliphatic amines any one, aniline, diphenylamine, ethylenimine, polyethylene imine based etc. can be illustrated.
Described activity methene compound can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, methyl acetoacetate etc.
Described pyrazole compound can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc.
Described mercaptan compound can illustrate: alkyl sulfhydryl, aryl mercaptan etc.
In photosensitive polymer combination of the present invention, spendable blocked isocyanate compound can be used as commercially available product and obtains, such as, can preferably use: Crow Nat (Coronate) AP stablizes (stable) M, Crow Nat (Coronate) 2503, Crow Nat (Coronate) 2515, Crow Nat (Coronate) 2507, Crow Nat (Coronate) 2513, Crow Nat (Coronate) 2555, rice Leo (Millionate) MS-50 (being Japanese polyurethane industry (stock) manufacture above), Plutarch Nat (Takenate) B-870, Plutarch Nat (Takenate) B-830, Plutarch Nat (Takenate) B-815N, Plutarch Nat (Takenate) B-820NSU, Plutarch Nat (Takenate) B-842N, Plutarch Nat (Takenate) B-846N, Plutarch Nat (Takenate) B-870N, Plutarch Nat (Takenate) B-874N, Plutarch Nat (Takenate) B-882N (being Mitsui Chemicals (stock) manufacture above), Du draws Nat (Duranate) 17B-60PX, Du draws Nat (Duranate) 17B-60P, Du draws Nat (Duranate) TPA-B80X, Du draws Nat (Duranate) TPA-B80E, Du draws Nat (Duranate) MF-B60X, Du draws Nat (Duranate) MF-B60B, Du draws Nat (Duranate) MF-K60X, Du draws Nat (Duranate) MFA-100, Du draws Nat (Duranate) MF-K60B, Du draws Nat (Duranate) E402-B80B, Du draws Nat (Duranate) SBN-70D, Du draws Nat (Duranate) SBB-70P, Du draws Nat (Duranate) K6000 (above is Asahi Chemical Industry's chemistry (stock) manufacture), De Shimo all (Desmodur) BL1100, De Shimo is (Desmodur) BL1265MPA/X, De Shimo is (Desmodur) BL3575/1, De Shimo is (Desmodur) BL3272MPA, De Shimo is (Desmodur) BL3370MPA, De Shimo is (Desmodur) BL3475BA/SN, De Shimo is (Desmodur) BL5375MPA, De Shimo is (Desmodur) VPLS2078/2, De Shimo is (Desmodur) BL4265SN, De Shimo is (Desmodur) PL340, De Shimo is (Desmodur) PL350, Su meter Du (Sumidur) BL3175 (above for firmly changing bayer urethane (stock) manufacture) etc.
<< alkoxysilane compound containing trialkylsilyl group in molecular structure >>
Photosensitive polymer combination of the present invention, except containing except (S) polymkeric substance, also can contain alkoxysilane compound containing trialkylsilyl group in molecular structure as adherence modifying agent.If use alkoxysilane compound containing trialkylsilyl group in molecular structure, then can improve the adherence of film and the substrate formed by photosensitive polymer combination of the present invention, or adjust the character of the film formed by photosensitive polymer combination of the present invention.In photosensitive polymer combination of the present invention, spendable alkoxysilane compound containing trialkylsilyl group in molecular structure preferably makes the inorganics becoming base material, the compound that the adherence of the metals such as silicon compound, gold, copper, molybdenum, titanium, aluminium such as such as silicon, monox, silicon nitride and dielectric film improves.Specifically, known silane coupling agent etc. are also effective.
Silane coupling agent include, for example: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl dialkoxy silicane, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane.In these, be more preferably γ-glycidyloxypropyl silane or γ-methacryloxypropyl trialkoxy silane, and then be preferably γ-glycidyloxypropyl silane, and then be more preferably 3-glycidoxypropyltrimewasxysilane.These one or combinationally use two or more of can be used alone.
Alkoxysilane compound containing trialkylsilyl group in molecular structure in photosensitive polymer combination of the present invention is not particularly limited to these compounds, can use known compound.
When photosensitive polymer combination of the present invention contains the situation of alkoxysilane compound containing trialkylsilyl group in molecular structure, relative to total solid composition 100 mass parts in photosensitive composite, the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably 0.1 mass parts ~ 30 mass parts, is more preferably 0.5 mass parts ~ 20 mass parts.
In addition, in the present invention, because of containing (S) composition, even if therefore allotment amount molecular weight being less than the alkoxysilane compound containing trialkylsilyl group in molecular structure of 1000 is set smaller than 0.1 quality % of the solid constituent of composition of the present invention, also can maintain high adherence.
<< alkali compounds >>
Photosensitive polymer combination of the present invention also can contain alkali compounds.Alkali compounds can be used in Chemical amplification resist any selection use.Include, for example the quarternary ammonium salt etc. of fatty amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic acid.These concrete example can enumerate the compound recorded in the numbered paragraphs 0204 ~ numbered paragraphs 0207 of Japanese Patent Laid-Open 2011-221494 publication, these contents is incorporated in present specification.
Specifically, fatty amine include, for example: trimethylamine, diethylamine, triethylamine, di-n-propylamine, Tri-n-Propylamine, two n-amylamines, tri-n-amyl amine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexylmethylamine etc.
Aromatic amine include, for example: aniline, benzylamine, DMA, diphenylamine etc.
Hetero ring type amine include, for example: pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenylimidazolyl, nicotine, nicotinic acid, niacinamide, quinoline, oxine, pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, 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 include, for example: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, hydroxide benzyltrimethylammon.um, hydroxide tetra-n-butyl ammonium, hydroxide four n-hexyl ammonium etc.
The quarternary ammonium salt of carboxylic acid include, for example: acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid tetra-n-butyl ammonium, benzoic acid tetra-n-butyl ammonium etc.
In the present invention, spendable alkali compounds can be used alone one, also can and with two or more.
When photosensitive polymer combination of the present invention contains the situation of alkali compounds, relative to total solid composition 100 mass parts in photosensitive polymer combination, the content of alkali compounds is preferably 0.001 mass parts ~ 3 mass parts, is more preferably 0.005 mass parts ~ 1 mass parts.
<< surfactant >>
Photosensitive polymer combination of the present invention also can contain surfactant.Surfactant can use negative ion system, kation system, nonionic system or both sexes any one, but preferred surfactant is non-ionic surfactant.Surfactant used in composition of the present invention such as can use: record in numbered paragraphs 0185 ~ numbered paragraphs 0188 that is that record in the numbered paragraphs 0201 ~ numbered paragraphs 0205 of Japanese Patent Laid-Open 2012-88459 publication or Japanese Patent Laid-Open 2011-215580 publication, these records be incorporated in present specification.
The example of nonionic system surfactant can be enumerated: polyoxyethylene senior alkyl ethers, polyoxyethylene senior alkyl phenyl ethers, the higher aliphatic acid diesters class of polyoxyethylene glycol, silicone-based, fluorine system surfactant.In addition, can be enumerated by following trade name: KP-341, X-22-822 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Pohle is Lip river (Polyflow) No.99C (common prosperity society chemistry (stock) manufacture) not, Ai Futuo (Eftop) (Mitsubishi Materials changes into company and manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (stock) manufactures), not rad Cécile Nowak (FloradNovec) FC-4430 (Sumitomo 3M (stock) manufacture), Sha Fulong (Surflon) S-242 (AGC beautifies clearly (AGCSeimiChemicals) company and manufactures), precious reason FOX (PolyFox) PF-6320 (manufacture of Europe Nova (OMNOVA) company), SH-8400 (Dong Li-DOW CORNING silicone (Toray-Dowcorningsilicone)), Fu Jite (Ftergent) FTX-218G (manufacture of Ni Aosi (Neos) company) etc.
In addition, about surfactant, can enumerate containing the structural unit A represented by following general formula (I-1-1) and structural unit B and the weight average molecular weight (Mw) of the polystyrene conversion utilizing the gel permeation chromatography using tetrahydrofuran (THF) as the situation of solvent to measure for 1, more than 000 and the multipolymer of 10, less than 000 as preference.
General formula (I-1-1)
[changing 29]
(in formula (I-1-1), R 401and R 403separately represent hydrogen atom or methyl, R 402represent carbon number more than 1 and the straight-chain alkyl-sub-of less than 4, R 404represent hydrogen atom or carbon number more than 1 and the alkyl of less than 4, L represents the alkylidene of carbon number more than 3 and less than 6, p and q is the quality percentage representing polymerization ratio, p represents more than 10 quality % and the numerical value of below 80 quality %, q represents more than 20 quality % and the numerical value of below 90 quality %, r represents more than 1 and the integer of less than 18, and s represents more than 1 and the integer of less than 10.)
Described L is preferably the branched alkylene groups represented by following general formula (I-1-2).R in general formula (I-1-2) 405represent carbon number more than 1 and the alkyl of less than 4, with regard to compatibility and to regard to the aspect of the wetting quality of applied, be preferably carbon number more than 1 and the alkyl of less than 3, be more preferably the alkyl of carbon number 2 or 3.P and q is preferably p+q=100, i.e. 100 quality % with (p+q).
General formula (I-1-2)
[changing 30]
The weight average molecular weight (Mw) of described multipolymer is more preferably 1, and more than 500 and 5, less than 000.
These surfactants can be used alone a kind of or used in combination two or more.
When photosensitive polymer combination of the present invention contains the situation of surfactant, relative to total solid composition 100 mass parts in photosensitive polymer combination, the addition of surfactant is preferably below 10 mass parts, be more preferably 0.001 mass parts ~ 10 mass parts, and then be preferably 0.01 mass parts ~ 3 mass parts.
<< antioxidant >>
Photosensitive polymer combination of the present invention also can contain antioxidant.Antioxidant can contain known antioxidant.By adding antioxidant, have can prevent cured film painted, maybe can reduce the advantage of thinning, the other heat resistant transparent excellence of thickness caused by decomposing.
This kind of antioxidant include, for example: phosphorous antioxidant, amide-type, hydrazides class, hindered amine system antioxidant, sulphur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc.In these, with regard to painted, the viewpoint that thickness is thinning of cured film, especially be preferably phenol system antioxidant, hindered amine system antioxidant, phosphorous antioxidant, acid amides system antioxidant, hydrazides system antioxidant, sulphur system antioxidant, most preferably be phenol system antioxidant.These antioxidants can be used alone one, also can be used in combination two or more.
Concrete example can be enumerated: these contents are incorporated in present specification by the compound recorded in the compound recorded in the numbered paragraphs 0026 ~ numbered paragraphs 0031 of Japanese Patent Laid-Open 2005-29515 publication, the numbered paragraphs 0106 ~ numbered paragraphs 0116 of Japanese Patent Laid-Open 2011-227106 publication.
Preferred commercially available product can be enumerated: Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-20, Ai Di Coase tower ripple (Adekastab) AO-80, Ai Di Coase tower ripple (Adekastab) LA-52, Ai Di Coase tower ripple (Adekastab) LA-81, Ai Di Coase tower ripple (Adekastab) AO-412S, Ai Di Coase tower ripple (Adekastab) PEP-36, this (Irganox) 1035 of gorgeous promise, this (Irganox) 1098 of gorgeous promise, refined (Tinuvin) 144 of ground slave.
When composition of the present invention contains the situation of antioxidant, relative to total solid composition 100 mass parts in photosensitive polymer combination, the content of antioxidant is preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.2 mass parts ~ 5 mass parts, be especially preferably 0.5 mass parts ~ 4 mass parts.By being set as described scope, the sufficient transparency of formed film can be obtained, and sensitivity when pattern is formed also becomes good.
<< acid proliferation generator >>
In order to improve sensitivity, photosensitive polymer combination of the present invention can use acid proliferation generator.
In the present invention, spendable acid proliferation generator is the compound producing acid further by acid catalyst reaction, make the acid concentration in reaction system increase, and the compound for stably existing under the state that there is not acid.
The concrete example of this kind of acid proliferation generator can enumerate the acid proliferation generator recorded in the numbered paragraphs 0226 ~ numbered paragraphs 0228 of Japanese Patent Laid-Open 2011-221494, its content is incorporated in present specification.
<< development accelerant >>
Photosensitive polymer combination of the present invention can contain development accelerant.
Development accelerant can refer to the development accelerant recorded in the numbered paragraphs 0171 ~ numbered paragraphs 0172 of Japanese Patent Laid-Open 2012-042837 publication, its content is incorporated in present specification.
Development accelerant can be used alone one, also can and with two or more.
When photosensitive polymer combination of the present invention contains the situation of development accelerant, with regard to the viewpoint of sensitivity and residual film ratio, relative to total solid composition 100 mass parts of photosensitive composite, the addition of development accelerant is preferably 0 mass parts ~ 30 mass parts, be more preferably 0.1 mass parts ~ 20 mass parts, most preferably be 0.5 mass parts ~ 10 mass parts.
In addition, other adjuvants also can use the hot radical recorded in the numbered paragraphs 0120 ~ numbered paragraphs 0121 of Japanese Patent Laid-Open 2012-8223 publication to produce the nitrogen-containing compound and thermal acid generator recorded in agent, WO2011/136074A1, these contents are incorporated in present specification.
[the 2nd form of the present invention]
Below, the 2nd form of composition of the present invention is illustrated.
The feature of composition of the present invention is to contain:
(A-2) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a2-1), there is the polymkeric substance that the structural unit of acidic group and (a2-2) have the structural unit of bridging property base,
(2) containing (a2-1), there is the polymkeric substance of the structural unit of acidic group and there is containing (a2-2) polymkeric substance of the structural unit of bridging property base;
(B-2) quinone di-azido compound;
(C-2) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) is selected from the polymkeric substance of the structural unit of the group (X) in the cohort that epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino forms with having at least one.
General formula (1)
[changing 31]
(in general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.)
< (A-2) component of polymer >
(A-2) component of polymer used in the present invention comprises at least one of following polymkeric substance: have the structural unit of acidic group containing (a2-1) and (a2-2) has the polymkeric substance of the structural unit of bridging property base and have the polymkeric substance of the structural unit of acidic group containing (a2-1) and have the polymkeric substance of the structural unit of bridging property base containing (a2-2).And then (A-2) component of polymer also can containing the polymkeric substance beyond these.
<< (a2-1) has the structural unit >> of acidic group
By having the structural unit of acidic group in (A-2) component of polymer containing (a2-1), be easily dissolved in the developer solution of alkalescence, can more effectively play effect of the present invention.Acidic group typically uses the monomer that can form acidic group and is set in polymkeric substance with the form of the structural unit with acidic group.Contain in polymkeric substance by the structural unit making this kind have acidic group, have the tendency in the developer solution being easily dissolved in alkalescence.
Acidic group used in the present invention can use identical with the structural unit containing acidic group in (a1-3) other structural units described in (A-1) component of polymer of the 1st form mentioned above, and except allotment amount, preferable range is also identical.
<< (a2-2) has the structural unit >> of bridging property base
In addition, the structural unit that (a2-2) has a bridging property base is preferably selected from by epoxy radicals, oxetanylmethoxy ,-NH-CH containing having 2the structural unit of at least one in the cohort that the group represented by-O-R (alkyl that R is hydrogen atom or carbon number 1 ~ 20), ethene unsaturated group form.
(a2-2) structural unit that (a1-2) had in the structural unit of bridging property base and (A-1) polymkeric substance mentioned above has bridging property base is synonymous, and except allotment amount, preferable range is also identical.
<< (a2-3) other structural units >>
And then, (A-2) in component of polymer, also can containing the structural unit (a2-3) beyond described structural unit (a2-1) and described structural unit (a2-2) together with described structural unit (a2-1) and described structural unit (a2-2).
Form structural unit (a2-3) if monomer be unsaturated compound beyond described structural unit (a2-1) and structural unit (a2-2), then there is no particular restriction.
Include, for example: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, dicyclo unsaturated compound class, maleimide compound class, unsaturated aromatics, conjugated diolefine based compound, other unsaturated compounds.Specifically can enumerate: N-N-cyclohexylmaleimide, tetrahydrofurfuryl methacrylate, styrene, acryloyl morpholine, lauryl methacrylate, methacrylic acid three ring [5.2.1.0 2 , 6] decane-8-base ester, acrylic acid-2-methyl cyclohexyl, to vinyl benzyl-2,3-glycidyl ethers, (methyl) acrylic acid etc.The monomer forming structural unit (a2-3) can be used alone or combinationally use two or more.
(A-2) in all structural units of component of polymer, be preferably the structural unit (a2-1) containing 3mol% ~ 70mol%, be more preferably containing 10mol% ~ 60mol%, and then be preferably containing 15mol% ~ 50mol%.
(A-2) in all structural units of component of polymer, be preferably the structural unit (a2-2) containing 3mol% ~ 70mol%, be more preferably containing 10mol% ~ 60mol%, and then be preferably containing 15mol% ~ 40mol%.
(A-2) in all structural units of component of polymer, be preferably the structural unit (a2-3) containing 1mol% ~ 80mol%, be more preferably containing 5mol% ~ 50mol%, and then be preferably containing 8mol% ~ 30mol%.
Composition of the present invention preferably contains (A-2) component of polymer with the ratio of more than the 70 quality % of the solid constituent of composition.
< (B-2) quinone di-azido compound >
Quinone di-azido compound used in composition of the present invention can use 1, the 2-quinone di-azido compound being produced carboxylic acid by the irradiation of radioactive ray.1,2-quinone di-azido compound can use: the condensation product of phenoloid or alcoholic compound (hereinafter referred to as " parent nucleus ") and 1,2-naphthoquinones two nitrine sulfonic acid halide.The concrete example of these compounds such as can refer to the record of the numbered paragraphs 0075 ~ numbered paragraphs 0078 of Japanese Patent Laid-Open 2012-088459 publication, its content is incorporated in present specification.
At phenoloid or alcoholic compound (parent nucleus) and 1, in the condensation reaction of 2-naphthoquinones two nitrine sulfonic acid halide, 1, the 2-naphthoquinones two nitrine sulfonic acid halide being equivalent to relative to the OH radix in phenoloid or alcoholic compound be preferably 30mol% ~ 85mol%, be more preferably 50mol% ~ 70mol% can be used.Condensation reaction can utilize known method to implement.
In addition, 1,2-quinone di-azido compound also preferably can use 1, the 2-naphthoquinones two nitrine sulfonamides, such as 2,3, the 4-triamido BP-1s that the ester bond of described illustrative parent nucleus are changed to amido link, 2-naphthoquinones two nitrine-4-sulfonamide etc.
These quinone di-azido compounds can be used alone or combinationally use two or more.Relative to total solid composition 100 mass parts in described photosensitive polymer combination, the allotment amount of the quinone di-azido compound in photosensitive polymer combination of the present invention is preferably 1 mass parts ~ 50 mass parts, be more preferably 2 mass parts ~ 40 mass parts, and then be preferably 10 mass parts ~ 25 mass parts.By the allotment amount of (B-2) quinone di-azido compound is set as described scope, photoactinic illuminated portion and non-irradiation unit divide the difference of the solubleness in the alkaline aqueous solution becoming developer solution large, patterning performance becomes good, and the solvent resistance of the cured film of gained becomes good in addition.
< (C-2) solvent >
Photosensitive polymer combination of the present invention contains solvent.The solvent used in photosensitive polymer combination of the present invention can use (C-1) solvent of the 1st form mentioned above, and preferable range is also identical.
Relative to all the components 100 mass parts in photosensitive polymer combination, the content of the solvent in photosensitive polymer combination of the present invention is preferably 50 mass parts ~ 95 mass parts, is more preferably 60 mass parts ~ 90 mass parts.Solvent only can use one, also can use two or more.When using two or more situations, being preferably its total amount becomes described scope.
< (S) polymkeric substance >
Composition of the present invention contains (S) polymkeric substance mentioned above.(S) polymkeric substance used in 2nd form can use (S) polymkeric substance of the 1st form mentioned above, and preferable range is also identical.
Relative to the gross mass of the photosensitive polymer combination of the 2nd form, (S) composition preferably contains with the ratio of 0.1 quality % ~ 20 quality %, be more preferably with the ratio of 0.1 quality % ~ 10 quality % and contain, and then preferably contain with the ratio of 1 quality % ~ 10 quality %, especially preferably contain with the ratio of 2 quality % ~ 5 quality %.(S) composition can be only one, also can be two or more.When (S) composition is two or more situation, being preferably its total amount becomes described scope.
Other compositions of < >
Composition of the present invention, except described composition, in the scope not undermining effect of the present invention, can optionally and preferably add crosslinking chemical mentioned above, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkali compounds, surfactant, antioxidant.And then, in photosensitive polymer combination of the present invention, development accelerant can be added, plasticiser, hot radical produce agent, thermal acid generator, ultraviolet light absorber, thickening agent and organic or inorganic the known adjuvant such as antisettling agent.These compositions and the 1st homomorphosis mentioned above, preferable range is also identical.
[the 3rd form of composition of the present invention]
The feature of composition of the present invention is to contain:
(A-3) polymerizable monomer;
(B-3) Photoepolymerizationinitiater initiater;
(A-4) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a4-1), there is the polymkeric substance that the structural unit of acidic group and (a4-2) have the structural unit of bridging property base,
(2) containing (a4-1), there is the polymkeric substance of the structural unit of acidic group and there is containing (a4-2) polymkeric substance of the structural unit of bridging property base;
(C-3) solvent; And (S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino.
General formula (1)
[changing 32]
(in general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.)
(A-3) polymerizable monomer
Polymerizable monomer used in the present invention suitably can select the monomer using and be applicable to this kind of composition, is wherein preferably and uses ethene unsaturated compound.
Ethene unsaturated compound is the polymerizable compound with at least one ethene unsaturated double-bond.The example of ethene unsaturated compound can be enumerated: unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) or its ester class, amide-type, preferably can use the amide-type of the ester of unsaturated carboxylic acid and aliphatic polybasic alcoholic compound, unsaturated carboxylic acid and aliphatic polybasic amines.
Include, for example the composition recorded in the paragraph 0031 ~ paragraph 0047 of composition or the Japanese Patent Laid-Open 2006-64921 publication recorded in the paragraph 0011 of Japanese Patent Laid-Open 2006-23696 publication, these records are incorporated in present specification.
In addition, use the carbamate addition polymerization compound manufactured by addition reaction of isocyanates and hydroxyl also preferred, Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-fair 2-32293 publication, such propenoic methyl carbamate class is recorded in Japanese Patent Laid-fair 2-16765 publication, or Jap.P. examined patent publication 58-49860 publication, Jap.P. examined patent publication 56-17654 publication, Jap.P. examined patent publication 62-39417 publication, the carbamate compounds class with skeletal oxirane recorded in Jap.P. examined patent publication 62-39418 publication is also preferred, these records are incorporated in present specification.
Other examples can be enumerated: record such polyester acrylate class in each publication of Japanese Patent Laid-Open No. Sho 48-64183 publication, Jap.P. examined patent publication 49-43191 publication, Jap.P. examined patent publication 52-30490 publication, make epoxy resin and (methyl) acrylic acid react polyfunctional acrylate or the methacrylates such as the Epoxy Acrylates of gained, these records are incorporated in present specification.And then, also can use the compound introduced as photo-hardening monomer and oligomer in " Japan is association's magazine then " (vol.20, No.7,300 pages ~ 308 pages (1984)).
About these ethene unsaturated compounds, its structure, be used alone or and the details of the using method such as use, addition can set arbitrarily according to the performance design of final sense material (sensitivematerial).Such as can select according to following viewpoint.
Polymerizable monomer is preferably multifunctional, be more preferably 3 officials can more than, and then be preferably 4 officials can more than.The upper limit does not exist especially, and 10 officials can be comparatively actual below.And then, by also regulating mechanical characteristic also effective with the compound of functional number difference and/or polymerism base difference (such as acrylate, methacrylate, distyryl compound, vinyl ether compound).
In addition, with regard to adjusting the viewpoint of developability, carboxylic polymerizable compound is also preferred.When described situation, crosslinked by resin and (C-3) composition, can improve mechanical characteristic, thus preferably.
And then, with regard to the adherence of substrate, with the viewpoint of the compatibility of radical polymerization initiator etc. with regard to, be also preferably containing oxirane (EO (EthyleneOxide)) modification body, amino-formate bond.
According to above viewpoint, be preferably pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three ((methyl) acryloyl-oxyethyl) isocyanuric acid ester, pentaerythrite four (methyl) acrylate EO modification body, dipentaerythritol six (methyl) acrylate EO modification body etc., and as Ka Yala get (KAYARAD) DPHA (Japanese chemical drug (stock) manufacture) of commercially available product, NK ester (NKEster) A-TMMT, NK ester (NKEster) A-TMPT, NK ester (NKEster) A-TMM-3, NK oligomerization (NKOligo) UA-32P, NK oligomerization (NKOligo) UA-7200 (being that Xin Zhong village chemical industry (stock) manufactures above), sub-Luo Nisi (Aronix) M-305, sub-Luo Nisi (Aronix) M-306, sub-Luo Nisi (Aronix) M-309, sub-Luo Nisi (Aronix) M-450, sub-Luo Nisi (Aronix) M-402, TO-1382 (above for East Asia synthesis (stock) manufactures), V#802 (Osaka Organic Chemical Industry (stock) manufacture).
The polymerizable monomer applied in the present invention is preferably the compound represented by following formula (A-3-1).
Formula (A-3-1)
[changing 33]
In formula (A-3-1), L represents the concatenating group of more than divalence.Concatenating group is not particularly limited, and can enumerate alkylidene, carbonyl, imino group, ether (-O-), thioether group (-S-) or these combination.The carbon number of concatenating group is not particularly limited, and is preferably 2 ~ 24, is more preferably 2 ~ 12.Wherein, the branched alkylene groups of described carbon number is preferably.
In formula (A-3-1), A represents polymerizable functional groups.Polymerizable functional groups is preferably vinyl or the group containing vinyl.Group containing vinyl can be enumerated: acryloyl group, methacryl, acryloxy, methacryloxy, ethenylphenyl etc.
In formula (A-3-1), Ra represents substituting group.Substituting group is not particularly limited, and can enumerate: alkyl (being preferably carbon number 1 ~ 21), thiazolinyl (being preferably carbon number 2 ~ 12), aryl (being preferably carbon number 6 ~ 24) etc.These substituting groups also can have substituting group further, and the substituting group that can have can be enumerated: hydroxyl, alkoxy (being preferably carbon number 1 ~ 6), carboxyl, acyl group (being preferably carbon number 1 ~ 6) etc.
In formula (A-3-1), na represents the integer of 1 ~ 10, is preferably 3 ~ 8.Nb represents the integer of 0 ~ 9, is preferably 2 ~ 7.Na+nb is less than 10, is preferably 2 ~ 8.When na, nb are more than 2, multiple structure positions of its defined also can be different.
Relative to total 100 mass parts of described (A-3) component of polymer, the content of polymerizable monomer is preferably 5 mass parts ~ 60 mass parts, is more preferably 10 mass parts ~ 50 mass parts, and then is preferably 15 mass parts ~ 45 mass parts.
Relative to total solid composition, photosensitive polymer combination of the present invention is preferably with the ratio of 5 quality % ~ 60 quality % containing polymerizable monomer, be more preferably and contain with the ratio of 10 quality % ~ 50 quality %, and then preferably contain with the ratio of 15 quality % ~ 45 quality %.
(B-3) Photoepolymerizationinitiater initiater
In the present invention, spendable Photoepolymerizationinitiater initiater is for photosensitive by exposure light, causes, promotes the compound of the polymerization of described polymerizable monomer.
In the present invention, spendable Photoepolymerizationinitiater initiater is photosensitive preferably by exposure light, causes, promotes the compound of the polymerization of described ethene unsaturated compound.
In the present invention so-called " radioactive ray ", as long as giving can produce by composition B-3 the active energy ray causing the energy of planting by its irradiation, then there is no particular restriction, comprises alpha ray, gamma-rays, X ray, ultraviolet (UV), luminous ray, electron beam etc. widely.
Photoepolymerizationinitiater initiater is that induction is preferably more than wavelength 300nm, is more preferably the actinic ray of wavelength 300nm ~ 450nm, causes, promotes the compound of the polymerization of described (A-3) polymerizable monomer.In addition, about the photoactinic Photoepolymerizationinitiater initiater directly not responding to more than wavelength 300nm, as long as also for responding to photoactinic compound of more than wavelength 300nm by also using with sensitizer, then can combine with sensitizer and preferably use.
Photoepolymerizationinitiater initiater include, for example: oxime ester compound, organic halogenation compound, oxygen base diazole compounds, carbonyls, ketal compound, styrax compound, acridine compounds, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, metallocene compound, six aryl united imidazoles, organic boric acid compounds, disulfonic acid compound, α aminoketone compounds, salt compound, acylphosphanes (oxide) compound.In these, with regard to the aspect of sensitivity, be preferably oxime ester compound, α aminoketone compounds, six aryl united imidazoles, be more preferably oxime ester compound or α aminoketone compounds.
The concrete example of these compounds such as can refer to the record of the numbered paragraphs 0061 ~ numbered paragraphs 0073 of Japanese Patent Laid-Open 2011-186398 publication, its content is incorporated in present specification.
Photoepolymerizationinitiater initiater also can use commercially available product, such as, can use gorgeous good solid (IRGACURE) OXE01, gorgeous good solid (IRGACURE) OXE02 (BASF (BASF) manufacture) etc.
Photoepolymerizationinitiater initiater can use one or combinationally use two or more.In addition, when use does not have the situation of the initiating agent of absorption to exposure wavelength, sensitizer must be used.
Relative to total 100 mass parts of described (A-3) component of polymer, the content of the Photoepolymerizationinitiater initiater in photosensitive polymer combination of the present invention is preferably 0.5 weight portion ~ 30 weight portion, is more preferably 2 weight portion ~ 20 weight portions.
Relative to total solid composition, photosensitive polymer combination of the present invention is preferably and contains Photoepolymerizationinitiater initiater with the ratio of 0.5 quality % ~ 30 quality %, is more preferably and contains with the ratio of 2 quality % ~ 20 quality %.
(A-4) component of polymer
(A-4) component of polymer used in the present invention contains at least one of following polymkeric substance: have the structural unit of acidic group containing (a4-1) and (a4-2) has the polymkeric substance of the structural unit of bridging property base and have the polymkeric substance of the structural unit of acidic group containing (a4-1) and have the polymkeric substance of the structural unit of bridging property base containing (a4-2).And then, also in (A-4) component of polymer, the structural unit (a4-3) beyond described structural unit (a4-1) and described structural unit (a4-2) can be contained together with described structural unit (a4-1) and described structural unit (a4-2).
(A-4) structural unit that (a4-1) contained by polymkeric substance has acidic group can adopt the structural unit with (a2-1) described in (A-2) component of polymer of the 2nd form mentioned above with acidic group identical, and preferable range is also identical.
(A-4) structural unit that (a4-2) contained by polymkeric substance has bridging property base can adopt the structural unit with (a2-2) described in (A-2) component of polymer of the 2nd form mentioned above with bridging property base identical, and preferable range is also identical.
(A-4) structural unit (a4-3) contained by polymkeric substance such as can adopt identical with (a2-3) other structural units described in (A-2) component of polymer of the 2nd form mentioned above, and preferable range is also identical.
The composition of the 3rd form of the present invention is preferably the ratio with more than 30 % by weight of total solid composition and contains component of polymer.
< (C-3) solvent >
Photosensitive polymer combination of the present invention contains solvent.Photosensitive polymer combination of the present invention is preferably the form of the solution of each component dissolves of the present invention in solvent to be prepared.
The solvent used in photosensitive polymer combination of the present invention can use (C-1) solvent of known solvent, the 1st form such as mentioned above.
Relative to total composition 100 mass parts in photosensitive polymer combination, the content of the solvent in photosensitive polymer combination of the present invention is preferably 50 mass parts ~ 95 mass parts, is more preferably 60 mass parts ~ 90 mass parts.Solvent only can use one, also can use two or more.When using two or more situations, being preferably its total amount becomes described scope.
< (S) polymkeric substance >
Composition of the present invention contains (S) polymkeric substance mentioned above.(S) polymkeric substance used in 3rd form can use (S) polymkeric substance of the 1st form mentioned above, and preferable range is also identical.Relative to the gross mass of photosensitive polymer combination, (S) composition preferably contains with the ratio of 0.1 quality % ~ 20 quality %, be more preferably with the ratio of 0.1 quality % ~ 10 quality % and contain, and then preferably contain with the ratio of 1 quality % ~ 10 quality %, especially preferably contain with the ratio of 2 quality % ~ 5 quality %.(S) composition can be only one, also can be two or more.When (S) composition is two or more situation, being preferably its total amount becomes described scope.
Other compositions of < >
Composition of the present invention, except described composition, in the scope not undermining effect of the present invention, optionally can preferably add crosslinking chemical mentioned above, alkoxysilane compound containing trialkylsilyl group in molecular structure, alkali compounds, surfactant, antioxidant.And then, in photosensitive polymer combination of the present invention, development accelerant can be added, plasticiser, hot radical produce agent, thermal acid generator, ultraviolet light absorber, thickening agent and organic or inorganic the known adjuvant such as antisettling agent.These compositions and the 1st homomorphosis mentioned above, preferable range is also identical.
The preparation method > of < photosensitive polymer combination
Arbitrary method is utilized to mix with set ratio each composition, stirring and dissolving and prepare photosensitive polymer combination.Such as, after also can be made into the solution be dissolved in advance respectively by composition in solvent, these solution are prepared resin combination with the mixing of set ratio.The composition solution prepared as described above also can be used after using the filtrator etc. in such as 0.2 μm, aperture to filter.
The manufacture method > of the cured film of < the 1st form of the present invention
The manufacture method of the cured film of the 1st form of the present invention preferably comprises the step of following (1-1) ~ (5-1).
(1-1) photosensitive polymer combination of the 1st form of the present invention is coated the step on substrate;
(2-1) in the photosensitive polymer combination be coated with, remove the step of solvent;
(3-1) step that actinic ray exposes the photosensitive polymer combination eliminating solvent is utilized;
(4-1) step that aqueous developer solution is developed to the photosensitive polymer combination through exposure is utilized;
(5-1) baking procedure after thermmohardening is carried out to the photosensitive polymer combination through development.
Below sequentially each step is illustrated.
In the application step of (1-1), be preferably the moistening film coated by photosensitive polymer combination of the present invention and substrate makes containing solvent.Being preferably photonasty being set before resin combination coats on substrate, carrying out the cleaning of the substrates such as alkali cleaning or plasma clean, being more preferably after base-plate cleaning, utilizing hexamethyldisilazane to process substrate surface further.By carrying out described process, there is the tendency that photosensitive polymer combination improves the adherence of substrate.Utilize hexamethyldisilazane to be not particularly limited the method that substrate surface processes, include, for example the method etc. of exposure of substrates in hexamethyldisilazane steam.
Described substrate can enumerate inorganic substrate, resin, resin composite materials etc.
Inorganic substrate include, for example: glass, quartz, silicone, silicon nitride, and evaporation has the composite base plate of molybdenum, titanium, aluminium, copper etc. on the substrate of these materials.
About resin, the substrate comprising following resin can be enumerated: polybutylene terephthalate, polyethylene terephthalate, Polyethylene Naphthalate, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyethersulfone, polyarylate, allyl diglycol carbonates, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, polycyclic alkene, norbornene resin, the fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomeric resins, cyanate ester resin, crosslinked dimethyl ester, cyclic polyolefin, aromatic ether, maleimide-alkene, cellulose, the synthetic resin such as episulfide compounds.
These substrates seldom directly use with described form, usually different depending on the form of final products and form the multilayer laminate constructions that such as TFT element is such.
The coating process of substrate is not particularly limited, such as, can uses: the methods such as slot coated method, spray-on process, roller rubbing method, method of spin coating, cast coating method, slit and rotary process.
Moistening thickness during coating is not particularly limited, and can be coated with the thickness corresponding with purposes, but usually uses in the scope of 0.5 μm ~ 10 μm.
And then, also can before be coated with composition used in the present invention on substrate, record such what is called in application Japanese Patent Laid-Open 2009-145395 publication and to prewet (pre-wet) method.
In the solvent removal step of (2-1), in the described film be coated with, remove solvent by decompression (vacuum) and/or heating etc., substrate forms dry coating.At the heating condition of solvent removal step is preferably 70 DEG C ~ 130 DEG C 30 second ~ 300 seconds about.When temperature and time is the situation of described scope, figuratum adherence is better and also can reduce the tendency of residue further.
In the step of exposure of (3-1), the substrate being provided with film is irradiated to the actinic ray of predetermined pattern.In described step, light acid producing agent decomposes and produces acid.Utilizing the catalyst action of the acid produced, by being coated with sour decomposability base hydrolysis contained in film component, generating carboxyl or phenolic hydroxyl group.
Utilize photoactinic exposure light source can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light emitting diode (LightEmittingDiode, LED) light source, excimer laser generation device etc., can preferably use i ray (365nm), h ray (405nm), g ray (436nm) etc. to have more than wavelength 300nm and the actinic ray of the wavelength of below 450nm.In addition, optionally also irradiation light is adjusted by point optical filter that long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter are such.Exposure is preferably 1mj/cm 2~ 500mj/cm 2.
Exposure device can use: the exposure machine of the various modes such as mirror surface projection alignment machine (mirrorprojectionaligner), stepper (stepper), scanner (scanner), close induction type (proximity), contact (contact), microlens array (microlensarray), lens scan device (lensscanner), laser explosure.
In the region generating acid catalyst, in order to make described hydrolysis reaction accelerate, can carry out exposing rear heating (postexposure bake (PostExposureBake) is hereinafter also referred to " PEB ").By PEB, can promote to generate carboxyl or phenolic hydroxyl group by sour decomposability base.The temperature of carrying out the situation of PEB is preferably more than 30 DEG C and less than 130 DEG C, is more preferably more than 40 DEG C and less than 110 DEG C, is especially preferably more than 50 DEG C and less than 100 DEG C.
Wherein, the activation evergy that the acid of sour decomposability base of the present invention is decomposed is low, and easy reason is exposed to the sun and photogenicly derived from the acid of acid producing agent and decompose, and generates carboxyl or phenolic hydroxyl group, therefore may not carry out PEB, also form eurymeric image by development.
In the development step of (4-1), alkaline-based developer is used to develop to the multipolymer with free carboxyl or phenolic hydroxyl group.By removing containing the region, exposure portion with the resin combination of carboxyl or phenolic hydroxyl group be easily dissolved in alkaline-based developer, and form eurymeric image.
In the developer solution used in development step, be preferably the aqueous solution containing alkali compounds.Alkali compounds such as can use: the alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide; The alkali carbonate classes such as sodium carbonate, sal tartari, cesium carbonate; The alkaline metal bicarbonate such as sodium bicarbonate, potassium bicarbonate class; The tetraalkylammonium hydroxide classes such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, diethyldimethylammonhydroxide hydroxide; The hydroxides such as choline (hydroxy alkyl) trialkyl ammonium class; The silicates such as sodium silicate, sodium metasilicate; The alkyl amines such as ethamine, propylamine, diethylamine, triethylamine; The alcamines such as dimethylethanolamine, triethanolamine; The ester ring type amines such as 1,8-diazabicyclo-[5.4.0]-7-hendecene, 1,5-diazabicyclo-[4.3.0]-5-nonene.
In these, be preferably NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, choline (hydroxide-2-hydroxyethyl trimethyl ammonium).
In addition, also the aqueous solution of adding the water-miscible organic solvents such as the methyl alcohol of appropriate amount or ethanol or surfactant in the aqueous solution of described bases can be 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.
Development time be preferably 30 second ~ 500 seconds, in addition, the method for development can be any one that cover liquid method (puddlemethod), spray process, infusion process etc.
After development, also rinsing step can be carried out.In rinsing step, by utilizing the substrate after the cleaning developments such as pure water, and carry out accompanying developer solution removal, the removal of development residue.ELUTION METHOD can use known method.Include, for example spray drip washing or dipping drip washing etc.
In the rear baking procedure of (5-1), the eurymeric image of gained is heated, make sour decomposability base carry out thermal decomposition and generate carboxyl or phenolic hydroxyl group, crosslinked with bridging property base, crosslinking chemical etc., can cured film be formed thus.Described heating is preferably and uses the heating arrangement such as hot plate or baking oven, the heating of given time is carried out at set temperature, such as 180 DEG C ~ 250 DEG C, if such as hot plate then carries out the heating of 5 minutes ~ 90 minutes, if baking oven then carries out the heating of 30 minutes ~ 120 minutes.By so carrying out cross-linking reaction like that, the more excellent diaphragm such as thermotolerance, hardness or interlayer dielectric can be formed.In addition, when heating, by carrying out in a nitrogen environment, also can further improve the transparency.
Before rear baking, also can carry out rear baking (in adding baking procedure) after toasting at relatively low temperature.During the situation of underway baking, be preferably and heat after 1 minute ~ 60 minutes at 90 DEG C ~ 150 DEG C, baking after carrying out under the high temperature more than 200 DEG C.In addition, also can the multistage in three stages more than be divided into heat middle baking, rear baking.By arranging baking, rear baking in this kind, the cone angle of adjustable pattern.The heating of these bakings can use the known heating means such as hot plate, baking oven, infrared heater.
Moreover, can before rear baking, after utilizing actinic ray to carry out exposing (post-exposure) again to the figuratum substrate of formation comprehensively, carry out rear baking, acid is produced thus by the light acid producing agent be present in unexposed portion, play function as promoting the catalyzer of cross-linking step, thus the sclerous reaction of film can be promoted.The preferred exposure comprising the situation of post-exposure step is preferably 100mJ/cm 2~ 3,000mJ/cm 2, be especially preferably 100mJ/cm 2~ 500mJ/cm 2.
And then, also the cured film by photosensitive polymer combination gained of the present invention can be used as dry-etching resist.When the cured film being carried out thermmohardening gained by rear baking procedure is used as the situation of dry-etching resist, about etch processes, the dry-etching process such as ashing, plasma etching, ozone etching can be carried out.
The manufacture method > of the cured film of < the 2nd form of the present invention
The manufacture method of the cured film of the 2nd form of the present invention preferably comprises the step of following (1-2) ~ (5-2).
(1-2) photosensitive polymer combination of the 2nd form of the present invention is coated the step on substrate;
(2-2) in the photosensitive polymer combination be coated with, remove the step of solvent;
(3-2) step that actinic ray exposes the photosensitive polymer combination eliminating solvent is utilized;
(4-2) step that aqueous developer solution is developed to the photosensitive polymer combination through exposure is utilized;
(5-2) baking procedure after thermmohardening is carried out to the photosensitive polymer combination through development.
Each step (the 1-2) ~ step (5-2) of the manufacture method of cured film of the present invention can be carried out respectively in the same manner as the step of (1-1) ~ (5-1) of the manufacture method of the cured film of the 1st form mentioned above, and optimum condition is also identical.
Also be can be used as etching resist by the cured film of composition gained of the present invention.
[manufacture method of the cured film of the 3rd form of the present invention]
The manufacture method of the cured film of the 3rd form of the present invention preferably comprises the step of following (1-3) ~ (5-3).
(1-3) photosensitive polymer combination of the 3rd form of the present invention is coated the step on substrate;
(2-3) in the photosensitive polymer combination be coated with, remove the step of solvent;
(3-3) step that actinic ray exposes the photosensitive polymer combination eliminating solvent is utilized;
(4-3) step that aqueous developer solution etc. is developed to the photosensitive polymer combination through exposure is utilized;
(5-3) baking procedure after thermmohardening is carried out to the photosensitive polymer combination through development.
Below sequentially each step is illustrated.
In the application step of (1-3), photosensitive polymer combination is coated on substrate.
About the preparation of photosensitive polymer combination, such as, also to can be made into described containing after composition is dissolved in the solution in solvent respectively in advance, these solution are prepared resin combination with the mixing of set ratio.The composition solution prepared as described above also can after using the filtrator etc. in such as 0.2 μm, aperture to filter in.
In the application step of (1-3), the substrate recorded in (1-1) step mentioned above can be used, in addition, the coating process recorded in (1-1) step mentioned above can be used.
In the solvent removal step of (2-3), in the photosensitive polymer combination be coated with, remove solvent preferably by decompression and/or heating, substrate forms dry coating.(2-3) heating condition of solvent removal step also look the kind of each composition or allotment than and different, preferably at 80 DEG C ~ 130 DEG C 30 second ~ 120 seconds about.
In the step of exposure of (3-3), be preferably the film of gained with set more than pattern-like illumination wavelength 300nm and the actinic ray of below 450nm.In described step, polymerizable monomer (polymerizable compound) is polymerized sclerosis by the effect of polymerization initiator.
About utilizing photoactinic exposure, the actinic ray enumerated in the explanation of the step of exposure in the manufacture method of the cured film of the 1st form mentioned above can be used.In addition, optionally also irradiation light is adjusted by point optical filter that long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter are such.
In the development step of (4-3), be preferably and use alkaline-based developer to develop.By being removed in the region, unexposed portion containing the resin combination with acidic group, and form minus image.
In the developer solution used in development step, be preferably containing alkali compounds.Alkali compounds such as can use the alkali compounds enumerated in the explanation of the development step in the manufacture method of the cured film of the 1st form mentioned above.
The pH value of developer solution is preferably 10.0 ~ 14.0.Development time be preferably 30 second ~ 180 seconds, in addition, the method for development can be any one that cover liquid method, infusion process etc.After development, can carry out 30 second ~ 90 seconds flowing water cleaning and formed needed for pattern.After development, also can carry out rinsing step in the same manner as the manufacture method of the cured film of the 1st form mentioned above.
In the rear baking procedure of (5-3), the minus image of gained is heated, thus remaining solvent composition is removed, optionally promote the crosslinked of resin, can cured film be formed thus.Described heating is preferably heated to the high temperature of more than 150 DEG C, is more preferably and is heated to 180 DEG C ~ 250 DEG C, is especially preferably heated to 200 DEG C ~ 240 DEG C.Heat time suitably can set, in the scope being preferably set as 10 minutes ~ 120 minutes according to heating-up temperature etc.Also toast in can implementing in the same manner as the manufacture method of the cured film of the 1st form mentioned above.
If increased before rear baking procedure, whole of developing pattern is irradiated to actinic ray, is preferably ultraviolet step (post-exposure step), then irradiate by actinic ray and promote cross-linking reaction.And then, also can be used as dry-etching resist by the cured film of photosensitive polymer combination gained of the present invention.
When the cured film rear baking procedure by (5-3) being carried out thermmohardening gained is used as the situation of dry-etching resist, about etch processes, the dry-etching process such as ashing, plasma etching, ozone etching can be carried out.
[cured film]
Cured film of the present invention is the cured film of the photosensitive polymer combination sclerosis gained making the 1st form of the present invention ~ the 3rd form mentioned above.
Cured film of the present invention preferably can be used as interlayer dielectric.In addition, cured film of the present invention is preferably the cured film of the formation method gained of the cured film of the 1st form of the present invention ~ the 3rd form by mentioned earlier.
Utilize photosensitive polymer combination of the present invention, even if insulativity excellence can be obtained and at high temperature when the situation of baking, also there is the interlayer dielectric of the high transparency.The interlayer dielectric of photosensitive polymer combination of the present invention is used to have the high transparency, and cured film physical properties excellent, thus useful in the purposes of liquid crystal indicator or organic EL display.
[liquid crystal indicator]
The feature of liquid crystal indicator of the present invention is to possess cured film of the present invention.
Liquid crystal indicator of the present invention uses except the planarization film that formed of described photosensitive polymer combination of the present invention or interlayer dielectric except having, and there is no particular restriction, can enumerate the known liquid crystal indicator adopting various structure.
Such as, the concrete example of thin film transistor (TFT) (Thin-FilmTransistor, TFT) that liquid crystal indicator of the present invention possesses can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention due to excellent electrical characteristic, therefore can combine with these TFT and preferably use.
In addition, the desirable liquid crystal drive mode of liquid crystal indicator of the present invention can be enumerated: twisted nematic (TwistedNematic, TN) mode, vertical orientated (VirticalAlignment, VA) mode, coplanar switching (In-Place-Switching, IPS) mode, fringing field switch (FringsFieldSwitching, FFS) mode, optical compensation curved (OpticalCompensatedBend, OCB) mode etc.
Form about panel, at colorful optical filter array (ColorFilteronAllay, also cured film of the present invention can be used in the liquid crystal indicator of COA) mode, such as, can be used as the organic insulating film (115) of Japanese Patent Laid-Open 2005-284291 or the organic insulating film (212) of Japanese Patent Laid-Open 2005-346054.In addition, the specifically aligned of the liquid crystal orientation film that liquid crystal indicator of the present invention is desirable enumerates friction orientation method, light orientation side etc.In addition, polymer stabilizing orientation (PolymerSustainedAlignment, the PSA) technology recorded in Japanese Patent Laid-Open 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication also can be utilized to carry out polymer orientation support.
In addition, photosensitive polymer combination of the present invention and cured film of the present invention are not limited to described purposes, can be used in various uses.Such as; except planarization film or interlayer dielectric, also can be preferably used for colored filter diaphragm or in order to the lenticule etc. the liquid crystal layer in liquid crystal indicator being held in certain thickness distance piece (spacer) or be arranged in solid-state imager on colored filter.
Fig. 2 is the conceptual sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.Described color liquid crystal display arrangement 10 is the liquid crystal panel on the back side with back light unit 12, and in liquid crystal panel, be configured with at the element being pasted with the corresponding TFT16 of all pixels of configuring between 2 sheet glass substrates 14 of light polarizing film, glass substrate 15.Be formed at each element on glass substrate by being formed at the contact hole 18 in cured film 17, and tin indium oxide (IndiumTinOxide, the ITO) transparency electrode 19 of the tangible pixel electrode of distribution.On ito transparent electrode 19, the layer being provided with liquid crystal 20 and RGB (RedGreenBlue, the RGB) colored filter 22 being configured with black matrix".
The light source of backlight is not particularly limited, and can use known light source.Include, for example multi-colored led, fluorescent light (cold-cathode tube), organic EL etc. of White LED, blue red green etc.
In addition, liquid crystal indicator can be set as three-dimensional (ThreeDimensions, 3D) (stereopsis) type, also can be set as touch screen type.And then also can be set as flexible type, can be used as the interlayer dielectric (520) recorded in the 2nd interlayer dielectric (48) recorded in Japanese Patent Laid-Open 2011-145686 publication or Japanese Patent Laid-Open 2009-258758 publication.
[organic EL display]
The feature of organic EL display of the present invention is to possess cured film of the present invention.
Organic EL display of the present invention uses except the planarization film that formed of described photosensitive polymer combination of the present invention or interlayer dielectric except having, there is no particular restriction, can enumerate the known various organic EL display or liquid crystal indicator that adopt various structure.
Such as, the concrete example of thin film transistor (TFT) (Thin-FilmTransistor, TFT) that organic EL display of the present invention possesses can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention due to excellent electrical characteristic, therefore can combine with these TFT and preferably use.
Fig. 1 is the formation concept map of an example of organic EL display.It represents the schematic cross sectional view of the substrate in the organic EL display of bottom emission type, has planarization film 4.
Glass substrate 6 is formed the TFT1 of bottom gate type, is formed with the state covering described TFT1 and comprise Si 3n 4dielectric film 3.Formed after omitting illustrated contact hole in dielectric film 3 herein, the distribution 2 (height 1.0 μm) being connected to TFT1 via described contact hole is formed on dielectric film 3.Distribution 2 is the distribution in order to connecting between TFT1 or be connected with TFT1 by the organic EL formed in subsequent step.
And then, in order to make, because of the concavo-convex planarization formed caused by distribution 2, to form planarization film 4 on the insulating film 3 with the concavo-convex state of landfill caused by distribution 2.
On planarization film 4, form the organic EL of bottom emission type.That is, on planarization film 4, be connected to distribution 2 via contact hole 7 and form the first electrode 5 comprising ITO.In addition, the first electrode 5 is equivalent to the anode of organic EL.
Forming the dielectric film 8 of the shape at the edge of covering first electrode 5, by arranging described dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and its subsequent step can be prevented.
And then, in Fig. 1 although not shown, but be situated between every required pattern mask sequentially evaporation hole transmission layer, organic luminous layer, electron transfer layer are set, then, whole of surface is formed the second electrode comprising A1, use ultraviolet ray hardening type epoxy resin and glass for sealing plate to fit, seal thus, obtain the organic EL display of the active array type each organic EL being connected to the TFT1 in order to drive described organic EL.
Photosensitive polymer combination of the present invention is due to hardening and cured film excellent, pretend as MEMS (micro electro mechanical system) (MicroelectromechanicalSystems, MEMS) structural elements of element, to the Resist patterns that formed of photosensitive polymer combination of the present invention be used as dividing wall, or enter as a part of group of Mechanical Driven part and use.This kind of MEMS element include, for example: surface acoustic wave (SurfaceAcousticWave, SAW) part such as wave filter, bulk acoustic wave (BulkAcousticWave, BAW) wave filter, gyrosensor (gyrosensor), display micro-shutter (microshutter), imageing sensor, Electronic Paper, ink gun, biochip (biochip), sealant.Example is illustrated in Jap.P. spy table 2007-522531, Japanese Patent Laid-Open 2008-250200, Japanese Patent Laid-Open 2009-263544 etc. more specifically.
Photosensitive polymer combination of the present invention is due to flatness or transparency excellence, therefore such as also can be used for being formed the accumulation horizon (16) and planarization film (57) recorded in Fig. 2 of Japanese Patent Laid-Open 2011-107476 publication, the dividing wall (12) recorded in Fig. 4 (a) of Japanese Patent Laid-Open 2010-9793 publication and planarization film (102), the accumulation horizon (221) recorded in Figure 10 of Japanese Patent Laid-Open 2010-27591 publication and the 3rd interlayer dielectric (216b), the 2nd interlayer dielectric (125) recorded in Fig. 4 (a) of Japanese Patent Laid-Open 2009-128577 publication and the 3rd interlayer dielectric (126), the planarization film (12) recorded in Fig. 3 of Japanese Patent Laid-Open 2010-182638 publication and pixel separation dielectric film (14) etc.In addition, also can be preferably used in order to the liquid crystal layer in liquid crystal indicator is held in certain thickness distance piece, or the crystalline substance of facsimile recorder (facsimile), electronic reprographic machine, solid-state imager etc. carries the imaging optical system of colored filter or the lenticule of the joints of optical fibre.
[embodiment]
Below enumerate embodiment more specifically to be illustrated the present invention.Material shown in following embodiment, use amount, ratio, contents processing, processing sequence etc. only otherwise depart from purport of the present invention, then can suitably change.Therefore, scope of the present invention is not limited to concrete example shown below.Moreover as long as no special instructions, then " part ", " % " are quality criteria.
In following synthesis example, following symbol represents following compound respectively.
MATHF: methacrylic acid-2-tetrahydrofuran ester (composite)
MAEVE: methacrylic acid-1-ethoxy ethyl ester (manufacturing with light pure pharmaceutical worker's industry company)
OXE-30: methacrylic acid-3-ethyl-3-oxetanylmethoxy methyl esters (manufacture of Osaka Organic Chemical Industry company)
GMA: glycidyl methacrylate (manufacturing with light pure pharmaceutical worker's industry company)
NBMA: n-butoxy methyl acrylamide (Tokyo changes into manufacture)
HEMA: hydroxyethyl methacrylate (manufacturing with Guang Chun medicine company)
MAA: methacrylic acid (manufacturing with light pure pharmaceutical worker's industry company)
MMA: methyl methacrylate (manufacturing with light pure pharmaceutical worker's industry company)
St: styrene (manufacturing with light pure pharmaceutical worker's industry company)
DCPM: methacrylic acid two ring pentyl ester
V-601: dimethyl-2,2 '-azo two (2 Methylpropionic acid ester) (manufacturing with light pure pharmaceutical worker's industry company)
V-65:2,2 '-azo two (2,4-methyl pentane nitrile) (manufacturing with light pure pharmaceutical worker's industry 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)
The synthesis > of <MATHF
Methacrylic acid (86g, 1mol) is cooled to 15 DEG C, adds camphorsulfonic acid (4.6g, 0.02mol).2-dihydrofuran (71g, 1mol, 1.0 equivalents) is dripped in described solution.Stir after 1 hour, add saturated sodium bicarbonate (500mL), ethyl acetate (500mL) is utilized to extract, utilize magnesium sulfate in addition after drying, by insolubles filter after below 40 DEG C reduced pressure concentration, by the yellow oil decompression distillation of residue, to obtain boiling point (bp.) with the form of colorless oil be 54 DEG C/the methacrylic acid tetrahydrochysene-2H-furans-2-base ester (MATHF) 125g (productive rate is for 80%) of 3.5mmHg ~ 56 DEG C/3.5mmHg cut.
The synthesis example > of < polymer A-1
In there-necked flask, add PGMEA (89g), be warming up to 90 DEG C in a nitrogen environment.In described solution with within 2 hours, to drip make MAA (becoming the amount of the 9.5mol% in all monomer components), MATHF (becoming the amount of the 43mol% in all monomer components), GMA (being equivalent to the 47.5mol% in all monomer components), V-65 (relative to all monomer components total amount 100mol% and be equivalent to 4mol%) be at room temperature dissolved in solution in PEGMEA (89g).Stir 2 hours at 70 DEG C after dropping terminates, reaction is terminated.Obtain polymer A-1 thus.Moreover the mode becoming 40% with the concentration of the composition (being called solid constituent) beyond solvent adjusts.
As shown in following table, change monomeric species etc., synthesize other polymkeric substance.
In described table, the numerical value not marking unit in table is especially in units of mol%.The numerical value of polymerization initiator and adjuvant is the mol% of situation monomer component being set as 100mol%.Solid component concentration represents with monomer mass/(monomer mass+solvent quality) × 100 (unit mass %).
The synthesis example > of < polymer P-1
In the flask possessing condenser pipe and stirring machine, adding 2,2 '-azo is two-(2,4-methyl pentane nitrile) 7 mass parts and diethylene glycol ethyl methyl ether 200 mass parts.Then; add methacrylic acid 12 mass parts, glycidyl methacrylate 50 mass parts, 3-(2-methacryloxyethyl) oxetanes 8 mass parts, N-N-cyclohexylmaleimide 10 mass parts, tetrahydrofurfuryl methacrylate 15 mass parts, acryloyl morpholine 5 mass parts and pentaerythrite four (3-mercaptopropionic acid ester) 2 mass parts and after carrying out nitrogen displacement, slowly start to stir.Make the temperature of solution rise to 70 DEG C, the moment reaching 70 DEG C in reaction solution temperature starts polymerization.Thereafter, auto polymerization starts after 30 minutes, drips N-N-cyclohexylmaleimide 3 mass parts in reaction solution, drips N-N-cyclohexylmaleimide 3 mass parts after 1 hour in reaction solution.Thereafter keep 3 hours, obtain the polymer solution comprising multipolymer (P-1) thus.The polystyrene conversion weight average molecular weight (Mw) of copolymer p-1 is 9,000, and molecular weight distribution (Mw/Mn) is 2.0.
About other polymkeric substance, monomer (monomer component (raw material of (a1) ~ (a3))), polymerization initiator, molecular weight adjusting agent, the solvent recorded in following table is also used to synthesize in the same manner as P-1.
In described table, the numerical value not marking unit in table is especially in units of mol%.The numerical value of polymerization initiator and adjuvant is the mol% of situation monomer component being set as 100mol%.Solid component concentration represents with monomer mass/(monomer mass+solvent quality) × 100 (unit mass %).
The preparation > of < photosensitive polymer combination
To become the mode of the solid constituent ratio recorded in following table, autohemagglutination polymer component, polymerizable monomer, (S) polymkeric substance, light acid producing agent, quinone di-azido compound, Photoepolymerizationinitiater initiater, sensitizer, alkali compounds, alkoxysilane compound containing trialkylsilyl group in molecular structure, in surfactant and other compositions, use the composition shown in each comparative example of each embodiment shown in following table respectively, in solvent (PGMEA), dissolve mixing becomes till 25% until solid component concentration, the teflon filtrator of bore 0.2 μm is utilized to filter, obtain the photosensitive polymer combination of various embodiment and comparative example.
Represent that the details of the abbreviation of each compound used in embodiment and comparative example is as follows.
(light acid producing agent)
Structure (synthesis example is by aftermentioned) shown in B-1:(is following
[changing 34]
Structure (method recorded in the paragraph 0108 according to Jap.P. spy table 2002-528451 publication is synthesized) shown in B-2:(is following
[changing 35]
B-3:PAG-103 (structure shown in following, BASF (BASF) company manufactures)
[changing 36]
((S) polymkeric substance)
S-1:X-12-981S (epoxide modified, silicone company of SHIN-ETSU HANTOTAI manufactures), weight average molecular weight is 870
S-2:X-12-984S (epoxide modified, silicone company of SHIN-ETSU HANTOTAI manufactures), weight average molecular weight is 1540
S-3:X-12-1154 (sulfhydryl modified, silicone company of SHIN-ETSU HANTOTAI manufactures), weight average molecular weight is 2510
S-4:X-12-1048 (acryl-modified, silicone company of SHIN-ETSU HANTOTAI manufactures), weight average molecular weight is 3180
S-5:X-12-972F (amino modified, silicone company of SHIN-ETSU HANTOTAI manufactures), weight average molecular weight is 1650
S-6: the structure (vinyl modified, composite) shown in following, weight average molecular weight is 2230
[changing 37]
S '-1:3-glycidoxypropyltrimewasxysilane (KBM-403, silicone company of SHIN-ETSU HANTOTAI manufactures)
S '-2:3-mercaptopropyi trimethoxy silane (KBM-803, silicone company of SHIN-ETSU HANTOTAI manufactures)
S '-3:3-acryloxypropyl trimethoxy silane (KBM-5103, silicone company of SHIN-ETSU HANTOTAI manufactures)
S '-4:3-TSL 8330 (KBM-903, silicone company of SHIN-ETSU HANTOTAI manufactures)
S '-5:(KBE-3026, silicone company of SHIN-ETSU HANTOTAI manufactures)
S '-6:(KBM-9659, silicone company of SHIN-ETSU HANTOTAI manufactures)
S '-7:(JER157S65, Mitsubishi Chemical Ind manufactures)
S '-8:(Ka Yala get (KAYARAD) DPHA, Japanese chemical drug (stock) manufactures)
(alkali compounds)
H-1: the compound of following structure
[changing 38]
(surfactant)
W-1: the non-ionic surfactant (F-554, Di Aisheng (DIC) manufacture) containing perfluoroalkyl shown in following structural formula
[changing 39]
W-2: silicone-based surfactant (" SH8400FLUID " that Dong Li-DOW CORNING (Toray-Dowcorning) (stock) manufactures)
W-3: fluorine system surfactant (FTX-218, Ni Aosi (Neos) (stock) manufactures)
(sensitizer)
DBA:9,10-dibutoxy anthracene (Kawasaki changes into company and manufactures)
(crosslinking chemical)
F-1:JER828 (manufacture of Daicel (Daicel) company)
F-2:EX-321L (long rapids (NagaseChemtex) company that changes into manufactures)
F-3: Plutarch Nat (Takenate) B870N (Mitsui Chemicals, Inc.'s manufacture)
F-4: Du draws Nat (Duranate) MF-K60X (manufacture of chemical company of Asahi Chemical Industry)
F-5: Du draws Nat (Duranate) MFA-100 (manufacture of chemical company of Asahi Chemical Industry)
(antioxidant)
F-6: this (Irganox) of gorgeous promise 1035 (manufacture of BASF (BASF) company)
F-7: this (Irganox) of gorgeous promise 1098 (manufacture of BASF (BASF) company)
(quinone di-azido compound)
Q-1:(4, the condensation product of 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride (3.0 moles))
The condensation product of Q-2:(1,1,1-tri-(p-hydroxybenzene) ethane (1.0 moles) and 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.0 moles))
(polymerizable monomer)
M-1: Ka Yala get (KAYARAD) DPHA (Japanese chemical drug (stock) manufacture)
(Photoepolymerizationinitiater initiater)
I-1: gorgeous good solid (IRGACURE) OXE02 (BASF (BASF) manufacture)
The synthesis > of <B-1
In the suspension solution of beta naphthal (10g), chlorobenzene (30mL), add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), mixed liquor be heated to 40 DEG C and react 2 hours.Under ice cooling, 4, in reactant liquor, drip the HCl aqueous solution (60mL) of 4N, add ethyl acetate (50mL) and carry out separatory.Sal tartari (19.2g) is added in organic layer, react at 40 DEG C after 1 hour, the HCl aqueous solution (60mL) of adding 2N carries out separatory, after organic layer is concentrated, utilize diisopropyl ether (10mL) by crystallization slurrying again, carry out filtering, dry and obtain ketonic compound (6.5g).
In the suspension solution of the ketonic compound (3.0g) of gained, methyl alcohol (30mL), add acetic acid (7.3g), 50 quality % aqueous hydroxylamine (8.0g), carry out adding hot reflux.After placing cooling, add water (50mL), the crystallization of separating out is filtered, to carry out after cold methanol cleaning in addition dry, obtain oxime compound (2.4g).
The oxime compound of gained (1.8g) is dissolved in acetone (20mL), adds triethylamine (1.5g), paratoluensulfonyl chloride (2.4g) under ice cooling, 4, be warming up to room temperature and react 1 hour.In reactant liquor, add water (50mL), after the crystallization of separating out is filtered, utilize methyl alcohol (20mL) to carry out slurrying again, carry out filtering, dry and obtain the compound (described structure) (2.3g) of B-1.
Moreover, B-1's 1h-nuclear magnetic resonance (NuclearMagneticResonance, NMR) spectrum (300MHz, CDCl 3) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
[table 4]
[table 5]
The evaluation > of adherence after < baking
On the glass substrate being formed with Mo (molybdenum) film after each photosensitive polymer combination of spin application, at 90 DEG C, on hot plate, carry out 120 seconds kind prebake conditions and solvent is volatilized, forming the photosensitive polymer combination layer of thickness 3.0 μm.Then, extra-high-pressure mercury vapour lamp is used to become 300mJ/cm with accumulative exposure 2(energy intensity: 20mW/cm 2, i ray) mode expose, thereafter, by described substrate in an oven at 230 DEG C heat 30 minutes, obtain cured film.
Then, cutter (cutter) are used to cured film, otch is cut in length and breadth with the interval of 1mm, adhesive tape (scotchtape) is used to carry out belt stripping test (100 lattice cross-cut methods: according to Japanese Industrial Standards (JapaneseIndustrialStandards, JIS) 5600).The adherence between cured film and substrate is evaluated according to the area of the cured film be transferred on the adhesive tape back side.The results are shown in following table.Numerical value is less then higher with the adherence of basal substrate, and more than 3 is realistic scale.
5: the area of transfer printing is less than 1%
4: the area of transfer printing is more than 1% and is less than 5%
3: the area of transfer printing is more than 5% and is less than 10%
2: the area of transfer printing is more than 10% and is less than 50%
1: the area of transfer printing is more than 50%
The evaluation > of the adherence after < high temperature and humidity test
On the glass substrate being formed with Mo (molybdenum) film after each photosensitive polymer combination of spin application, at 90 DEG C, on hot plate, carry out 120 seconds prebake conditions and solvent is volatilized, forming the photosensitive polymer combination layer that thickness is 3.0 μm.Then, extra-high-pressure mercury vapour lamp is used to become 300mJ/cm with accumulative exposure 2(energy intensity: 20mW/cm 2, i ray) mode expose, thereafter, described substrate is heated 30 minutes and obtain cured film in an oven at 230 DEG C.By the substrate after baking through being adjusted to 100 DEG C, leaving standstill 24 hours under the environment of RH100%.
Then, cutter are used to cured film, cuts otch in length and breadth with the interval of 1mm, use adhesive tape to carry out belt stripping test (100 lattice cross-cut methods: according to JIS5600).The adherence between cured film and substrate is evaluated according to the area of the cured film be transferred on the adhesive tape back side.The results are shown in following table.Numerical value is less then higher with the adherence of basal substrate, and more than 3 is realistic scale.
5: the area of transfer printing is less than 1%
4: the area of transfer printing is more than 1% and is less than 5%
3: the area of transfer printing is more than 5% and is less than 10%
2: the area of transfer printing is more than 10% and is less than 50%
1: the area of transfer printing is more than 50%
The evaluation > of < sensitivity
By glass substrate (Iger (EAGLE) XG, 0.7mm thick (manufacture of healthy and free from worry (Corning) company)) under hexamethyldisilazane (HMDS) steam, exposed for 30 seconds, after each photosensitive polymer combination of spin application, carry out on hot plate at 90 DEG C 120 second prebake conditions and solvent is volatilized, form the photosensitive polymer combination layer that thickness is 3.0 μm.
Then, to the MPA5500CF (high-pressure mercury-vapor lamp) that the photosensitive polymer combination layer of gained uses Canon (Canon) (stock) to manufacture, being situated between exposes every set mask.Then, after utilizing alkaline developer (the tetramethyl ammonium hydroxide aqueous solution of 0.4%) to carry out development in 60 seconds to the photosensitive polymer combination layer after exposure at 23 DEG C, ultrapure water drip washing 20 second is utilized.Using the suitableeest i x ray exposure x amount (Eopt) when being resolved the hole of 5 μm by these operations as sensitivity.
5: be less than 20mJ/cm 2
4:20mJ/cm 2above and be less than 40mJ/cm 2
3:40mJ/cm 2above and be less than 80mJ/cm 2
2:80mJ/cm 2above and be less than 160mJ/cm 2
1:160mJ/cm 2above
The evaluation > of < hole cone-shaped
By glass substrate (Iger (EAGLE) XG, 0.7mm thick (manufacture of healthy and free from worry (Corning) company)) under hexamethyldisilazane (HMDS) steam, exposed for 30 seconds, after each photosensitive polymer combination of spin application, carry out on hot plate at 90 DEG C 120 second prebake conditions and solvent is volatilized, form the photosensitive polymer combination layer that thickness is 3.0 μm.
Then, the MPA5500CF (high-pressure mercury-vapor lamp) using Canon (Canon) (stock) to manufacture to the photosensitive polymer combination layer of gained is situated between and exposes every set mask.Then, after utilizing alkaline developer (the tetramethyl ammonium hydroxide aqueous solution of 0.4%) to carry out development in 60 seconds to the photosensitive polymer combination layer after exposure at 23 DEG C, ultrapure water is utilized to carry out drip washing in 20 seconds.Thereafter, use baking oven at 230 DEG C, carry out baking in 30 minutes.
Cut off by the substrate of gained, beamship is observed to carrying out sweep electron microscope (ScanningElectronMicroscope, SEM) to described hole shape, is measured at angle formed by substrate interface portion and wall surface of the hole as cone angle.The results are shown in following table.With regard to the viewpoint of high analyticity, be preferably more than 3 points.
5: cone angle is more than 60 degree
More than 4:40 degree be less than 60 degree
More than 3:30 degree be less than 40 degree
More than 2:20 degree be less than 30 degree
1: be less than 20 degree
The evaluation > of < ease gas
By glass substrate (Iger (EAGLE) XG, 0.7mm thick (manufacture of healthy and free from worry (Corning) company)) under hexamethyldisilazane (HMDS) steam, exposed for 30 seconds, after each photosensitive polymer combination of spin application, carry out on hot plate at 90 DEG C 120 second prebake conditions and solvent is volatilized, form the photosensitive polymer combination layer that thickness is 3.0 μm.
Then, the MPA5500CF (high-pressure mercury-vapor lamp) using Canon (Canon) (stock) to manufacture to the photosensitive polymer combination layer of gained is situated between and exposes every set mask.Then, after utilizing alkaline developer (the tetramethyl ammonium hydroxide aqueous solution of 0.4%) to carry out development in 60 seconds to the photosensitive polymer combination layer after exposure at 23 DEG C, ultrapure water is utilized to carry out drip washing in 20 seconds.Thereafter, use baking oven at 230 DEG C, carry out baking in 30 minutes.
The cured film of scraping gained, utilize thermogravimetric analyzer (ThermoGravimetricAnalyzer, TGA) weight phenomenon amount is analyzed under the condition of analytical equipment (manufacture of Q-5000SA, TA instrument (TAInstruments) company) under programming rate 10 DEG C/min, maintenance temperature 230 DEG C, 60 minutes retention times, nitrogen environment.
5: weight minimizing is less than 1%
4: weight is reduced to more than 1% and is less than 3%
3: weight is reduced to more than 3% and is less than 5%
2: weight is reduced to more than 5% and is less than 10%
1: weight is reduced to more than 10%
< solution conservatory evaluation >
By the keeping at-20 DEG C of allocated photosensitive polymer combination, evaluate until solution starts to become the muddy time.
More than 5:6 month
More than 4:3 month and be less than 6 months
More than 3:1 month and be less than 3 months
More than 2:2 week be less than 1 month
1: be less than 2 weeks
[table 6]
[table 7]
[table 8]
Learnt by described table, containing in the embodiment 1 ~ embodiment 57 of (S) polymkeric substance, adherence, sensitivity, hole cone-shaped, ease gas and solution keeping quality all become good result.Learn relative to this, not containing (S) polymkeric substance comparative example 1, comparative example 10, not only adherence is poor for comparative example 15, and hole cone-shaped and escape gas also poor.And learn, use alkoxy and group (X) be respectively S '-1 ~ S '-4 of simple function comparative example 2 ~ comparative example 5, comparative example 11 ~ comparative example 14, also not only adherence is poor for comparative example 16 ~ comparative example 19, and hole cone-shaped and the gas that escapes also poor.And learn, use there is not group (X) and have the S '-5 of multifunctional alkoxy, the comparative example 6 of S '-6, comparative example 7 adherence poor.Learn in addition, use there is not alkoxy and the adherence of group (X) comparative example 8 that is polyfunctional S '-7, S '-8, comparative example 9 and hole cone-shaped poor.
Learn according to embodiment 11, embodiment 12, embodiment 13, embodiment 48, embodiment 49, embodiment 56 and embodiment 57, by the group (X) in (S) polymkeric substance is set as epoxy radicals or sulfydryl, adherence improves further.In addition, learn according to embodiment 10, embodiment 12, embodiment 47, embodiment 49, embodiment 55 and embodiment 57, by the group (X) in (S) polymkeric substance being set as the group beyond sulfydryl or amino, solution keeping quality improves further.
In addition, learn according to embodiment 24, embodiment 25, embodiment 27 and embodiment 28, by being set as in given area by the allotment amount of (S) polymkeric substance, effect of the present invention improves further.Learnt by these situations, about group (X), excellent with the order of the double bond bases such as epoxy radicals, sulfydryl, (methyl) acryloyl group, amino.
The making > of < display device
(embodiment 101)
Utilize following methods to make the organic EL display (with reference to Fig. 1) using thin film transistor (TFT) (TFT).
Glass substrate 6 is formed the TFT1 of bottom gate type, is formed with the state covering described TFT1 and comprise Si 3n 4dielectric film 3.Then, formed in described dielectric film 3 after omitting illustrated contact hole herein, the distribution 2 (being highly 1.0 μm) being connected to TFT1 via described contact hole is formed on dielectric film 3.Described distribution 2 is the distribution in order to connecting between TFT1 or be connected with TFT1 by the organic EL formed in subsequent step.
And then, in order to make, because of the concavo-convex planarization formed caused by distribution 2, to form planarization film 4 on the insulating film 3 with the concavo-convex state of landfill caused by distribution 2.The formation of planarization film 4 is on the insulating film 3 by the photosensitive polymer combination slot coated of embodiment 1 on substrate, after hot plate carries out prebake conditions (90 DEG C, 2 minutes), uses high-pressure mercury light irradiation 45mJ/cm above mask 2(illumination is 20mW/cm 2) i ray (365nm) after, utilize alkaline aqueous solution to carry out developing and forming pattern, at 230 DEG C, carry out the heating of 60 minutes.
Coating during photosensitive resin coating composition well, in exposure, development, is calcined in the cured film of rear gained, generation of arriving gauffer or be full of cracks unconfirmed.And then the average jump of distribution 2 is 500nm, the thickness of made planarization film 4 is 2,000nm.
Then, the planarization film 4 of gained is formed the organic EL of bottom emission type.First, on planarization film 4, be connected to distribution 2 via contact hole 7 and form the first electrode 5 comprising ITO.Thereafter, be coated with commercially available resist and carry out prebake conditions, the mask be situated between every required pattern exposes, and develops.Using described Resist patterns as mask, carry out pattern processing by using the Wet-type etching of ITO etchant.Thereafter, anticorrosive additive stripping liquid controlling (removing liquid (Remover) 100, AZ Electronic Materials Corp to manufacture) is used to be peeled off by described Resist patterns at 50 DEG C.First electrode 5 of gained like this is equivalent to the anode of organic EL.
Then, the dielectric film 8 of the shape at the edge of covering first electrode 5 is formed.About dielectric film 8, use the photosensitive polymer combination of embodiment 1, utilize method same as above to form dielectric film 8.By arranging described dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and its subsequent step can be prevented.
And then, in vacuum deposition apparatus, be situated between every required pattern mask sequentially evaporation hole transmission layer, organic luminous layer, electron transfer layer are set.Then, whole of surface forms the second electrode comprising A1.The described substrate of gained is taken out in evaporator, uses glass for sealing plate and ultraviolet ray hardening type epoxy resin to fit, seal thus.
Obtain the organic EL display of the active array type each organic EL being connected to the TFT1 in order to drive described organic EL as described above.Apply voltage via driving circuit, result demonstrates good display characteristic, learns that it is the organic EL display that reliability is high.
(embodiment 102)
In embodiment 101, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 16, in addition, make organic EL display in the same manner as embodiment 101.Apply driving voltage to the organic EL display of gained, result demonstrates good display characteristic, learns that it is the organic EL display that reliability is high.
(embodiment 103)
In embodiment 101, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 23, in addition, make organic EL display in the same manner as embodiment 101.Apply driving voltage to the organic EL display of gained, result demonstrates good display characteristic, learns that it is the organic EL display that reliability is high.
(embodiment 104)
In embodiment 101, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 30, in addition, make organic EL display in the same manner as embodiment 101.Apply driving voltage to the organic EL display of gained, result demonstrates good display characteristic, learns that it is the organic EL display that reliability is high.
(embodiment 105)
In embodiment 101, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 34, in addition, make organic EL display in the same manner as embodiment 101.Apply driving voltage to the organic EL display of gained, result demonstrates good display characteristic, learns that it is the organic EL display that reliability is high.
(embodiment 106)
In the active array type LCD recorded in Fig. 1 of Jap.P. No. 3321003 publication, form cured film 17 as described below as interlayer dielectric, obtain the liquid crystal indicator of embodiment 106.That is, use the photosensitive polymer combination of embodiment 1, utilize the method identical with the formation method of the planarization film 4 of the organic EL display in described embodiment 101, form cured film 17 as interlayer dielectric.
Apply driving voltage to the liquid crystal indicator of gained, result demonstrates good display characteristic, learns that it is the liquid crystal indicator that reliability is high.
(embodiment 107)
In embodiment 106, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 16, in addition, make liquid crystal indicator in the same manner as embodiment 106.Apply driving voltage to the liquid crystal indicator of gained, result demonstrates good display characteristic, learns that it is the liquid crystal indicator that reliability is high.
(embodiment 108)
In embodiment 106, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 23, in addition, make liquid crystal indicator in the same manner as embodiment 106.Apply driving voltage to the liquid crystal indicator of gained, result demonstrates good display characteristic, learns that it is the liquid crystal indicator that reliability is high.
(embodiment 109)
In embodiment 106, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 30, in addition, make liquid crystal indicator in the same manner as embodiment 106.Apply driving voltage to the liquid crystal indicator of gained, result demonstrates good display characteristic, learns that it is the liquid crystal indicator that reliability is high.
(embodiment 112)
In embodiment 106, the photosensitive polymer combination of embodiment 1 is changed into the photosensitive polymer combination of embodiment 34, in addition, make liquid crystal indicator in the same manner as embodiment 106.Apply driving voltage to the liquid crystal indicator of gained, result demonstrates good display characteristic, learns that it is the liquid crystal indicator that reliability is high.
The explanation of symbol
1:TFT (thin film transistor (TFT))
2: distribution
3: dielectric film
4: planarization film
5: the first electrodes
6: glass substrate
7: contact hole
8: dielectric film
10: liquid crystal indicator
12: back light unit
14,15: glass substrate
16：TFT
17: cured film
18: contact hole
19:ITO transparency electrode
20: liquid crystal
22: colored filter

Claims (15)

1. a photosensitive polymer combination, contains:
(A-1) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a1-1), there is the polymkeric substance that the structural unit of the group that acidic group is protected through sour decomposability base and (a1-2) have the structural unit of bridging property base,
(2) containing (a1-1), there is the polymkeric substance of the structural unit of the group that acidic group is protected through sour decomposability base and there is containing (a1-2) polymkeric substance of the structural unit of bridging property base;
(B-1) light acid producing agent;
(C-1) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino;
In general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.
2. a photosensitive polymer combination, contains:
(A-2) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a2-1), there is the polymkeric substance that the structural unit of acidic group and (a2-2) have the structural unit of bridging property base,
(2) containing (a2-1), there is the polymkeric substance of the structural unit of acidic group and there is containing (a2-2) polymkeric substance of the structural unit of bridging property base;
(B-2) quinone di-azido compound;
(C-2) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino;
In general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.
3. a photosensitive polymer combination, contains:
(A-3) polymerizable monomer;
(B-3) Photoepolymerizationinitiater initiater;
(A-4) component of polymer of the polymkeric substance of at least one meeting following (1) and (2) is comprised,
(1) containing (a4-1), there is the polymkeric substance that the structural unit of acidic group and (a4-2) have the structural unit of bridging property base,
(2) containing (a4-1), there is the polymkeric substance of the structural unit of acidic group and there is containing (a4-2) polymkeric substance of the structural unit of bridging property base;
(C-3) solvent; And
(S) structural unit containing the part-structure had represented by following general formula (1) with there is the polymkeric substance that at least one is selected from the structural unit of the group (X) in the cohort be made up of epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl and amino;
In general formula (1), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2.
4. photosensitive polymer combination according to any one of claim 1 to 3, wherein said group (X) is for being selected from least one in the cohort that is made up of epoxy radicals, sulfydryl and (methyl) acryloyl group.
5. photosensitive polymer combination according to any one of claim 1 to 3, wherein said group (X) is epoxy radicals.
6. photosensitive polymer combination according to any one of claim 1 to 5, wherein (S) polymkeric substance contains the structural unit represented by following general formula (I) and the structural unit represented by following general formula (II);
In general formula (I), R 1and R 2separately represent the alkyl of carbon number 1 ~ 4, n represents the integer of 0 ~ 2; R 3and R 4separately represent hydrogen atom or methyl;
In general formula (II), R 5represent epoxy radicals, sulfydryl, (methyl) acryloyl group, vinyl or amino, L 1and L 2separately the atomicity of expression singly-bound or linking part is the concatenating group of 1 ~ 6.
7. photosensitive polymer combination according to claim 6, the L in its formula of (I) 1and L 2separately represent that the atomicity of linking part is the concatenating group of 2 ~ 6.
8. photosensitive polymer combination according to any one of claim 1 to 7, wherein relative to total solid composition, the allotment amount of (S) polymkeric substance is 0.1 quality % ~ 10 quality %.
9. photosensitive polymer combination according to any one of claim 1 to 8, wherein the weight average molecular weight of (S) polymkeric substance is more than 800.
10. photosensitive polymer combination according to any one of claim 1 to 9, the bridging property base in the wherein said structural unit with bridging property base is for being selected from by epoxy radicals, oxetanylmethoxy and-NH-CH 2at least one in the cohort that group represented by-O-R forms; Wherein, R represents the alkyl of hydrogen atom or carbon number 1 ~ 20.
11. photosensitive polymer combinations according to any one of claim 1,4 to 10, wherein (B-1) light acid producing agent is oxime sulfonate compounds and/or salt compound.
The manufacture method of 12. 1 kinds of cured films, comprising:
(1) photosensitive polymer combination according to any one of claim 1 to 11 is coated the step on substrate;
(2) in the described photosensitive polymer combination be coated with, remove the step of solvent;
(3) step that active radioactive ray expose the described resin combination eliminating solvent is utilized;
(4) step that aqueous developer solution is developed to the described resin combination through exposure is utilized; And
(5) baking procedure after thermmohardening is carried out to the described resin combination through development.
13. 1 kinds of cured films, it the photosensitive polymer combination according to any one of claim 1 to 11 is hardened form.
14. cured films according to claim 13, it is interlayer dielectric.
15. liquid crystal indicator or an organic EL display, there is the cured film according to claim 13 or 14.
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)

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