CN103226290B - Photosensitive polymer combination, the forming method of cured film, cured film, organic electroluminescence display device and method of manufacturing same and liquid crystal display device - Google Patents

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

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Publication number
CN103226290B
CN103226290B CN201310037511.6A CN201310037511A CN103226290B CN 103226290 B CN103226290 B CN 103226290B CN 201310037511 A CN201310037511 A CN 201310037511A CN 103226290 B CN103226290 B CN 103226290B
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ingredient
base
structural unit
photosensitive polymer
formula
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CN103226290A (en
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崎田享平
川岛敬史
山田悟
米泽裕之
柏木大助
安藤豪
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The purpose of the present invention is to provide forming method, cured film, organic electroluminescence display device and method of manufacturing same and the liquid crystal display device of the substrate adhesion after hardening is excellent, can inhibit pattern heat flow photosensitive polymer combination, cured film.It is 130 compound and (ingredient D) solvent less than 1,000 that the photosensitive polymer combination of the present invention, which is characterized in that the ingredient, (ingredient B) photoacid generator, (the ingredient C) that meet following (1) or (2) containing (ingredient A) have 1 or more 8 or less acidic groups molecular weight of residue made of the protection of sour decomposability base,.(1) include the polymer of (a1) with the acidic group structural unit of structural unit and (a2) with bridging property base of residue made of the protection of sour decomposability base.(2) include (a1) have acidic group by sour decomposability base protection made of residue structural unit polymer and comprising (a2) structural unit with bridging property base polymer.

Description

Photosensitive polymer combination, the forming method of cured film, cured film, organic electroluminescence hair Electro-optical display device and liquid crystal display device
Technical field
The present invention relates to a kind of photosensitive polymer combination, the forming method of cured film, cured film, organic electroluminescents (Electro Luminescence, EL) display device and liquid crystal display device.
Background technology
It is equipped in organic EL display device or liquid crystal display device etc. and forms figuratum interlayer dielectric.In the interlayer In the formation of insulating film, from it is necessary to obtain pattern form the number of steps of it is few and obtain sufficient flatness etc. Consider, photosensitive polymer combination is widely used.
Figuratum interlayer dielectric or planarization film are formed for using photosensitive polymer combination as described above, Other than the transparency, also require its be to the pattern of electrode formation used in etching solution or anticorrosive additive stripping liquid controlling it is resistance to By the high cured film of reliabilities such as property (solvent resistance) or liquid crystal pollution (electrical characteristic) be excellent.Moreover, in recent years in order to make Organic EL display device or the display characteristic that liquid crystal display device is fine, also requirement can have no photosensitive polymer combination It is unevenly coated on substrate, and there is high-resolution.Moreover, it has been known that there is patent documents 1 for existing photosensitive polymer combination Recorded photosensitive polymer combination in~patent document 3.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2000-298344 bulletins
[patent document 2] Japanese Patent Laid-Open 6-167811 bulletins
[patent document 3] Japanese Patent Laid-Open 2011-221494 bulletins
Invention content
It is excellent the purpose of the present invention is to provide the substrate adhesion after hardening and can inhibit the photosensitive of the heat flow of pattern Property resin combination.
The above subject of the present invention can be by below<1>、<7>、<9>、<11>Or<12 >In recorded means and solve Certainly.With as preferred embodiment<2>~<6>、<8>And<10>It is described below together.
<1>A kind of photosensitive polymer combination, it is characterised in that contain：
Ingredient, (ingredient B) photoacid generator, (the ingredient C) that (ingredient A) meets following (1) or (2) have 1 or more acid Compound and (ingredient D) solvent of the molecular weight of residue made of base is protected by sour decomposability base less than 1,000,
(1) structural unit of residue and (a2) are with crosslinking made of being protected by sour decomposability base with acidic group comprising (a1) The polymer of the structural unit of property base,
(2) include (a1) have acidic group by sour decomposability base protect made of residue structural unit polymer and comprising (a2) polymer of the structural unit with bridging property base；
<2>According to above-mentioned<1>The photosensitive polymer combination, it is characterised in that：
Ingredient C is the molecular weight of residue made of being protected by sour decomposability base with 1 or more carboxyl and/or phenolic hydroxyl group Compound less than 1,000；
<3>According to above-mentioned<1>Or<2>The photosensitive polymer combination, it is characterised in that：
Photosensitive polymer combination is chemically amplified positive photosensitive polymer combination；
<4>According to above-mentioned<1>~<3>Any one of described in photosensitive polymer combination, it is characterised in that：
Ingredient C is protected by the base represented by following formula (c1) or formula (c2) with 1 or more carboxyl and/or phenolic hydroxyl group Made of residue molecular weight be less than 1,000 compound,
[changing 1]
(in formula (c1) and formula (c2), R1、R2、R4And R5Separately indicate hydrogen atom or alkyl, wherein R1With R2It is Except the case where hydrogen atom, R3Indicate can also there is heteroatomic alkyl or aryl, R6Expression can also have heteroatomic alkylene The divalent concatenating group that base, arlydene or the base are composed, R1Or R2With R3Also it can link and form cyclic ether)；
<5>According to above-mentioned<4>The photosensitive polymer combination, it is characterised in that：
Ingredient C is the compound represented by following formula (c3) or formula (c4),
[changing 2]
(in formula (c3) and formula (c4), R7It indicates also to may include the n valency alkyls that the carbon number of O atom or S atom is 1~16, R8 And R9Separately expression-COO- or-O-, R10It separately indicates also to may include that the carbon number of O atom or S atom is 1~8 1 valency alkyl, X1Separately indicate the base represented by the formula (c1), X2Indicate the base represented by the formula (c2), n tables Show 2) 1~3 integer, m indicate；
<6>According to above-mentioned<1>~<5>Any one of described in photosensitive polymer combination, it is characterised in that：
Ingredient C is that the molecular weight of residue made of being protected by sour decomposability base with 1 or more aliphatic carboxylic is less than 1, 000 compound；
<7>A kind of forming method of cured film, it is characterised in that comprise the following steps：(1) application step, will be according to above-mentioned <1>~<6>Any one of described in photosensitive polymer combination be coated on substrate；(2) solvent removal stage, from what is be coated with Solvent is removed in photosensitive polymer combination；(3) step of exposure, using actinic ray to the photosensitive resin composition of removing solvent Object is exposed；(4) development step develops to the photosensitive polymer combination after exposure using aqueous developer；And (5) post-baking step carries out thermmohardening to the photosensitive polymer combination after development；
<8>According to above-mentioned<7>The forming method of the cured film, it is characterised in that comprise the following steps：
After the development step and before post-baking step, to including the substrate of the photosensitive polymer combination after development The step of carrying out blanket exposure；
<9>A kind of cured film, it is characterised in that：
Cured film is utilized according to above-mentioned<7>Or<8>The forming method of the cured film and formed；
<10>Root is above-mentioned<9>The cured film, it is characterised in that：
Cured film is interlayer dielectric；
<11>A kind of organic EL display device, it is characterised in that include：
According to above-mentioned<9>Or<10>The cured film；
<12>A kind of liquid crystal display device, it is characterised in that include：
According to above-mentioned<9>Or<10>The cured film.
It is excellent according to the present invention can provide the substrate adhesions after hardening, can inhibit the photoresist of the heat flow of pattern Composition.
Description of the drawings
Fig. 1 is the composition concept map of an example for indicating organic EL display device.Indicate the organic EL displays dress of bottom emission type The model utility sectional view of substrate in setting, including planarization film 4.
Fig. 2 is the composition concept map of an example for indicating liquid crystal display device.Indicate the active-matrix in liquid crystal display device The model utility sectional view of substrate has the cured film 17 as interlayer dielectric.
[explanation of symbol]
1、16：TFT (thin film transistor (TFT))
2：Wiring
3、8：Insulating film
4：Planarization film
5：First electrode
6、14、15：Glass substrate
7、18：Contact hole
10：Liquid crystal display device
12：Back light unit
17：Cured film
19：Ito transparent electrode
20：Liquid crystal
22：Colored filter
Specific implementation mode
Hereinafter, the present invention is described in detail.
In addition, in the present invention, indicate the record of " lower limit~upper limit " of numberical range indicate " it is more than lower limit, the upper limit with Under ", the record of " upper limit~lower limit " indicates " below the upper limit, more than lower limit ".Also that is, indicating the numerical value model comprising the upper limit and lower limit It encloses.Moreover, by " (ingredient A) meets the ingredient of (1) or (2) " etc. referred to as " ingredient A " etc., by " (a1) has acidic group by sour point Structural unit of residue made of Xie Xingji protections " etc. is referred to as " structural unit (a1) " etc..
In addition, in the statement of base (atomic group) in the present specification, substituted and unsubstituted statement is not recorded and is wrapped Base (atomic group) containing the base (atomic group) for not having substituent group and with substituent group.Such as so-called " alkyl " includes not only not Have the alkyl (unsubstituted alkyl) of substituent group, and includes the alkyl (substituted alkyl) with substituent group.
Moreover, the method for the structural unit contained by the polymer imported used in the present invention can be polymerization, It can be high molecular weight reactive method.In polymerization, after the pre-synthesis monomer containing regulation functional group, those monomers is made to be copolymerized. In high molecular weight reactive method, after carrying out polymerisation, reactive base contained in the structural unit using the polymer of gained and Necessary functional group is directed into structural unit.Herein, functional group can illustrate：To in the protection acid such as carboxyl or phenolic hydroxyl group Protecting group, epoxy group or the oxa- ring fourth decomposed in the presence of acid, preferably strong acid while base and keep those acidic groups free The bridging properties such as base base and alkali-soluble base (acidic group) etc. as phenolic hydroxyl group or carboxyl.
(photosensitive polymer combination)
The photosensitive polymer combination (being also referred to simply as below " resin combination ") of the present invention is characterized in that：(at Point A) there is 1 or more acidic group to be protected the ingredient, (ingredient B) photoacid generator, (the ingredient C) that meet following (1) or (2) Residue molecular weight less than 1,000 compound and (ingredient D) solvent.
(1) structural unit of residue and (a2) are with crosslinking made of being protected by sour decomposability base with acidic group comprising (a1) The polymer of the structural unit of property base
(2) include (a1) have acidic group by sour decomposability base protect made of residue structural unit polymer and comprising (a2) polymer of the structural unit with bridging property base
The ingredient of (1) described in satisfaction is the polymer for having together structural unit (a1) and structural unit (a2), meets institute The ingredient for stating (2) be have the polymer of structural unit (a1) with the polymer of structural unit (a2), (2) described in satisfaction Embodiment is the embodiment at least having 2 kinds of polymer.
The photosensitive polymer combination of the present invention is positive type photosensitive organic compound.Moreover, the photonasty tree of the present invention Oil/fat composition is preferably positive type photosensitive organic compound (the chemically amplified positive photosensitive resin composition of chemical amplification type Object).
Hereinafter, sequentially illustrating the preferred embodiment of each ingredient about the photosensitive polymer combination of the present invention.
(ingredient A) meets the ingredient of (1) or (2)
The photosensitive polymer combination of the present invention contains the ingredient that (ingredient A) meets following (1) or (2).
(1) structural unit of residue and (a2) are with crosslinking made of being protected by sour decomposability base with acidic group comprising (a1) The polymer of the structural unit of property base
(2) include (a1) have acidic group by sour decomposability base protect made of residue structural unit polymer and comprising (a2) polymer of the structural unit with bridging property base
From from the viewpoint of intermiscibility, photosensitive polymer combination of the invention preferably comprises the ingredient of (1) described in satisfaction As ingredient A.
On the other hand, from from the viewpoint of the degree of freedom of MOLECULE DESIGN, photosensitive polymer combination of the invention preferably contains There is the ingredient of (2) described in meeting as ingredient A.
In addition, containing the ingredient of (1) described in satisfaction, also can further contain has acidic group quilt comprising (a1) The polymer of the structural unit of residue made of sour decomposability base protection and/or the structural unit comprising (a2) with bridging property base Polymer.
Moreover, containing the ingredient of (2) described in satisfaction, further contain has acidic group by acid point comprising (a1) The structural unit of residue and (a2) made of Xie Xingji protections have the case where polymer of the structural unit of bridging property base suitable In containing the ingredient of (1) described in satisfaction the case where.
Polymer in ingredient A is preferably the resin of addition polymerization type, more preferably include be originated from (methyl) acrylic acid and/ Or the polymer of the structural unit of its ester.In addition, the structure list other than the structural unit from (methyl) acrylic acid and/or its ester Member also may include the structural unit for example originating from styrene or the structural unit etc. from vinyl compound.
Polymer in ingredient A is preferably with respect to the source containing 50 moles of % or more for all structural units of polymer Particularly preferably include only source from (methyl) acrylic acid and/or the structural unit of its ester, further preferably 90 moles of % or more From (methyl) acrylic acid and/or the polymer of the structural unit of its ester.
It is known as " structural acrylic unit " in addition, also " (methyl) acrylic acid and/or the structural unit of its ester will be originated from ". Moreover, " (methyl) acrylic acid " expression " methacrylic acid and/or acrylic acid ".
Polymer in ingredient A can also contain it other than the structural unit (a1) and/or structural unit (a2) His structural unit (a3).
Polymer in ingredient A is preferably alkali-insoluble, and the preferably sour decomposability possessed by structural unit (a1) Base becomes the resin of alkali-soluble when decomposing.Herein, so-called sour decomposability base is the function for indicating to decompose in the presence of acid Base.Also that is, the structural unit of protected carboxyl made of being protected by sour decomposability base with carboxyl causes to protect due to acid Base decomposes, therefore produces carboxyl, and with phenolic hydroxyl group protected phenolic hydroxyl group made of the protection of sour decomposability base Structural unit cause protecting group to decompose due to acid, produce phenolic hydroxyl group.Herein, so-called " alkali in the present invention Solubility " refers to by the solution coating of the compound (resin) in the chemical combination on substrate, heating 2 minutes and being formed at 90 DEG C The film (thickness be 3 μm) of object (resin) is for the solution rate of 23 DEG C of 0.4 mass % tetramethylammonium hydroxide aqueous solutions 0.01 μm/sec or more, it is so-called it is " alkali-insoluble " refer to by the solution coating of the compound (resin) on substrate, 90.At DEG C Heating 2 minutes and the film (thickness be 3 μm) of the compound (resin) that is formed are for 23.DEG C 0.4 mass % tetramethyl hydrogen The solution rate for aoxidizing aqueous ammonium is less than 0.01 μm/sec.
Polymer in ingredient A also may include aftermentioned from carboxyl, the structural unit of carboxylic acid anhydrides and/or with phenol hydroxyl Other structures unit of base etc..Wherein, in the case where importing acidic groups, preferably polymer entirety is remained it is alkali-insoluble In the range of import.
Hereinafter, being illustrated respectively to structural unit (a1), structural unit (a2).
<(a1) structural unit of residue made of being protected by sour decomposability base with acidic group>
At least one kind of of polymer in ingredient A has acidic group residue made of the protection of sour decomposability base comprising (a1) Structural unit.
(a1) acidic group in the structural unit of residue made of being protected by sour decomposability base with acidic group can enumerate carboxyl, phenol Property hydroxyl, sulfonic group, phosphate and hydroxyl fluoroalkyl etc..Wherein preferred carboxyl and/or phenolic hydroxyl group.
Moreover, the structural unit of (a1) with acidic group residue made of the protection of sour decomposability base is more preferably with sour The structural unit of protected carboxyl made of the protection of decomposability base has protected made of the protection of sour decomposability base The structural unit of phenolic hydroxyl group.
The resin combination of the present invention is used as ingredient A by containing the polymer comprising structural unit (a1), can be made into sense The extremely high photosensitive polymer combination of luminosity.
Hereinafter, sequentially respectively to the structural unit (a1- with protected carboxyl made of being protected by sour decomposability base 1) it, is illustrated with the structural unit (a1-2) with protected phenolic hydroxyl group made of being protected by sour decomposability base.
<<(a1-1) there is the structural unit of protected carboxyl made of being protected by sour decomposability base>>
The structural unit (a1-1) with protected carboxyl made of being protected by sour decomposability base is with as follows The structural unit of protected carboxyl：The carboxyl of structural unit with carboxyl is by sour decomposability explained in detail below Protected carboxyl made of base protection.
It is described to have the structural unit (a1-1) of the protected carboxyl made of the protection of sour decomposability base is middle can be used The structural unit with carboxyl, can there is no particular restriction ground use well known structural unit.
Structural unit-with carboxyl
Structural unit with carboxyl can for example enumerate the structural unit from following compound：Unsaturated monocarboxylic, no Saturated dicarboxylic acid, unsaturated tricarboxylic acids etc. have the unsaturated carboxylic acid etc. of at least one carboxyl in the molecule.
Act person set forth below can be used in unsaturated carboxylic acid to obtain the structural unit with carboxyl.Also that is, it is unsaturated Monocarboxylic acid is such as can enumerate acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid.Moreover, unsaturated dicarboxyl Acid is such as can enumerate maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid.Moreover, to obtain the monomer with carboxyl The unsaturated polybasic carboxylic acid of unit can also be its acid anhydrides.Maleic anhydride, itaconic anhydride, citraconic anhydride can specifically be enumerated Deng.Moreover, unsaturated polybasic carboxylic acid can also be list (2- methacryloxyalkyls) ester of polybasic carboxylic acid, such as can enumerate Mono succinate (2- acryloyl-oxyethyls) ester, mono succinate (2- methacryloxyethyls) ester, phthalic acid list (2- Acryloyl-oxyethyl) ester, phthalic acid list (2- methacryloxyethyls) ester etc..
In addition, unsaturated polybasic carboxylic acid can also be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, example ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates can such as be enumerated.
Moreover, unsaturated carboxylic acid can also use acrylic acid -2- carboxyethyls, methacrylic acid -2- carboxyethyls, Malaysia Sour monoalkyl ester, monoalkyl esters, 4- carboxyl styrenes etc..
Wherein, from the viewpoint of autography, in order to form the structural unit with carboxyl, it is preferable to use acrylic acid, first The acid anhydrides etc. of base acrylic acid or unsaturated polybasic carboxylic acid, more preferably uses acrylic or methacrylic acid.
Structural unit with carboxyl can include individually a kind, can also include two or more.
Moreover, the structural unit with carboxyl can also be the knot of monomeric unit and anhydride reaction and gained with hydroxyl Structure unit.
Well known acid anhydrides can be used in acid anhydrides, can specifically enumerate maleic anhydride, succinic anhydride, itaconic anhydride, adjacent benzene two The dibasic acid anhydrides such as formic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride；Trimellitic anhydride, equal benzene The acid anhydrides such as tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydrides.In those acid anhydrides, the viewpoint of autography is examined Consider, preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.
From the viewpoint of autography, acid anhydrides is preferably that 10 moles of %~100 are rubbed relative to the reactivity of the hydroxyl You are %, more preferably 30 moles of %~100 mole %.
Sour decomposability base-workable for institute in structural unit (a1-1)
As with it is described by sour decomposability base protect made of protected carboxyl structural unit (a1-1) in can The sour decomposability base used, can be used the base known as sour decomposability base, is not particularly limited.In previous, sour decomposability Base it has been known that there is the base for being easier to decompose due to acid (such as the acetals such as THP trtrahydropyranyl functional group) or compare be difficult to due to Sour and decomposition base (such as the tertiary butyls class such as tertiary butyl ester group, tert-butyl carbonate base functional group).
In those sour decomposability bases, basic physical properties, particularly sensitivity or pattern form, the shape of contact hole from resist Become second nature, from the viewpoint of the storage stability of photosensitive polymer combination, it is however preferred to have carboxyl by acetal form protection and At protected carboxyl structural unit.In addition, from from the viewpoint of sensitivity, carboxyl quilt is more preferably in sour decomposability base Protected carboxyl made of the form protection of acetal represented by following formula (a1-1).In addition, in carboxyl by following formula (a1- 1) in the case of protected carboxyl made of the form protection of the acetal represented by, the entirety of protected carboxyl becomes-(C =O)-O-CR101R102(OR103) structure.
[changing 3]
(in formula (a1-1), R101And R102Separately indicate hydrogen atom or alkyl, wherein R101With R102It is hydrogen atom The case where except, R103Indicate alkyl, R101Or R102Acceptable and R103Link and forms cyclic ether.)
In the formula (a1-1), R101~R103Separately indicate that hydrogen atom or alkyl, the alkyl can be straight chains It is shape, branched, cricoid any number of.Herein, R101And R102Both sides and uneven expression hydrogen atom, R101And R102At least one party's table Show alkyl.
In the formula (a1-1), R101、R102And R103In the case of indicating alkyl, abovementioned alkyl can be straight-chain, branch Shape or it is cricoid any one.
The preferred carbon number of the alkyl of the straight-chain or branched is 1~12, and more preferable carbon number is 1~6, even more preferably Carbon number is 1~4.Can specifically enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, N-pentyl, neopentyl, n-hexyl, 2,3- dimethyl -2- butyl (thexyl), n-heptyl, n-octyl, 2- ethylhexyls, positive nonyl Base, positive decyl etc..
The preferred carbon number of cyclic alkyl is 3~12, and more preferable carbon number is 4~8, and even more preferably carbon number is 4~6. The cyclic alkyl can for example enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, different ice Chip base etc..
The alkyl can also have substituent group, substituent group that can illustrate halogen atom, aryl, alkoxy.With halogen original In the case that son is used as substituent group, R101、R102And R103As alkylhalide group, with aryl as substituent group, R101、 R102And R103As aralkyl.
The halogen atom can illustrate fluorine atom, chlorine atom, bromine atom, iodine atom, and preferably fluorine atom or chlorine is former in those Son.
Moreover, the aryl that the preferred carbon number of aryl is 6~20, more preferable carbon number is 6~12.Benzene can specifically be illustrated Base, Alpha-Methyl phenyl, naphthalene etc., it is all as the alkyl being substituted with aryl, that is, aralkyl can illustrate benzyl, Alpha-Methyl benzyl Base, phenethyl, naphthyl methyl etc..
The alkoxy that the preferred carbon number of alkoxy is 1~6, the alkoxy that more preferable carbon number is 1~4 are further more excellent Select methoxy or ethoxy.
Moreover, in the case where the alkyl is naphthenic base, it is 1~10 straight-chain that the naphthenic base, which can also have carbon number, Or the alkyl of branched, as substituent group, in the case where alkyl is the alkyl of straight-chain or branched, it is 3 that can also have carbon number ~12 naphthenic base is as substituent group.
Those substituent groups also can be further substituted with such substituents as described above.
In the formula (a1-1), R101、R102And R103Indicate aryl in the case of, the preferred carbon number of aryl be 6~ 12, more preferable carbon number is 6~10.The aryl can also have substituent group, and it is 1~6 that the substituent group, which preferably illustrates carbon number, Alkyl.The aryl can for example enumerate phenyl, tolyl, xylyl (xylyl group) silylation, cumenyl, 1- naphthalenes Base etc..
Moreover, R101、R102And R103The carbon atom that can be mutually bonded and be bonded with those bases is formed together ring.R101With R102、R101With R103Or R102With R103Ring structure in the case of bond can for example enumerate cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl Base, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc..
In addition, in the formula (a1-1), preferably R101And R102Either side be hydrogen atom or methyl.
To form the free-radical polymerised of the structural unit with the protected carboxyl represented by the formula (a1-1) Commercially available free radical polymerization monomer can be used in monomer, can also be free-radical polymerised using being synthesized by well known method Monomer.Such as conjunction recorded in 0037~paragraph of paragraph 0040 of Japanese Patent Laid-Open 2011-221494 bulletins can be passed through It is synthesized at method etc..
Structural unit (a1-1) with protected carboxyl made of the protection by sour decomposability base is preferably following Shown in structural unit.
[changing 4]
(in formula, R121Indicate the alkyl that hydrogen atom or carbon number are 1~4, L1Indicate carbonyl, R122~R128Independently earth's surface Show the alkyl that hydrogen atom or carbon number are 1~4.)
Moreover, with the preferred of the structural unit (a1-1) of protected carboxyl made of the protection by sour decomposability base Concrete example can illustrate following structural units.In addition, R indicates hydrogen atom or methyl.
[changing 5]
<<(a1-2) there is the structural unit of protected phenolic hydroxyl group made of being protected by sour decomposability base>>
The structural unit (a1-2) with protected phenolic hydroxyl group made of being protected by sour decomposability base is that have The structural unit of following protected phenolic hydroxyl group：The structural unit of phenolic hydroxyl group is by sour decomposability explained in detail below Protected phenolic hydroxyl group made of base protection.
Structural unit-with phenolic hydroxyl group
The structural unit with phenolic hydroxyl group can enumerate hydroxy styrenes class formation unit or novolaks resinoid In structural unit, from the viewpoint of self-induced transparency, hydroxy styrenes or Alpha-Methyl hydroxyl are preferably originated from those structural units The structural unit of styrene.From the viewpoint of self-induced transparency, sensitivity, preferred following formula in the structural unit with phenolic hydroxyl group (a1-2) structural unit represented by.
[changing 6]
(in formula (a1-2), R220Indicate hydrogen atom or methyl, R221Indicate singly-bound or the concatenating group of divalent, R222Indicate halogen The alkyl for the straight or branched that atom or carbon number are 1~5, a indicate 1~5 integer, and b indicates 0~4 integer, a+b be 5 with Under.In addition, there are 2 or more R222In the case of, those R222Can it is mutually different also can be identical.)
In the formula (a1-2), R220Indicate hydrogen atom or methyl, preferably methyl.
Moreover, R221Indicate singly-bound or bivalence linking base.For singly-bound, sensitivity can be made to improve, and can be into One step make cured film the transparency improve because and it is preferred that.R221Bivalence linking base can illustrate alkylidene, R221For alkylidene Concrete example can enumerate methylene, ethylidene, propylidene, isopropylidene, sub- normal-butyl, isobutylidene, sub- tertiary butyl, pentylidene, Isoamylidene, sub- neopentyl, hexylidene etc..Wherein, R221Preferably singly-bound, methylene, ethylidene.Moreover, the divalent connection Base can also have substituent group, substituent group that can enumerate halogen atom, hydroxyl, alkoxy etc..
Moreover, a indicates 1~5 integer, but from from the aspect of the viewpoint of the effect of the present invention or manufacture readily, preferably a It is 1 or 2, more preferable a is 1.
Moreover, will be with R221When the carbon atom of bond is as benchmark (1), the binding site of the hydroxyl in phenyl ring is preferred To be bonded on 4.
R222It is the alkyl for the straight or branched that halogen atom or carbon number are 1~5.
Fluorine atom, chlorine atom, bromine atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl can specifically be enumerated Base, tertiary butyl, amyl, isopentyl, neopentyl etc..Wherein, from manufacture readily from the aspect of, preferably chlorine atom, bromine atom, Methyl or ethyl.
Moreover, b indicates 0 or 1~4 integer.
The sour decomposability base-that can be used in structural unit (a1-2)
As can it is described have by sour decomposability base protect made of protected phenolic hydroxyl group structural unit (a1- 2) the sour decomposability base used in, with can it is described have protected by sour decomposability base made of protected carboxyl knot Well known sour decomposability base similarly can be used in the sour decomposability base used in structure unit (a1-1), is not particularly limited. In sour decomposability base, from the basic physical properties, particularly sensitivity or pattern form of resist, the guarantor of photosensitive polymer combination From the viewpoint of depositing stability, the formative of contact hole, it is however preferred to have quilt made of phenolic hydroxyl group is protected by the form of acetal The structural unit of the phenolic hydroxyl group of protection.In addition, from from the viewpoint of sensitivity, phenolic hydroxyl group is more preferably in sour decomposability base Protected phenolic hydroxyl group made of form protection by the acetal represented by the formula (a1-1).In addition, in phenolic hydroxyl group quilt In the case of protected phenolic hydroxyl group made of the form protection of acetal represented by the formula (a1-1), protected phenol The entirety of hydroxyl becomes-Ar-O-CR101R102(OR103) structure.In addition, Ar indicates arlydene.
The preference of the acetal ester structure of phenolic hydroxyl group can illustrate R101=R102=R103=methyl or R101=R102=first Base and R103The combination of=benzyl.
Moreover, as forming protected phenolic hydroxyl group made of the form protection with phenolic hydroxyl group by acetal The free radical polymerization monomer of structural unit, such as the 1- alkoxyalkyls protective of hydroxy styrenes, hydroxy benzenes second can be enumerated The THP trtrahydropyranyl protective of alkene, 1- alkoxyalkyls protective, the Alpha-Methyl-hydroxy styrenes of Alpha-Methyl-hydroxy styrenes THP trtrahydropyranyl protective, methacrylic acid -4- hydroxylphenyl esters 1- alkoxyalkyls protective, methacrylic acid -4- hydroxyls The THP trtrahydropyranyl protective of base phenyl ester, the 1- alkoxyalkyls of 4-HBA (1- methacryloxymethyls) ester are protected Watch box, the THP trtrahydropyranyl protective of 4-HBA (1- methacryloxymethyls) ester, 4-HBA (2- first Base acryloyl-oxyethyl) ester 1- alkoxyalkyls protective, 4-HBA (2- methacryloxyethyls) ester THP trtrahydropyranyl protective, 4-HBA (3- methacryloxypropyls) ester 1- alkoxyalkyls protective, The THP trtrahydropyranyl protective of 4-HBA (3- methacryloxypropyls) ester, 4-HBA (3- methyl-props Alkene acyloxy -2- hydroxypropyls) ester 1- alkoxyalkyls protective, 4-HBA (3- methacryloxy -2- hydroxyls Base propyl) ester THP trtrahydropyranyl protective etc..
In those free radical polymerization monomers, from the viewpoint of self-induced transparency, preferred methacrylic acid -4- hydroxylphenyl esters The THP trtrahydropyranyl protective of 1- alkoxyalkyls protective, methacrylic acid -4- hydroxylphenyl esters.
The concrete example of the acetal protecting group of phenolic hydroxyl group can enumerate 1- alkoxyalkyls, such as can enumerate 1- ethyoxyl second Base, 1- methoxy ethyls, 1- n-butoxyethyls, 1- isobutoxyethies, 1- (2- chloroethoxies) ethyl, 1- (2- ethyl hexyls Oxygroup) ethyl, 1- positive propoxies ethyl, 1- cyclohexyloxies ethyl, 1- (2- cyclohexylethoxy radicals) ethyl, 1- Benzyloxyethyls Deng those bases can be used alone or two or more is applied in combination.
To form the structural unit (a1- with the protected phenolic hydroxyl group made of the protection of sour decomposability base 2) commercially available free radical polymerization monomer can be used in free radical polymerization monomer, can also use closed by well known method At free radical polymerization monomer.Such as can by make to have the compound of phenolic hydroxyl group in the presence of acid catalyst with ethylene Ether is reacted and is synthesized.Above-mentioned synthesis can also be to make to have the monomer of phenolic hydroxyl group to be copolymerized in advance with other monomers, thereafter in acid It is reacted with vinethene in the presence of catalyst.
There is the structural unit (a1-2) of protected phenolic hydroxyl group made of the protection of sour decomposability base as described Preferred concrete example can illustrate following structural units, but the present invention is not limited to those structural units.In addition, R indicates hydrogen Atom or methyl.
[changing 7]
<<The preferred embodiment of structural unit (a1)>>
Described in ingredient A is satisfaction in the case of the ingredient of (2), have acidic group by sour decomposability base comprising (a1) constituting In all monomeric units of the polymer of the structural unit of residue made of protection, the monomeric unit of structural unit (a1) is formed Content is preferably 5 moles of %~90 mole %, more preferably 20 moles of %~80 mole %.
Include (a1) constituting from from the viewpoint of sensitivity described in ingredient A is satisfaction in the case of the ingredient of (1) The structural unit of structural unit and (a2) with bridging property base of residue made of being protected by sour decomposability base with acidic group gathers In all monomeric units for closing object, the content for forming the monomeric unit of structural unit (a1) is preferably 3 moles of %~70 mole %, More preferably 10 moles of %~60 mole %.Moreover, the acid that can be especially used in the structural unit (a1) decomposes Property base be with carboxyl by acetal form protection made of protected carboxyl structural unit in the case of, composition includes (a1) structural unit of structural unit and (a2) with bridging property base of residue made of being protected by sour decomposability base with acidic group Polymer all monomeric units in formation structural unit (a1) monomeric unit content be more preferably 10 moles of %~ 40 moles of %.
It is described with by sour decomposability base protect made of protected carboxyl structural unit (a1-1) with it is described Structural unit (a1-2) with protected phenolic hydroxyl group made of being protected by sour decomposability base in comparison develops faster Feature.Therefore, in the case where wanting rapid development, it is however preferred to have protected carboxyl made of being protected by sour decomposability base Structural unit (a1-1).On the contrary, in the case where wanting to keep development slack-off, it is preferable to use with by sour decomposability base protection and At protected phenolic hydroxyl group structural unit (a1-2).
<(a2) structural unit with bridging property base>
At least one kind of of polymer in ingredient A includes the structural unit (a2) with bridging property base.
The bridging property base is then not particularly limited if the base that can generate sclerous reaction by heat treatment.It is preferred that The aspect of the structural unit with bridging property base can enumerate with selected from by oxiranyl, oxetanylmethoxy, alkoxy hydroxyl The structural unit of at least one base for the group that methyl and ethylene unsaturated group are constituted.
Wherein, the photosensitive polymer combination as the present invention, at least one kind of of polymer in more preferable ingredient A is packet Polymer containing the structural unit at least one in oxiranyl and oxetanylmethoxy particularly preferably includes to have The polymer of the structural unit of oxetanylmethoxy.Following person can more specifically be enumerated.
<<(a2-1) structural unit with oxiranyl and/or oxetanylmethoxy>>
At least one kind of structure list preferably comprised with oxiranyl and/or oxetanylmethoxy of polymer in ingredient A First (structural unit (a2-1)).The cyclic ether group of 3 Yuans rings is also known as oxiranyl, and the cyclic ether group of 4 Yuans rings also becomes Oxetanylmethoxy.
The structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy is preferably with oxiranyl And/or the structural unit of oxetanylmethoxy, more preferably there is the structural unit of oxetanylmethoxy.
The structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy in 1 structural unit if having There are at least one oxiranyl or oxetanylmethoxy, can also have 1 or more oxiranyl and 1 or more oxa- ring Butyl, 2 or more oxiranyls or 2 or more oxetanylmethoxy, are not particularly limited, and preferably have total 1~3 A oxiranyl and/or oxetanylmethoxy more preferably have total 1 or 2 oxiranyls and/or oxetanylmethoxy, Even more preferably there is 1 oxiranyl or oxetanylmethoxy.
As the concrete example of the free radical polymerization monomer to form the structural unit with oxiranyl, such as can Enumerate glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-propyl propylene Acid glycidyl ester, 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- epoxycyclohexanecarboxylates, vinylbenzyl glycidyl ether, contract to vinyl benzyl at adjacent vinylbenzyl glycidyl ether Water glycerin ether, No. 4168443 bulletins of Japanese Patent No. 0031~paragraph of paragraph 0035 in recorded contain ester ring type epoxy The compound etc. of compound skeleton.
As the concrete example of the free radical polymerization monomer to form the structural unit with oxetanylmethoxy, such as can There is oxa- ring fourth recorded in enumerating in 0011~paragraph of paragraph 0016 of Japanese Patent Laid-Open 2001-330953 bulletins (methyl) acrylate of base etc..
As forming the free radical of the structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy The concrete example of polymerizable monomer, the preferably monomer containing metacrylic acid ester structure, the monomer containing acrylate structural.
In those monomers, preferred monomer is the 0034~paragraph of paragraph 0035 of No. 4168443 bulletins of Japanese Patent No. In the recorded compound containing alicyclic epoxy object skeleton and Japanese Patent Laid-Open 2001-330953 bulletins paragraph Recorded (methyl) acrylate with oxetanylmethoxy in 0011~paragraph 0016, particularly preferred monomer are Japanese special Recorded (methyl) third with oxetanylmethoxy in 0011~paragraph of paragraph 0016 of sharp special open 2001-330953 bulletins Olefin(e) acid ester.Glycidyl methacrylate, acrylic acid -3,4- epoxycyclohexanecarboxylate, metering system are preferably in those Acid -3,4- epoxycyclohexanecarboxylates, acrylic acid (3- Ethyloxetane -3- bases) methyl esters and methacrylic acid (3- ethyl oxygen Azetidine -3- bases) methyl esters, most preferably acrylic acid (3- Ethyloxetane -3- bases) methyl esters and methacrylic acid (3- Ethyloxetane -3- bases) methyl esters.Those structural units, which can be used alone, or two or more to be applied in combination by a kind.
The structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy is preferably with selected from by following formula (a2-1-1) and the structure of group that is constituted of formula (a2-1-2).
[changing 8]
The structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy is with above-mentioned formula (a2-1-1) institute The arbitrary structures of 3 structures indicated be indicate to remove 1 or more hydrogen atom with the structure represented by the formula (a2-1-1) and The base of gained.
The structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy is more preferably with 3,4- epoxies Cyclohexyl, 2,3- epoxycyclohexyls, 2,3- epoxycyclopentyls.
[changing 9]
(in formula (a2-1-2), R1bAnd R6bSeparately indicate hydrogen atom or alkyl, R2b、R3b、R4b、R5b、R7b、R8b、 R9b、R10bSeparately indicate hydrogen atom, halogen atom, alkyl or aryl.)
In the formula (a2-1-2), R1bAnd R6bSeparately indicate hydrogen atom or alkyl, preferably hydrogen atom or carbon number For 1~8 alkyl, the alkyl (hereinafter referred to as " low alkyl group ") that more preferably hydrogen atom or carbon number are 1~5.
R2b、R3b、R4b、R5b、R7b、R8b、R9bAnd R10bSeparately indicate hydrogen atom, halogen atom, alkyl or aryl.
The halogen atom can illustrate fluorine atom, chlorine atom, bromine atom, iodine atom, more preferable fluorine atom and chlorine atom, into The more preferable fluorine atom of one step.
The alkyl can be straight-chain, branched, it is cricoid any one, and can also have substituent group.Straight-chain and branch The preferred carbon number of alkyl of chain is 1~8, and more preferable carbon number is 1~6, and even more preferably carbon number is 1~4.The cyclic alkyl It is preferred that carbon number is 3~10, more preferable carbon number is 4~8, and even more preferably carbon number is 5~7.In addition, straight-chain and branched Alkyl can also be replaced by cyclic alkyl, and cyclic alkyl can also be replaced by straight-chain and/or branched-chain alkyl.
The aryl that the preferred carbon number of aryl is 6~20, the aryl that more preferable carbon number is 6~10.
The alkyl, aryl also can further have a substituent group, alkyl the substituent group that can also have can illustrate halogen original Son, aryl, aryl the substituent group that can also have can illustrate halogen atom, alkyl.
In those bases, R2b、R3b、R4b、R5b、R7b、R8b、R9bAnd R10bSeparately be more preferably hydrogen atom, fluorine atom, The perfluoroalkyl that alkyl, phenyl or the carbon number that carbon number is 1~4 are 1~4.
Base with the structure represented by the formula (a2-1-2) preferably illustrates (3- Ethyloxetane -3- bases) Methyl.
The preferred concrete example of the structural unit (a2-1) with oxiranyl and/or oxetanylmethoxy can illustrate Following structural units.In addition, R indicates hydrogen atom or methyl.
[changing 10]
In the present invention, from from the viewpoint of sensitivity, preferred oxetanylmethoxy.Moreover, from transmissivity (transparency) Viewpoint consideration, preferably oxiranyl and oxetanylmethoxy.As can be observed from the foregoing：In the present invention, oxiranyl and/or oxygen Heterocycle butyl is preferably oxiranyl and oxetanylmethoxy, particularly preferred oxetanylmethoxy.
<<(a2-2) structural unit with ethylene unsaturated group>>
As one of the structural unit (a2) with bridging property base, the structure with ethylene unsaturated group can be enumerated Unit (a2-2) (is also known as " structural unit (a2-2) ") below.As the structural unit with ethylene unsaturated group (a2-2), preferably there is the structural unit of ethylene unsaturated group in side chain, more preferably there is ethylene unsaturated group in end And it is the structural unit of 3~16 side chain to have carbon number, even more preferably has following formula (a2-2-1) represented in side chain Base structural unit.
[changing 11]
(in formula (a2-2-1), R301Indicate that carbon number is 1~13 bivalence linking base, R302Indicate hydrogen atom or methyl, wave Line part indicates the position with the connection of the main chain of the structural unit (a2) with bridging property base.)
R301It is the bivalence linking base that carbon number is 1~13, preferably alkylidene, cycloalkylidene, arlydene or those base groups Base made of conjunction, and also may include the keys such as ester bond, ehter bond, amido bond, ammonia ester bond.Moreover, bivalence linking base can be in office Position anticipate with substituent groups such as hydroxyl, carboxyls.R301Concrete example can enumerate following bivalence linking bases.
[changing 12]
In base represented by the formula (a2-2-1), including the R301Represented divalent concatenating group and preferably aliphatic Base.
Moreover, ethylene unsaturated group is preferably with respect to ingredient A's contained in base represented by the formula (a2-2-1) Include 1 mole for total content 150g~2,000g, includes 1 mole more preferably relative to 200g~1, for 300g.
In the present invention, the structural unit (a2-2) with ethylene unsaturated group is preferably following formula (a2-2-2) Represented structural unit.
[changing 13]
(in formula (a2-2-2), R311With the R in the formula (a2-2-1)301Synonymous, preferred range is also identical.R312And R313Separately indicate hydrogen atom or methyl.)
Obtaining, there is the method for the structural unit (a2-2) of the base represented by the formula (a2-2-1) to be not particularly limited, example Free radical polymerization polymerization such as can be advanced with and generate the polymer with specific functional group, make its with with its spy Determine the base of functional group's reaction and in end there is the compound (hereinafter referred to as specific compound) of ethylene unsaturated group to react, by This can be made into the copolymer for including the structural unit (a2-2) with the base represented by the formula (a2-2-1).
Herein, the specific functional group can enumerate carboxyl, epoxy group, hydroxyl, the amino of active hydrogen, phenolic hydroxyl group, Isocyanate group etc..About for example rear institute of the monomer with specific functional group to synthesize the polymer with specific functional group It states.
The specific functional group with and the specific compound possessed by the combination of base reacted of specific functional group can arrange It lifts：The combination of carboxyl and epoxy group, the combination of carboxyl and oxetanylmethoxy, hydroxyl and isocyanate group combination, phenolic hydroxyl group The group of the combination of combination, carboxyl and isocyanate group, the combination of amino and isocyanate group, hydroxyl and acid chloride group with epoxy group Close etc..
Moreover, the specific compound can enumerate glycidyl methacrylate, glycidyl acrylate, methyl-prop Olefin(e) acid -3,4- epoxycyclohexanecarboxylate, acrylic acid -3,4- epoxycyclohexanecarboxylate, methacrylic acid isocyanatoethyl, third Olefin(e) acid isocyanatoethyl, methacrylic chloride, acryloyl chloride, methacrylic acid, acrylic acid etc..
The preferred specific functional group and the combination of the specific compound can be enumerated as the specific functional group Carboxyl is with the combination of the glycidyl methacrylate as the specific compound and as the hydroxyl of the specific functional group The combination of base and the methacrylic acid isocyanatoethyl as the specific compound.
It is exemplified below described required described with specific functional group with the polymer of specific functional group in order to obtain Monomer concrete example, but be not limited to those.
The monomer with carboxyl can for example enumerate acrylic acid, methacrylic acid, crotonic acid, phthalic acid list (2- (acryloxy) ethyl) ester, phthalic acid list (2- (methacryloxy) ethyl) ester, N- (carboxyl phenyl) Malaysia acyl Imines, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl phenyl) acrylamide etc..
The monomer with epoxy group can for example enumerate glycidyl methacrylate, glycidyl acrylate, Allyl glycidyl ether, 3- vinyl -7- oxabicyclos [4.1.0] heptane, 1,2- epoxy -5- hexenes, 1,7- octadiene lists Epoxides, methacrylic acid -3,4- epoxycyclohexanecarboxylate, acrylic acid -3,4- epoxycyclohexanecarboxylate etc..
The monomer with hydroxyl can for example enumerate 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy methacrylates, Acrylic acid -2- hydroxy-propyl esters, methacrylic acid -2- hydroxy propyl esters, acrylic acid -4- hydroxybutyls, methacrylic acid -4- hydroxyls Butyl ester, acrylic acid -2,3- dihydroxy propyl ester, methacrylic acid -2,3- dihydroxy propyl ester, diethylene glycol monoacrylate, diethyl Monomethacryiate, caprolactone -2- (methacryloxy) ethyl ester, gathers caprolactone -2- (acryloxy) ethyl ester (ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5- acryloxy -6- hydroxy norbomenes - 2- carboxyl -6- lactones, 5- methacryloxy -6- hydroxy norbomene -2- carboxyl -6- lactones etc..
The monomer of the amino with active hydrogen can enumerate acrylic acid -2- amino ethyl esters, methacrylic acid -2- amino Ethyl ester etc..
The monomer with phenolic hydroxyl group can for example enumerate hydroxy styrenes, N- (hydroxy phenyl) acrylamide, N- (hydroxyls Base phenyl) Methacrylamide, N- (hydroxy phenyl) maleimide etc..
In addition, the monomer with isocyanate group can for example enumerate isocyanic acid acryloylethyl, isocyanatomethyl Acryloylethyl, tetramethyl xylene isocyanate etc..
Moreover, in the present invention, when obtaining the polymer with specific functional group, there is particular functional by aforementioned The monomer of base with as (a1) have by sour decomposability base protection made of protected carboxyl structural unit or with sour The monomer of the structural unit of protected phenolic hydroxyl group made of the protection of decomposability base is used in combination.In addition, can and with as aftermentioned (a1) monomer of the other structures unit (a3) and other than (a2).
The method for obtaining the polymer with specific functional group used in the present invention is not particularly limited, such as It can obtain in the following way：Draw making the monomer with specific functional group, monomer in addition to this and polymerization optionally In the solvent that hair agent etc. coexists, it is made to carry out polymerisation at a temperature of 50 DEG C~110 DEG C.If at this point, used solvent For the solvable monomer for being deconstructed into the polymer with specific functional group and the solvent of the polymer with specific functional group, then have no It is particularly limited to.Concrete example can enumerate solvent recorded in aftermentioned (ingredient D) solvent.As described above and gained have it is specific The polymer of functional group is usually dissolved in the state of the solution in solvent.
Secondly, the polymer with specific functional group of gained can be made to be reacted with specific compound, obtained at the end of side chain Hold the structural unit (a2-2) with ethylene unsaturated group.At this point, usually by the solution of the polymer with specific functional group It is supplied to reaction.Such as in the solution of the acrylic polymer with carboxyl, in catalyst such as benzyltriethylammoinium chlorides In the presence of, at a temperature of 80 DEG C~150 DEG C, glycidyl methacrylate is made to react, obtain structural unit (a2- therefrom 2)。
Moreover, in order to form structural unit (a2-2), it, also can be by first other than using high molecular weight reactive as described above Base allyl acrylate, allyl acrylate etc. are used as free radical polymerization monomer.Those structural units can be used alone or Two or more is applied in combination.
<<(a2-3) structural unit with alkoxy methyl>>
As one of the structural unit (a2) with bridging property base, the structural unit with alkoxy methyl can be enumerated (a2-3) (it is also known as " structural unit (a2-3) " below).
Structural unit (a2-3) has the base represented by following formula (a2-3-1).
[changing 14]
(in formula (a2-3-1), R1Indicate carbon number be 1~20 alkyl, alkyl can branch can also form ring.)
The structural unit (a2-3) with alkoxy methyl is preferably the structure list represented by following formula (a2-3-2) Member.
[changing 15]
(in formula (a2-3-2), R1Indicate that carbon number is 1~20 alkyl, R2Indicate hydrogen atom or methyl.)
R in formula (a2-3-2)1It can be straight-chain, can also have branch, can also have ring structure.Moreover, formula (a2-3- 2) R in1Carbon number be preferably 1~9, more preferably 1~4.
R in formula (a2-3-2)1Concrete example can enumerate cyclohexyl, n-hexyl, normal-butyl, isobutyl group, methyl.It is wherein excellent Select isobutyl group, normal-butyl or methyl.
<<The preferred embodiment of structural unit (a2)>>
In all monomeric units of all polymer of composition of ingredient A, be formed by certainly the various tolerances of film with it is transparent Property from the viewpoint of, the content of monomeric unit for forming structural unit (a2) is preferably 5 moles of %~60 mole %, more preferably 10 moles of %~55 mole % are even more preferably 20 moles of %~50 mole %.
Described in ingredient A is satisfaction in the case of the ingredient of (2), structural unit that there is bridging property base comprising (a2) is constituted Polymer all monomeric units in, the content of monomeric unit for constituting structural unit (a2) is preferably that 5 moles of %~90 are rubbed You are %, more preferably 20 moles of %~80 mole %.If in above-mentioned numberical range, then obtained by photosensitive polymer combination The transparency and resistance to oxidation indium tin (ITO) sputter of cured film become good.
Described in ingredient A is satisfaction in the case of the ingredient of (1), constituting comprising (a1) there is acidic group to be protected by sour decomposability base The structural unit of residue made of shield and (a2) have in all monomeric units of the polymer of the structural unit of bridging property base, from From the viewpoint of sensitivity, the content for constituting the monomeric unit of structural unit (a2) is preferably 3 moles of %~70 mole %, more excellent It is selected as 10 moles of %~60 mole %.If in above-mentioned numberical range, then by the cured film obtained by photosensitive polymer combination The transparent and sputter of resistance to ITO becomes good.
<(a3) other structures unit>
In the present invention, the polymer of ingredient A other than the structural unit (a1) and the structural unit (a2) also It may include other structures unit (a3).
Phenylethylene, (methyl) alkyl acrylate, (first can for example be enumerated by forming the monomer of other structures unit (a3) Base) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, bicyclic unsaturated compound class, horse Come imide compound class, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic, unsaturated dicarboxyl Acid, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.
Styrene, t-butoxystyrene, methyl styrene, hydroxy styrenes, Alpha-Methyl benzene second can specifically be enumerated Alkene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, vinyl Ethyl benzoate, 4-HBA (3- methacryloxypropyls) ester, (methyl) acrylic acid, (methyl) acrylic acid first Ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) propylene The structural unit of sour isobornyl thiocyanoacetate, glycidyl methacrylate, acrylonitrile etc..Japan Patent spy can be enumerated in addition to this Open compound recorded in 0021~paragraph of paragraph 0024 of 2004-264623 bulletins.
Wherein, from from the viewpoint of film-strength, preferably have it is (final) heat treatment in structural unit (a2) or separately The other structures unit (a3) of the base of the crosslinking agent reaction of outer addition.
Specifically, it is preferable that (methyl) tertiary alkyl acrylates, more preferable (methyl) tert-butyl acrylate and (methyl) third Olefin(e) acid -2- hydroxy methacrylates, particularly preferred methacrylic acid -2- hydroxy methacrylates (HEMA).
The content of other structures unit (a3) in all monomeric units of all polymer of constituent A is preferably 1 Mole %~50 mole %, more preferably 5 moles of %~40 mole %, particularly preferably 10 moles of %~30 mole %.
Moreover, from from the aspect of sensitivity, having not in all monomeric units of all polymer of constituent A The total content of the structural unit of protected carboxyl and structural unit with unprotected phenolic hydroxyl group is preferably 1 to rub You are %~50 mole %, more preferably 3 moles of %~40 mole %, particularly preferably 5 moles of %~20 mole %.
The monomer of structural unit with unprotected carboxyl or phenolic hydroxyl group described in being formed has well known to can enumerating The monomer of carboxyl or phenolic hydroxyl group, wherein it is preferred that (methyl) acrylic acid, more preferable methacrylic acid.
The monomer for forming the other structures unit (a3) can be used alone and a kind or two or more be applied in combination.
Moreover, from from the viewpoint of electrical characteristic, other structures unit (a3) preferably originate from phenylethylene structural unit, Structural unit with aliphatic ring type skeleton.Can specifically enumerate styrene, t-butoxystyrene, methyl styrene, Hydroxy styrenes, α-methylstyrene, (methyl) acrylic acid bicyclopentyl ester, (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid benzyl ester etc..
Moreover, from from the viewpoint of adhesion, the monomer for forming other structures unit (a3) is preferably (methyl) acrylic acid Nalka base ester.(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (first can specifically be enumerated Base) butyl acrylate etc..
The knot comprising (a1) with acidic group residue made of the protection of sour decomposability base as the ingredient for meeting (1) Structure unit and (a2) have the polymer of the structural unit of bridging property base, having comprising (a1) as the ingredient for meeting (2) The polymer of the structural unit of residue made of thering is acidic group to be protected by sour decomposability base and the knot comprising (a2) with bridging property base Any one of the polymer of structure unit can have structural unit (a3) ingredient, can also be used together by more than one.
In the present invention, ingredient A preferably comprises following polymer, and the polymer includes to have the quilt in the form of acetal The carboxyl of protection or the structural unit of phenolic hydroxyl group, the structural unit with unprotected carboxyl or phenolic hydroxyl group.
<The molecular weight of polymer in ingredient A>
The molecular weight of polymer in ingredient A is polystyrene converted weight average molecular weight, preferably 1,000~200, 000, more preferable 2,000~50,000.If in above-mentioned numberical range, then sensitivity and ITO adaptabilities are good.
Moreover, the number average molecular weight of polymer in ingredient A and the ratio (dispersion degree) of weight average molecular weight are preferred It is 1.0~5.0, more preferably 1.5~3.5.
<The manufacturing method of polymer in ingredient A>
Moreover, the synthetic method about the polymer in ingredient A, it is known to which various methods can be by such as if enumerating an example Under type and synthesize：Using radical polymerization initiator, make to include at least in organic solvent to be respectively formed the structure The free radical polymerization monomer mixture of the free radical polymerization monomer of unit (a1) and the structural unit (a2) is polymerize.
As the structural unit of residue made of being protected by sour decomposability base with acidic group comprising (a1) and (a2) with friendship The concrete example of the polymer of the structural unit of connection property base, can enumerate：
Methacrylic acid -1- ethoxy ethyl esters/methacrylic acid/methacrylic acid (3- Ethyloxetane -3- bases) Methyl esters/methacrylic acid -2- hydroxyethyl copolymers (45/8/35/12),
Methacrylic acid -1- ethoxy ethyl esters/methacrylic acid/glycidyl methacrylate/methacrylic acid alkene Propyl ester/methacrylic acid bicyclopentyl ester/styrol copolymer (35/10/30/5/15/15),
Methacrylic acid -1- cyclohexyl oxygroup ethyl ester/methacrylic acid/glycidyl methacrylate/metering system Acid -2- hydroxy methacrylates/styrol copolymer (40/8/35/12/5),
Methacrylic acid tetrahydrofuran -2- base esters/methacrylic acid/methacrylic acid (3- Ethyloxetanes -3- Base) methyl esters/glycidyl methacrylate/methacrylic acid -2- hydroxy methacrylates/styrol copolymer (35/10/15/15/ 15/10)、
Methacrylic acid -1- ethoxy ethyl esters/methacrylic acid/methacrylic acid (3- Ethyloxetane -3- bases) Methyl esters/N- methoxies acrylamide/methacrylic acid -2- hydroxy methacrylates copolymer (40/5/40/5/10),
Methacrylic acid oxinane -2- base esters/methacrylic acid/methacrylic acid (3- Ethyloxetanes -3- Base) methyl esters/methacrylic acid -2- hydroxy methacrylates/methacrylic acid bicyclopentyl ester copolymer (42/11/25/18/4) etc..
The polymer and packet of structural unit as residue made of comprising (a1) there is acidic group to be protected by sour decomposability base The concrete example containing (a2) with the polymer of the structural unit of bridging property base, can enumerate：
Methacrylic acid -1- ethoxy ethyl esters/methacrylic acid/methacrylic acid -2- hydroxy methacrylates/methacrylic acid benzyl Base ester copolymer (60/10/10/20) and methacrylic acid (3- Ethyloxetane -3- bases) methyl esters/methacrylic acid -2- The combination of hydroxy methacrylate/benzyl methacrylate copolymer (60/10/20),
Methacrylic acid oxinane -2- base esters/methacrylic acid/methacrylic acid -2- hydroxy methacrylates/methacrylic acid Bicyclopentyl ester copolymer (65/5/10/20) and glycidyl methacrylate/N- methoxies acrylamide/methyl The combination etc. of acrylic acid/methacrylic acid bicyclopentyl ester/styrol copolymer (50/15/5/15/15).
The content of ingredient A in the resin combination of the present invention is preferred for all solid contents of resin combination It is even more preferably 60 matter of mass %~95 for the 20 mass % of mass %~99, the more preferably 40 mass % of mass %~97 Measure %.If the content is in this range, then patternability when developing becomes good, and obtains the higher hardening thing of refractive index.Separately Outside, the solid object amount of so-called resin combination is the amount for indicating to remove the volatile ingredients such as solvent.
In addition, the present invention resin combination in, can not interfere the present invention effect in the range of and at Divide the resin other than A.Wherein, the content of the resin other than ingredient A is preferably smaller than the content of ingredient A.
(ingredient B) photoacid generator
The photosensitive polymer combination of the present invention contains (ingredient B) photoacid generator.
Photoacid generator used in the present invention preferably incude wavelength be 300nm or more, preferably wavelength 300nm~ The actinic ray of 450nm and generate acid compound, there is no restriction for chemical constitution.Moreover, being about not directly induction wavelength Photoactinic photoacid generator of 300nm or more incudes the light that wavelength is 300nm or more if by being used in combination with sensitizer Change ray to generate acid compound, then can be combined with sensitizer and it is preferable to use.
Photoacid generator used in the present invention preferably generates the photoacid generator that pKa is 4 acid below, more preferably produces Raw pKa is the photoacid generator of 3 acid below.
The example of photoacid generator can enumerate trichloromethyl-s-triazine, sulfosalt or salt compounded of iodine, quaternary ammonium salt, diazonium Methane compounds, acid imide sulfonate compound and oxime sulfonate compound etc..In those photoacid generators, self-insulating property From the viewpoint of, it is preferable to use oxime sulfonate compound.Those photoacid generators can be used alone a kind or by two or more group It closes and uses.Trichloromethyl-s-triazine, Diaryl iodonium salt, triaryl sulfonium salts class, quaternary ammonium salt and diazomethane spread out The concrete example of biology can illustrate recorded in 0083~paragraphs of paragraph 0088 of Japanese Patent Laid-Open 2011-221494 bulletins Compound.
It is represented that oxime sulfonate compound that is, compound with oxime sulfonate structure preferably illustrate following formula (B1) Oxime sulfonate compound.
[changing 16]
(in formula (B1), R21Indicate that alkyl or aryl, wave part indicate the key with other bases.)
Arbitrary base can be substituted, R21In alkyl can be straight-chain also can be branch-like also can be cyclic annular.Below to institute The substituent group allowed is illustrated.
R21The preferred carbon number of alkyl be 1~10 straight-chain or branch-like alkyl.R21Alkyl also can by carbon number be 6~ (including 7,7- dimethyl -2- oxo norbornies etc. have bridge-type fat for 11 aryl, the alkoxy that carbon number is 1~10 or naphthenic base Ring group, preferably bicyclic alkyl etc.) substitution.
R21The preferred carbon number of aryl be 6~11 aryl, more preferable phenyl or naphthyl.R21Aryl also can be by lower alkyl Base, the substitution of alkoxy or halogen atom.
Oxime sulfonate compound represented by the formula (B1) is preferably the oxime sulfonate chemical combination represented by following formula (B2) Object.
[changing 17]
(in formula (B2), R42Indicate alkyl or aryl, X indicate alkyl, alkoxy or halogen atom, m4 indicate 0~3 it is whole Number, when m4 is 2 or 3, multiple X can it is identical also can be different.)
The straight-chain or branch-like alkyl that the preferred carbon number of alkyl as X is 1~4.
The straight-chain or branch-like alkoxy that the preferred carbon number of alkoxy as X is 1~4.
The preferred chlorine atom of halogen atom as X or fluorine atom.
M4 is preferably 0 or 1.
Particularly preferably in the formula (B2), m4 1, X are methyl, and the position of substitution of X is ortho position, R42For carbon number be 1~ 10 straight-chain alkyl, 7,7- dimethyl -2- oxos norbornylmethyl or the compound to toluyl groups.
Oxime sulfonate compound represented by the formula (B1) is more preferably the oxime sulfonate represented by following formula (B3) Close object.
[changing 18]
(in formula (B3), R43With the R in formula (B2)42It is synonymous, X1Indicate halogen atom, hydroxyl, carbon number be 1~4 alkyl, Alkoxy, cyano or the nitro that carbon number is 1~4, n4 indicate 0~5 integer.)
R in the formula (B3)43Preferably methyl, ethyl, n-propyl, normal-butyl, n-octyl, trifluoromethyl, five fluorine second Base, perfluor n-propyl, perfluoro-n-butyl group, p-methylphenyl, 4- chlorphenyls or pentafluorophenyl group, particularly preferred n-octyl.
X1It is preferred that the alkoxy that carbon number is 1~5, more preferable methoxyl group.
N4 is preferably 0~2, and particularly preferably 0~1.
The concrete example of compound represented by the formula (B3) can enumerate α-(mesyloxy imino group) benzyl cyanide, α- (ethanesulfonyloxy group imino group) benzyl cyanide, α-(n-propyl sulfonyloxyimino) benzyl cyanide, α-(normal-butyl sulfonyloxy imido Base) benzyl cyanide, α-(4- tosyloxies imino group) benzyl cyanide, α-[(mesyloxy imino group) -4- methoxyphenyls] Acetonitrile, α-[(ethylsulfonyl oxygroup imino group) -4- methoxyphenyls] acetonitrile, α-[(n-propyl sulfonyloxyimino) -4- first Phenyl] acetonitrile, α-[(normal-butyl sulfonyloxyimino) -4- methoxyphenyls] acetonitrile, α-[(4- tosyloxies Imino group) -4- methoxyphenyls] acetonitrile.
The concrete example of preferred oxime sulfonate compound can enumerate following compounds (i)~compound (viii) etc., can be single It solely uses a kind or be two kinds or more.Compound (i)~compound (viii) can be used as commercially available product and obtain.Moreover, also It can combine and use with other kinds of (ingredient B) photoacid generator.
[changing 19]
The compound represented by oxime sulfonate compound also preferably following formula (OS-1) represented by the formula (B1).
[changing 20]
In the formula (OS-1), R101Indicate hydrogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl Base, sulfamoyl, sulfo group, cyano, aryl or heteroaryl.R102Indicate alkyl or aryl.
X101Expression-O- ,-S- ,-NH- ,-NR105-、-CH2-、-CR106H- or-CR105R107, R105~R107Indicate alkane Base or aryl.
R121~R124Separately indicate hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxy carbonyl Base, alkyl-carbonyl, aryl carbonyl, amide groups, sulfo group, cyano or aryl.R121~R124In 2 also can mutually be bonded respectively And form ring.
Also R is preferably enumerated121~R124Preferably hydrogen atom, halogen atom and alkyl, and R121~R124In at least 2 aspects for being mutually bonded and being formed aryl.Wherein, from from the viewpoint of sensitivity, preferably R121~R124Any one be The aspect of hydrogen atom.
The functional group also can further have substituent group.
Compound represented by the formula (OS-1) is more preferably the compound represented by following formula (OS-2).
[changing 21]
In the formula (OS-2), R101、R102、R121~R124Respectively with the R in formula (OS-1)101、R102、R121~R124Together Justice, preference are also identical.
R in those in more preferable formula (OS-1) and the formula (OS-2)101It is optimal for the aspect of cyano or aryl Choosing is indicated, R with the formula (OS-2)101For the aspect of cyano, phenyl or naphthyl.
Moreover, in the oxime sulfonate compound, about oxime or the stereochemical structure (E, Z etc.) of benzothiazole ring, respectively It can be either side, also can be mixture.
The concrete example for the compound represented by the formula (OS-1) that suitable can be used in the present invention can be enumerated Japanese special Recorded compound (exemplary compounds b-1~example in 0128~paragraph of paragraph 0132 of sharp special open 2011-221494 bulletins Show compound b-34), but the present invention is not limited to this.
In the present invention, the oxime sulfonate compound represented by the formula (B1) is preferably following formula (OS-3), following formula (OS-4) or the oxime sulfonate compound represented by following formula (OS-5).
[changing 22]
(in formula (OS-3)~formula (OS-5), R22、R25And R28Separately indicate alkyl, aryl or heteroaryl, R23、 R26And R29Separately indicate hydrogen atom, alkyl, aryl or halogen atom, R24、R27And R30Separately indicate halogen Atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X1~X3Separately indicate oxygen atom or Sulphur atom, n1~n3Separately indicate 1 or 2, m1~m3Separately indicate 0~6 integer.)
In the formula (OS-3)~formula (OS-5), R22、R25And R28In alkyl, aryl or heteroaryl also can have substitution Base.
In the formula (OS-3)~formula (OS-5), R22、R25And R28In alkyl be preferably also can with substituent group total carbon The alkyl that number is 1~30.
Moreover, in the formula (OS-3)~formula (OS-5), R1In heteroaryl preferably also can with substituent group total carbon number For 4~30 heteroaryl.
In the formula (OS-3)~formula (OS-5), R22、R25And R28If heteroaryl at least one ring in is heteroaromatic, Such as heteroaromatic also can contracting ring with phenyl ring.
In the formula (OS-3)~formula (OS-5), R23、R26And R29Preferably hydrogen atom, alkyl or aryl, more preferably hydrogen Atom or alkyl.
In the formula (OS-3)~formula (OS-5), there are 2 or more R in preferred compound23、R26And R29In 1 or 2 are alkyl, aryl or halogen atom, and more preferable 1 is alkyl, aryl or halogen atom, and particularly preferred 1 is alkyl, and Remaining is hydrogen atom.
In the formula (OS-3)~formula (OS-5), R23、R26And R29In alkyl or aryl can also have substituent group.
R23、R26And R29In alkyl be preferably also can with substituent group total carbon number be 1~12 alkyl, more preferably also There can be the alkyl that total carbon number of substituent group is 1~6.
R23、R26And R29In aryl be preferably also can with substituent group total carbon number be 6~30 aryl.
In the formula (OS-3)~formula (OS-5), X1~X3Separately indicate O or S, preferably O.
In the formula (OS-3)~formula (OS-5), including X1~X3Ring as ring person is 5 Yuans rings or 6 Yuans rings.
In formula (OS-3)~(OS-5), n1~n31 or 2 is separately indicated, in X1~X3It is excellent in the case of for O Select n1~n3It is separately 1；And in X1~X3In the case of for S, preferably n1~n3It is separately 2.
In the formula (OS-3)~formula (OS-5), R24、R27And R30Separately indicate halogen atom, alkyl, alcoxyl Base, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.Wherein, preferably R24, R27And R30It is separately alkyl or alcoxyl Base.
R24、R27And R30In alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl also can have substitution Base.
In the formula (OS-3)~formula (OS-5), R24、R27And R30In alkyl be preferably also can with substituent group total carbon The alkyl that number is 1~30.
In the formula (OS-3)~formula (OS-5), R24、R27And R30In alkoxy be preferably also can be with substituent group it is total The alkoxy that carbon number is 1~30.
Moreover, in the formula (OS-3)~formula (OS-5), m1~m3The separately integer of expression 0~6, preferably 0~ 2 integer, more preferably 0 or 1, particularly preferably 0.
Moreover, each substituent group about the formula (OS-3)~formula (OS-5), Japanese Patent Laid-Open 2011-221494 The preferred range of the substituent group of recorded formula (OS-3)~formula (OS-5) is also same in 0092~paragraph of paragraph 0109 of bulletin Sample it is preferred.
The concrete example of oxime sulfonate compound represented by the formula (OS-3)~formula (OS-5) can enumerate Japan Patent spy Compound recorded in 0114~paragraph of paragraph 0120 of 2011-221494 bulletins is opened, but the present invention is not limited to this A little compounds.
In the photosensitive polymer combination of the present invention, relative to the ingredient A100 mass parts in photosensitive polymer combination For, it is preferable to use 0.1 mass~10 mass parts (ingredient B) photoacid generator, more preferably using the mass of 0.5 mass~10 Part.Also two or more may be used.
The photosensitive polymer combination of the present invention also may include that 1,2-, bis- nitrine naphtoquinone compounds are photoactinic as incuding Photoacid generator.1,2- bis- nitrine naphtoquinone compounds generate carboxyl due to gradually type photochemical reaction, but its quantum yield must It is 1 or less.
The molecular weight of residue made of (ingredient C) there is 1 or more acidic group to be protected by sour decomposability base is less than 1,000 change Close object
The photosensitive polymer combination of the present invention contain (ingredient C) protected by sour decomposability base with 1 or more acidic group and At residue molecular weight be less than 1,000 compound.
Acidic group in ingredient C can enumerate carboxyl, phenolic hydroxyl group, sulfonic group, sulfoamido, phosphate and hydroxyl fluoroalkyl Deng.It is preferably wherein carboxyl and/or phenolic hydroxyl group, more preferably carboxyl, is even more preferably aliphatic carboxylic.
Ingredient C is preferably point of residue made of being protected by sour decomposability base with 1 or more carboxyl and/or phenolic hydroxyl group Compound of the son amount less than 1,000, sour decomposability protecting group can enumerate alkoxyalkyl, tertiary alkyl, tertiary alkoxy carbonyl alkyl Deng more preferably there is 1 or more carboxyl and/or phenolic hydroxyl group to be protected by the base represented by following formula (c1) or formula (c2) Residue molecular weight be less than 1,000 compound.
[changing 23]
(in formula (c1) and formula (c2), R1、R2、R4And R5Separately indicate hydrogen atom or alkyl, wherein R1With R2It is Except the case where hydrogen atom, R3Indicate can also there is heteroatomic alkyl or aryl, R6Expression can also have heteroatomic alkylene The divalent concatenating group that base, arlydene or those bases are composed, R1Or R2It also can be with R3Link and forms cyclic ether.)
R in formula (c1)1、R2、R4And R5Separately indicate that hydrogen atom or alkyl, the alkyl can be straight-chain, branch Chain, it is cricoid any one.Wherein, R1And R2Both sides and R4And R5Both sides and uneven indicate hydrogen atom, R1And R2And R4 And R5At least one party indicate alkyl.Moreover, the R in formula (c1)3Indicate can also there is heteroatomic alkyl or aryl, the alkane Base can be straight-chain, branched, it is cricoid any one.
The preferred carbon number of the alkyl of the straight-chain or branched is 1~12, and more preferable carbon number is 1~6, further more excellent It is 1~4 to select carbon number.Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth can specifically be enumerated Base, n-pentyl, neopentyl, n-hexyl, 2,3- dimethyl -2- butyl (thexyl), n-heptyl, n-octyl, 2- ethylhexyls, just Nonyl, positive decyl etc..
The preferred carbon number of cyclic alkyl is 3~12, and more preferable carbon number is 4~8, and even more preferably carbon number is 4~6. The cyclic alkyl can for example enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, different ice Chip base etc..
The alkyl can also have substituent group, substituent group that can illustrate halogen atom, aryl, alkoxy.With halogen original In the case that son is used as substituent group, R1、R2、R3As alkylhalide group；With aryl as substituent group, R1、R2、R3At For aralkyl.
Moreover, the alkyl can also have ethylene unsaturated bond.
The halogen atom can illustrate fluorine atom, chlorine atom, bromine atom, iodine atom, and preferably fluorine atom or chlorine is former in those Son.
Moreover, the aryl that the preferred carbon number of aryl is 6~20, more preferable carbon number is 6~12, can specifically illustrate benzene Base, Alpha-Methyl phenyl, naphthalene etc., the entirety that is, aralkyl of the alkyl being substituted with aryl can illustrate benzyl, α-methylbenzyl, Phenethyl, naphthyl methyl etc..
The alkoxy that the preferred carbon number of alkoxy is 1~6, more preferable carbon number are 1~4, more preferable methoxyl group or ethoxy Base.
Moreover, in the case where the alkyl is naphthenic base, it is 1~10 straight-chain that the naphthenic base, which can also have carbon number, Or the alkyl of branched is as substituent group；In the case where alkyl is the alkyl of straight-chain or branched, it is 3 that can also have carbon number ~12 naphthenic base is as substituent group.
Those substituent groups also can be further substituted with such substituents as described above.
The R3In also can have heteroatomic alkyl can enumerate alkoxyalkyl etc..The hetero atom is preferably oxygen original Son or sulphur atom, more preferably oxygen atom.
In the R3In the case of indicating aryl, the preferred carbon number of aryl is 6~12, and more preferable carbon number is 6~10.Institute Stating aryl can also have substituent group, the substituent group preferably to illustrate the alkyl that carbon number is 1~6.The aryl can for example illustrate Phenyl, tolyl, xylyl, cumenyl, 1- naphthalenes etc..
Moreover, R1、R2And R3It can mutually be bonded, the carbon atom being bonded with those is formed together ring.In R1With R2、R1With R3 Or R2With R3Ring structure in the case of bond can for example enumerate cyclobutyl, cyclopenta, cyclohexyl, suberyl, tetrahydrofuran base, Adamantyl and THP trtrahydropyranyl etc..
Particularly preferred tetrahydrofuran base in those.
Moreover, in the formula (c1), R1And R2Either side be preferably hydrogen atom or methyl.
R in formula (c1)6Indicating also can be with heteroatomic alkylidene, arlydene or those divalent being composed connection Base, the alkylidene can be straight-chain, branched, it is cricoid any one.Moreover, the alkylidene can also have ethylene insatiable hunger And key.
The carbon number of the alkylidene is preferably 1~12, and more preferably 1~8, it is even more preferably 1~6, particularly preferably It is 4~6.
The carbon number of the arlydene is preferably 6~20, and more preferably 6~12.
Moreover, the R6Carbon number be preferably 2~20, more preferably 2~12, be even more preferably 2~8.
The R6In the part of the methylene that also can preferably enumerate alkylidene with heteroatomic alkylidene be taken On behalf of the base of ehter bond.The hetero atom is preferably oxygen atom or sulphur atom, more preferably oxygen atom.
R6 in formula (c1) is preferably that a part for the methylene of alkylidene or alkylidene is substituted by the base of ehter bond.
Moreover, ingredient C is more preferably the compound represented by following formula (c3) or formula (c4).
[changing 24]
(in formula (c3) and formula (c4), R7 indicates also to may include the n valency alkyls that the carbon number of O atom or S atom is 1~16, R8 And R9 separately expression-COO- or-O-, R10 separately indicate also to may include the carbon number of O atom or S atom be 1~ 81 valency alkyl, X1 separately indicate that the base represented by the formula (c1), X2 indicate the base represented by the formula (c2), n Indicate that 1~3 integer, m indicate 2.)
In addition, in the case that R8 or R9 is-O- in formula (c3) and formula (c4), the R8 or R9 and the aryl in R7 or R10 Ring is bonded.
N in formula (c3) is particularly preferably 2.
R7 in formula (c3) preferably also may include the n valency alkyls of O atom, more preferably also may include the divalent hydrocarbon of O atom Base, the even more preferably part for alkylidene or the methylene of alkylidene are substituted by the base of ehter bond, particularly preferably sub- Alkyl.
The alkylidene can be straight-chain, branched, it is cricoid any one, and can also have ethylene unsaturated bond.
Moreover, the carbon number of the R7 is preferably 1~10, more preferably 1~8, particularly preferably 4~6.
Formula (c3) and R8 in formula (c4) and R9 separately expression-COO- or-O-, preferably-COO-.
The X1 and the formula (c1) in X2 or the base represented by formula (c2) of formula (c3) and formula (c4) and previously described formula (c1) or formula (c2) base represented by is synonymous, and preferred embodiment is also identical.
R10 in formula (c4) preferably also may include 1 valency alkyl of O atom, preferably alkyl or aryl.
The alkyl can be straight-chain, branched, it is cricoid any one, and can also have ethylene unsaturated bond.
Moreover, the carbon number of the R10 is preferably 1~10, and more preferably 1~8, it is even more preferably 1~6, it is especially excellent It is selected as 6.
Ingredient C is more preferably less than with 1 or more carboxyl molecular weight of base made of the base protection represented by formula (c1) 1,000 compound, particularly preferably point with 1 or more aliphatic carboxylic base made of the base protection represented by formula (c1) Compound of the son amount less than 1,000.
Moreover, the molecular weight of ingredient C is preferably less than 800, particularly preferably it is less than 600.Also, it is preferred that being 130 or more.
Acidic group residue number made of protecting in ingredient C is preferably 1~8, more preferably 1~4, even more preferably for 1~3, particularly preferably 2 or 3, most preferably 2.
Acidic group residue made of protecting can be imported according to well known synthetic method.Such as it can be by acid catalyst In the presence of or have no under the heating of catalyst, so that the compound with carboxyl or phenolic hydroxyl group is reacted and is synthesized with vinethene.
[changing 25]
In above-mentioned flow, R indicates also can also there is substituent group with alkyl, aryl, the heteroaryl of substituent group, Ar expressions Aryl.
R4And R5As-CH (R4)(R5) and with the R in the formula (c1)2It is synonymous, R6With the R in the formula (c1)1It is synonymous, R7With the R in the formula (c1)3It is synonymous, and those preferred scope is also identical.
The preferred concrete example of ingredient C can illustrate following C-1~C-26, but that the present invention is not limited to those is specific Example.
[changing 26]
[changing 27]
[changing 28]
The content of ingredient C in the photosensitive polymer combination of the present invention is relative to all solid of photosensitive polymer combination It is preferably the 0.01 mass % of mass %~20, more preferably 0.1 mass %~15 mass % for shape object, particularly preferably 0.2 The mass of quality %~10 %.
(ingredient D) solvent
The photosensitive polymer combination of the present invention contains (ingredient D) solvent.
The photosensitive polymer combination of the present invention is preferably modulated in (ingredient D) solvent dissolved with as essential component Mentioned component A~ingredient C, as the molten of aftermentioned ingredient E~ingredient I of preferred component etc. and aftermentioned any ingredient Liquid.
Well known solvent can be used in (ingredient D) solvent used in the photosensitive polymer combination of the present invention, can illustrate Ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, third Glycol dialkyl ether class, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate Esters, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone Class, amides, lactone etc..
The concrete example of (ingredient D) solvent used in the photosensitive polymer combination of the present invention can also enumerate Japan Patent Recorded solvent in 0174~paragraph of paragraph 0178 of special open 2011-221494 bulletins.
Moreover, also further can optionally add benzylisoeugenol, hexyl ether, ethylene glycol list phenyl in those solvents Ether acetic acid ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1- octanols, 1 nonyl alcohol, Benzyl alcohol, methyl phenyl ethers anisole, acetic acid benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, carbonic acid third Diester equal solvent.Those solvents, which can be used alone, or to be used in mixed way two or more by a kind.Solvent workable for institute in the present invention It is preferred that being used alone a kind or being used in combination 2 kinds, more preferably and with 2 kinds, even more preferably by propylene-glycol monoalky lether acetate esters Or dialkyl ether, oxalic acid esters and diethylene glycol dialkyl ether class or esters and butanediol alkylether acetates class are simultaneously With.
Moreover, the preferred boiling points of ingredient D be 130 DEG C less than 160 DEG C of solvent, the solvent that boiling point is 160 DEG C or more, Or the mixture of those solvents, more preferable boiling point be 130 DEG C less than 160 DEG C solvent, boiling point be 160 DEG C or more 200 The mixture of DEG C solvent or those solvents below, even more preferably boiling point are 130 DEG C less than 160 DEG C of solvent With the mixture that boiling point is 160 DEG C or more 200 DEG C of solvents below.
Boiling point is 130 DEG C can illustrate propylene glycol methyl ether acetate (boiling point 146 less than 160 DEG C of solvent DEG C), propylene glycol monoethyl ether acetate (boiling point is 158 DEG C), propylene glycol methyl-n-butyl ether (boiling point is 155 DEG C), propylene glycol first Base-n-propyl ether (boiling point is 131 DEG C).
The solvent that boiling point is 160 DEG C or more can illustrate 3- ethoxyl ethyl propionates (boiling point is 170 DEG C), diethylene glycol methyl (boiling point is for ethylether (boiling point is 176 DEG C), propylene glycol monomethyl ether propionate (boiling point is 160 DEG C), dipropylene glycol methyl ether acetic acid esters 213 DEG C), 3- methoxyl group butyl ether acetic acid esters (boiling point is 171 DEG C), diethylene glycol diethyl ether (boiling point is 189 DEG C), diethylene glycol (boiling point is for dimethyl ether (boiling point is 162 DEG C), propylene-glycol diacetate (boiling point is 190 DEG C), diethylene glycol monoethyl ether acetic acid esters 220 DEG C), dimethyl ether (boiling point is 175 DEG C), 1,3-BDO diacetate esters (boiling point is 232 DEG C).
The content of (ingredient D) solvent in the photosensitive polymer combination of the present invention is preferably in photosensitive polymer combination In every 100 mass parts of all resin components in be 50 mass parts~3,000 mass parts, more preferably 100 mass parts~2,000 Mass parts are even more preferably 150 mass parts~1,500 mass parts.
<Other compositions>
In the photosensitive polymer combination of the present invention other than ingredient A~ingredient D, (ingredient optionally can be preferably added E) sensitizer, (ingredient F) crosslinking agent, (ingredient G) contiguity modifying agent, (ingredient H) alkali compounds, (ingredient I) surfactant. In addition, plasticizer, hot radical producing agent, antioxidant, hot acid production can be added in the photosensitive polymer combination of the present invention Give birth to additive well known to antisettling agent of agent, ultra-violet absorber, thickener and organic or inorganic etc..
(ingredient E) sensitizer
The photosensitive polymer combination of the present invention is in the combination with (ingredient B) photoacid generator, in order to promote its decomposition And preferably comprise sensitizer.
Sensitizer absorbs actinic ray or radioactive ray and becomes excited electronic state.As the sensitizer and light of excited electronic state Acid producing agent contacts, and generates the effects that electronics is mobile, energy is mobile, fever.Thus photoacid generator generates chemical change and divides Solution generates acid.The example of preferred sensitizer, which can be enumerated, belongs to compounds below, and in the wave band of 350nm~450nm Compound with absorbing wavelength in arbitrary wavelength.
The polynuclear aromatic same clan (such as pyrene, benzophenanthrene, anthracene, 9,10- dibutoxies anthracene, 9,10- diethoxies anthracene, 3,7- Dimethoxy anthracene, 9,10- dipropoxies anthracene), oxa anthracenes (such as fluorescein, eosin, erythrosine, rhodamine B, Bangladesh's rose It is rare red), xanthone (such as xanthone, thioxanthones, dimethyl thioxanthone, diethyl thioxanthone), flower cyanines class (such as thiophene Carbon Jing, Evil carbon cyanines), merocyanine class (such as merocyanine, carbon merocyanine) if, red cyanines class, oxonols class, thiazide (such as thionine, Methylene blue, toluidine blue), acridine (such as acridine orange, chloroflavin, acriflavine), acridine ketone (such as acridone, 10- Butyl -2- chloro-acridines ketone), Anthraquinones (such as anthraquinone), Squarylium type (such as side sour cyanines), phenylethylene, basicity styrene class (such as 2- { 2- [4- (dimethylamino) phenyl] vinyl } benzoxazole), Coumarins (such as 7- diethylamino -4- first Butylcoumariii, Hymecromone, 2,3,6,7- tetrahydrochysene -9- methyl-1s H, 5H, 11H [1] chromenes simultaneously [6,7, 8-ij] quinolizine -11- ketone).
In those sensitizers, preferably the polynuclear aromatic same clan, acridine ketone, phenylethylene, basicity styrene class, cumarin Class, the more preferable polynuclear aromatic same clan.Most preferably anthracene derivant in the polynuclear aromatic same clan.
Light of the additive amount of sensitizer in the photosensitive polymer combination of the present invention relative to photosensitive polymer combination It is preferably 0 mass parts~1,000 mass parts for 100 mass parts of acid producing agent, the mass parts of more preferably 10 mass parts~500, Even more preferably it is the mass parts of 50 mass parts~200.
Sensitizer can be used alone a kind, can also be used in combination of two or more.
(ingredient F) crosslinking agent
It is preferred that the photosensitive polymer combination of the present invention is optionally containing the crosslinking agent other than ingredient A.It is crosslinked by adding Agent, can make by the present invention photosensitive polymer combination and gained cured film become stronger film.
Then there is no restriction if the crosslinking agent that can generate cross-linking reaction due to heat for crosslinking agent.Such as it can add as described below In the molecule have 2 or more epoxy groups or the compound of oxetanylmethoxy, crosslinking agent or tool containing alkoxy methyl There is the compound of at least one ethylene unsaturated bond.
In those crosslinking agents, preferably there is 2 or more epoxy groups or the compound of oxetanylmethoxy in the molecule, especially Preferred epoxy.
Institute of the additive amount of crosslinking agent in the photosensitive polymer combination of the present invention relative to photosensitive polymer combination There are a mass parts of preferably 0.01 mass parts for 100 mass parts of solid content~50, the mass parts of more preferably 0.5 mass parts~30, Even more preferably it is the mass parts of 2 mass parts~10.By being added in the range, mechanical strength and solvent resistant can get The excellent cured film of property.Crosslinking agent can be also used together by more than one, and crosslinking agent all adds up in this case and calculates content.
<Compound with 2 or more epoxy groups or oxetanylmethoxy in the molecule>
The concrete example of the compound with 2 or more epoxy groups can enumerate bisphenol A type epoxy resin, Bisphenol F in the molecule Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc..
Those compounds can be used as commercially available product and obtain.Such as Japanese Patent Laid-Open 2011-221494 bulletins can be enumerated Paragraph 0189 in recorded commercially available product etc..
ADEKA RESIN EP-4000S, ADEKA RESINEP-4003S, ADEKA can be also enumerated in addition to this RESINEP-4010S, ADEKA RESINEP-4011S (being manufactured above by Ai Dike (ADEKA) limited liability company), NC- 2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (being manufactured above by Ai Dike limited liability companies), DENACOL EX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX- 313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX- 832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX- 850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 are (above by the rapids chemical conversion of length (Nagasechemtex) limited liability company manufacture), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (with On by chemistry limited liability company of Nippon Steel manufacture) etc..
Those compounds, which can be used alone, or two or more to be applied in combination by a kind.
In those compounds, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type are more preferably enumerated Epoxy resin and aliphatic epoxy resin, aliphatic epoxy resin, particularly preferably enumerate bisphenol A type epoxy resin.
ARONEOXETANE OXT- can be used in the concrete example of the compound with 2 or more oxetanylmethoxies in the molecule 121, OXT-221, OX-SQ, PNOX (limited liability company's manufacture is synthesized by East Asia above).
Moreover, other crosslinking agents also preferably use 0107~section of paragraph of Japanese Patent Laid-Open 2012-8223 bulletins Fall the crosslinking agent containing alkoxy methyl recorded in 0108 and the compound at least one ethylene unsaturated double-bond Deng.
(ingredient G) touches modifying agent
The photosensitive polymer combination of the present invention can also contain (ingredient G) and touch modifying agent.The photoresist of the present invention In composition workable for (ingredient G) contiguity modifying agent be inorganic matter (such as silicon, silica, the silicon nitride for becoming base material Equal silicon compounds, the metals such as gold, copper, aluminium) compound with the adhesion raising of insulating film.It can specifically enumerate silane coupled Agent, sulfur alcohol compound etc..The silane coupling agent for touching modifying agent as (the ingredient G) used in the present invention is with surface Compound for the purpose of modification, is not particularly limited, and well known contiguity modifying agent can be used.
Preferred silane coupling agent can for example enumerate gamma-amino propyl trimethoxy silicane, gamma-amino propyl triethoxy Silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ- Methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chlorine third Base trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4- epoxycyclohexyl) ethyltrialkoxysilanes, second Alkenyl trialkoxy silane.More preferable γ-glycidyloxypropyl silane or γ-first in those silane coupling agents Base acryloxy propyl trialkoxy silane, even more preferably γ-glycidyloxypropyl silane, into one Walk more preferable 3- glycidoxypropyltrimewasxysilanes.Those compounds can be used alone a kind or by two or more group It closes and uses.Those compounds can effectively improve the adhesion with substrate, and the effectively cone angle of adjustment and substrate.
The content of (ingredient G) contiguity modifying agent in the photosensitive polymer combination of the present invention is relative to photoresist group Close for 100 mass parts of all solid contents in object the preferably mass parts of 0.1 mass parts~30, more preferably 0.5 mass parts~ 10 mass parts.
(ingredient H) alkali compounds
The photosensitive polymer combination of the present invention can also contain (ingredient H) alkali compounds.(ingredient H) alkali compounds can It arbitrarily selects and uses in compound used in from Chemical amplification resist.Such as can enumerate aliphatic amine, aromatic amine, The quaternary ammonium salt etc. of hetero ring type amine, quaternary ammonium hydroxide and carboxylic acid.The concrete example of those compounds can enumerate Japanese Patent Laid-Open Recorded compound in 0204~paragraph of paragraph 0207 of 2011-221494 bulletins.
The content of (ingredient H) alkali compounds in the photosensitive polymer combination of the present invention is relative to photoresist group Close for 100 mass parts of all solid contents in object the preferably mass parts of 0.001 mass parts~1, more preferably 0.005 mass parts ~0.2 mass parts.
(ingredient I) surfactant
The photosensitive polymer combination of the present invention can also contain (ingredient I) surfactant.
Anionic species, cationic, nonionic class or the arbitrary surfaces of both sexes can be used to live for (ingredient I) surfactant Property agent, preferably nonionic class surfactant.
The example of nonionic class surfactant can enumerate polyoxyethylene higher alkyl ether, polyoxyethylene higher alkylbenzene Base ethers, two esters of higher aliphatic acid of polyoxyethylene glycol, silicone, fluorine class surfactant.Moreover, following commodity can be enumerated Name KP (Shin-Estu Chemical Co., Ltd's manufacture), Polyflow (manufacture of chemistry limited liability company of common prosperity society), Eftop (manufacture of Ke Jim (JEMCO) company), Megafac (enlightening likes auspiciousness (DIC) limited liability company manufacture), Fluorad (are lived The manufacture of friendly 3M limited liability companies), Asahi Guard, Surflon (manufacture of Asahi Glass limited liability company), (Europe PolyFox Promise method (OMNOVA) company manufactures), each series of SH-8400 (manufacture of Dong Li DOW CORNINGs limited liability company) etc..
Moreover, surfactant can be listed below copolymer as preference, the copolymer includes following formula (1) institute table The structural unit A and structural unit B shown, gel permeation chromatography is measured when by tetrahydrofuran (THF) as solvent The weight average molecular weight (Mw) of polystyrene conversion is 1,000 or more 10,000 or less.
[changing 29]
(in formula (1), R401And R403Separately indicate hydrogen atom or methyl, R402Indicate that carbon number is 1 or more 4 below Straight-chain alkyl-sub, R404Indicate that hydrogen atom or carbon number are 1 or more 4 alkyl below, L indicates that carbon number is 3 or more 6 alkylenes below Base, p and q are the quality percentages for indicating polymerization ratio, and p indicates that 10 mass % or more, 80 mass % numerical value below, q indicate 20 matter 90 mass % numerical value below of % or more is measured, r indicates that 1 or more 18 integer below, s indicate 1 or more 10 integer below.)
The L is preferably the branched alkylene groups represented by following formula (2).R405 in formula (2) indicates that carbon number is 1 or more 4 Alkyl below, in intermiscibility with from the aspect of the wetability to being applied face, preferably carbon number is 1 or more 3 alkyl below, The alkyl that more preferable carbon number is 2 or 3.P and q's and (p+q) be preferably p+q=100, also as 100 mass %.
[changing 30]
The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more 5,000 or less.
Those surfactants, which can be used alone, or to be used in mixed way two or more by a kind.
The additive amount of (ingredient I) surfactant in the photosensitive polymer combination of the present invention is relative to photoresist It is preferably 10 below mass part, the matter of more preferably 0.001 mass parts~50 for 100 mass parts of all solid contents in composition Part is measured, is even more preferably the mass parts of 0.01 mass parts~10.
<Antioxidant>
The photosensitive polymer combination of the present invention can also contain antioxidant.Antioxidant can contain well known anti-oxidant Agent.By addition antioxidant, the coloring of cured film can be prevented, or the Mo Hou Minus that can lower caused by decomposing few, and And have the advantages that heat resistant transparent is excellent.
It is anti-oxidant that such antioxidant can for example enumerate phosphorus antioxidants, hydrazides, hindered amines antioxidant, sulphur class Agent, phenol antioxidant, Vitamin C acids, zinc sulfite, carbohydrate, nitrite, sulphite, thiosulfate, azanol spread out Biology etc..In those compounds, from the viewpoint of the coloring of self-hardening film, film thickness are reduced, particularly preferred phenol antioxidant.It should A little compounds can be used alone a kind, can also be mixed with two or more.
The commercially available product of phenol antioxidant can for example enumerate the Adekastab AO- of Ai Dike limited liability companies manufacture 20、Adekastab AO-30、Adekastab AO-40、Adekastab AO-50、Adekastab AO-60、Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Sumitomo Chemical limited liability company manufacture sumilizerGM, SumilizerGS, sumilizerMDP-S, sumilizerBBM-S, sumilizerWX-R, sumilizerGA-80, Japanese vapour IRGANOX1010, IRGANOX1035 of bar (Ciba Japan) limited liability company manufacture, IRGANOX1076, IRGANOX1098、IRGANOX1135、IRGANOX1330、IRGANOX1726、IRGANOX1425WL、IRGANOX1520L、 IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295, API company (API Corporation) manufacture Yoshinox BHT, Yoshinox BB, Yoshinox2246G, Yoshinox425, Yoshinox250, Yoshinox930, Yoshinox SS, Yoshinox TT, Yoshinox917, Yoshinox314 etc..
Wherein preferred Adekastab AO-60, Adekastab AO-80 are (above by Ai Dike limited liability companies system Make), Irganox1098 (Japanese Qi Ba limited liability companies manufacture).
The content of antioxidant for all solid contents of photosensitive polymer combination be preferably 0.1 mass %~ 10 mass %, the more preferably 0.2 mass % of mass %~5, particularly preferably 0.5 mass of mass %~4 %.It should by making it be Range can get the sufficient transparency for being formed by film, and sensitivity when pattern formation also becomes good.
Moreover, as the additive other than antioxidant, it can also be by " new extension (the daily magazine industry of polymeric additive Limited liability company of news agency) " in recorded various ultra-violet absorbers or metal deactivator etc. make an addition to the sense of the present invention In photosensitive resin composition.
<Acid proliferation generator>
The photosensitive polymer combination of the present invention can use acid proliferation generator to improve sensitivity.
Acid proliferation generator workable for institute is can be reacted by acid catalyst by further generate acid in the present invention, to make The compound that acid concentration in reaction system rises, and be the steadily existing compound in the state of there is no acid.It is such Compound can increase by 1 or more acid in 1 secondary response, therefore so that reaction is accelerated with the progress of reaction, be produced Raw acid itself induces self and decomposes, therefore it is 3 hereinafter, special that the intensity of acid generated here, which is preferably acid dissociation constant pKa, It You Xuanwei 2 or less.
The concrete example of acid proliferation generator can enumerate 0203~paragraph of paragraph of Japanese Patent Laid-Open 10-1508 bulletins 0223,0016~paragraph of paragraph 0055 of Japanese Patent Laid-Open 10-282642 bulletins and the flat 9- of Japanese Patent Laid Recorded compound in No. 512498 bulletins the 2nd row of the 12nd row~47th page of page 39.
Following compounds etc. can specifically be enumerated.
[changing 31]
The acid proliferation generator that can be used in the present invention, which can be enumerated, to be decomposed due to acid caused by acid producing agent, generate Following pKa is the compound of 3 acid below：Dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl Phosphonic acids etc..
As content of the acid proliferation generator in photosensitive polymer combination, the dissolving contrast from exposure portion Yu unexposed portion From the viewpoint of, it is preferably 10 mass parts~1,000 mass parts for 100 mass parts of photoacid generator, more preferably The mass parts of 20 mass parts~500.
Moreover, 0120~paragraph of paragraph of Japanese Patent Laid-Open 2012-8223 bulletins also can be used in other additives Recorded hot radical producing agent and thermal acid generator in 0121.
(forming method of cured film)
Secondly, the forming method of the cured film of the present invention is illustrated.
The forming method of the cured film of the present invention is characterized in that the step of comprising following (1)~(5).
(1) photosensitive polymer combination of the present invention is coated on substrate by application step；
(2) solvent removal stage removes solvent from the photosensitive polymer combination being coated with；
(3) step of exposure is exposed the photosensitive polymer combination for removing solvent using actinic ray；
(4) development step develops to the photosensitive polymer combination after exposure using aqueous developer；
(5) post-baking step carries out thermmohardening to the photosensitive polymer combination after development.
Hereinafter, being sequentially illustrated to each step.
In the application step of (1), preferably the photosensitive polymer combination of the present invention is coated on substrate and packet is made Solvent-laden moistening film.
In the solvent removal stage of (2), removed from the above-mentioned film being coated with by decompression (vacuum) and/or heating molten Agent and in forming desciccator diaphragm on substrate.
Moreover, the thickness for being formed by photosensitive polymer combination on substrate can arbitrarily be set according to it using purpose Fixed, preferably 0.0005mm or more 10mm ranges below, the easiness of printing resistance and laser engraving from galley consider, more Preferably 0.005mm or more 7mm ranges below.It also can the optionally different material of a variety of compositions of lamination.
In the step of exposure of (3), the film illumination wavelength to gained is 300nm or more 450nm actinic rays below. In the step, (ingredient B) photoacid generator decomposes and generates acid.It is contained in ingredient A due to the catalyst action of generated acid The hydrolysis of sour decomposability base and generate acidic group, such as generate carboxyl or phenolic hydroxyl group.
In order to have the region of acid catalyst that above-mentioned hydrolysis is made to accelerate in generation, and heat after being exposed (Post Exposure Bake, hereinafter referred to as " PEB ").It can promote to generate acidic group, such as carboxyl by sour decomposability base by PEB Or phenolic hydroxyl group.Carry out PEB when temperature be preferably 30 DEG C or more 130 DEG C hereinafter, more preferably 40 DEG C or more 110 DEG C hereinafter, Particularly preferably 50 DEG C or more 100 DEG C or less.
The activation energy that the acid of the sour decomposability base in structural unit (a1) in the present invention decomposes is low, is easy by exposing institute What is generated decomposes from the acid of photoacid generator, generates acidic group, such as carboxyl or phenolic hydroxyl group, therefore can need not also carry out PEB and by development form eurymeric image.Alternatively, it is also possible to by carrying out PEB under relatively low temperature, not generate cross-linking reaction Ground promotes the hydrolysis of sour decomposability base.
In the development step of (4), such as it is preferable to use alkaline-based developers to free carboxyl or phenolic hydroxyl group Polymer develops.By removing comprising the resin group with carboxyl or phenolic hydroxyl group for being easy to be dissolved in alkaline-based developer It closes the exposure portion region of object and is readily formed eurymeric image.
It in the post-baking step of (5), is heated as the eurymeric image to obtained by, the acid in structural unit (a1) point Xie Xingji is thermally decomposed and is generated carboxyl or phenolic hydroxyl group, to the crosslinkings such as the bridging property base of structural unit (a2), crosslinking agent, by This can form cured film.The heating is preferably heated to 150 DEG C or more of high temperature, is more preferably heated to 180 DEG C~250 DEG C, especially It is preferably heated to 200 DEG C~240 DEG C.Heating time can be preferably set to 10 minutes~120 according to heating temperature etc. and suitable for setting In the range of minute.
If, can plus the step of irradiating actinic ray, preferably ultraviolet light comprehensively to developing pattern before post-baking step Promote cross-linking reaction since actinic ray irradiates generated acid.
In addition, also can be used as dry-etching resist (dry by the cured film obtained by photosensitive polymer combination of the invention etching resist)。
Feelings of the cured film of gained as dry-etching resist by using the post-baking step by (5) to carry out thermmohardening Under condition, the dry-etchings processing such as etching process can be ashed, plasma etching, ozone etch.
Secondly, the forming method of the cured film for the photosensitive polymer combination for using the present invention is illustrated.
<The modulator approach of photosensitive polymer combination>
The essential component of ingredient A~ingredient D is mixed with defined ratio and arbitrary method, is stirred dissolving Or disperses and modulate photosensitive polymer combination.Such as it also can be made into and be dissolved or dispersed in ingredient A~ingredient C in advance respectively After liquid made of in (ingredient D) solvent, those liquid are mixed and resin composition modulation with defined ratio.As above After composition solution that is described and modulating also aperture can be used to be filtered for 0.2 μm of filter etc., it is supplied to use.
<Application step and solvent removal stage>
Photosensitive polymer combination is coated on defined substrate, is removed by depressurizing and/or heating (preliminary drying) molten Thus agent can form desired desciccator diaphragm.The substrate can for example illustrate in the manufacture of liquid crystal display element：Polarisation is set Plate is further optionally arranged black-matrix layer, color filter layers, is further provided with the glass plate of transparent conductive circuit layer Deng.It is coated on the method on substrate as by photosensitive polymer combination, there is no particular restriction, wherein preferably will in the present invention Photosensitive polymer combination is coated on substrate.The coating method being coated on substrate is not particularly limited, such as can be used narrow Stitch the methods of rubbing method, spray-on process, rolling method, method of spin coating.Wherein, preferably narrow from from the viewpoint of being suitable for large substrate Stitch rubbing method.If being manufactured with large substrate, productivity it is high and it is preferred that.It is 1m that so-called large substrate, which refers to each side, herein The substrate of above size.
Moreover, the heating condition of (2) solvent removal stage is the structural unit (a1) in ingredient A in unexposed portion In, sour decomposability base decomposes, and ingredient A is made not become soluble range in alkaline-based developer, because each ingredient type or Mixing ratio and it is different, be 30 seconds~120 seconds degree preferably at 80 DEG C~130 DEG C.
<Step of exposure and development step (pattern forming method)>
In step of exposure, via the mask with predetermined pattern, actinic ray is irradiated to the substrate equipped with film.It is exposing After light step, after optionally being heated (PEB), in development step using alkaline-based developer remove exposure portion region and Form picture pattern.
Using in photoactinic exposure can be used Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, Light emitting diode (Light Emitting Diode, LED) light source, excimer laser generating means etc. preferably uses g lines (436nm), i lines (365nm), h lines (405nm) etc. have the actinic ray of the above 450nm of wavelength 300nm wavelength below.And And it also can be optionally by being divided filter as long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter And adjust irradiation light.
It is preferred that the developer solution used in development step contains alkali compounds.Hydrogen-oxygen for example can be used in alkali compounds Change the alkali metal hydroxides such as lithium, sodium hydroxide, potassium hydroxide；The Alkaline metal carbonate salts such as sodium carbonate, potassium carbonate；Bicarbonate The Alkaline metal bicarbonate salts such as sodium, saleratus；The hydrogen-oxygens such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, bursine Change ammonium class；The aqueous solution of sodium metasilicate, sodium metasilicate etc..Moreover, can will also be added with appropriate amount in the aqueous solution of above-mentioned bases Methanol or the aqueous solution of the water-miscible organic solvents such as ethyl alcohol or surfactant be used as developer solution.
The pH of developer solution is preferably 10.0~14.0.
Developing time is preferably 30 seconds~180 seconds, and the gimmick developed can be that liquid pool method, infusion process etc. are any number of. After development, flowing water cleaning in 30 seconds~90 seconds can be carried out and form desired pattern.
It can also be rinsed step after development.In rinsing step, by being carried out to the substrate after development with pure water etc. It rinses, the developer solution of attachment is removed, remove development residue.Well known method can be used in purging method.Such as spray can be enumerated Flushing or immersion rinse etc..
<Post-baking step (cross-linking step)>
About the pattern corresponding with unexposed area of gained by development, using heating devices such as hot plate or baking ovens, At defined temperature (such as 180 DEG C~250 DEG C) carry out the stipulated time (such as if on hot plate be 5 minutes~90 minutes, If baking oven then be 30 minutes~120 minutes) heat treatment, cross-linking reaction is thus carried out, so as to form heat resistance, hardness Etc. excellent protective film or interlayer dielectric.Moreover, in heat treatment, can also be made by carrying out in a nitrogen environment Bright property improves.
Before rear baking, dried after being carried out after can also being toasted under relatively low temperature (additional intermediate baking procedure).Into In the case of the intermediate baking of row, after heating in 1 minute~60 minutes is preferably carried out at 90 DEG C~150 DEG C, in 200 DEG C or more of height It is dried after the lower progress of temperature.Moreover, also can centre baking, rear baking be divided into for 3 the multistage more than stage and heated.By such The effort that centre is toasted, dried afterwards can adjust the cone angle of pattern.The public affairs such as hot plate, baking oven, infrared heater can be used in those heating The heating means known.
In addition, before heat treatment, after preferably being exposed again to the figuratum substrate of formation with actinic ray, carry out (expose again/then dry) is dried afterwards, the ingredient B present in the unexposed portion generates acid therefrom, makes it as promoting cross-linking step Catalyst and function.
Also that is, the forming method of the cured film of the present invention includes to expose step again preferably between development step and post-baking step Suddenly, that is, with actinic ray to the substrate comprising the photosensitive polymer combination after development exposed again.As exposing step again Exposure in rapid is carried out by method same as the step of exposure, in the step of exposure again, preferably to substrate By the present invention photosensitive polymer combination and formed film side carry out blanket exposure.
The preferred light exposure of step of exposure is 100mJ/cm again2~1,000mJ/cm2。
(cured film)
The cured film of the present invention is hardened and the cured film of gained to the photosensitive polymer combination of the present invention.
The cured film of the present invention can suitably be used as interlayer dielectric.Moreover, the cured film of the present invention is preferably by this The forming method of the cured film of invention and the cured film of gained.
Even if obtaining the feelings that insulating properties is excellent, is toasted at high temperature using the photosensitive polymer combination of the present invention Also there is the interlayer dielectric of the high transparency under condition.Interlayer dielectric made of photosensitive polymer combination using the present invention With the high transparency, and cured film physical properties excellent, it is useful on the way in the use of organic EL display device or liquid crystal display device.
(organic EL display device and liquid crystal display device)
The organic EL display device and liquid crystal display device of the present invention is characterized in that including the cured film of the present invention.
The organic EL display device or liquid crystal display device of the present invention is in addition to including the photonasty tree for using the present invention Oil/fat composition and there is no particular restriction other than the planarization film or interlayer dielectric that are formed, the public affairs using various structures can be enumerated The various organic EL display devices or liquid crystal display device known.
Moreover, the photosensitive polymer combination of the present invention and the cured film of the present invention exist in which can be not limited to the purposes It is used in various uses.For example, other than planarization film or interlayer dielectric, the guarantor of colored filter also may be suitably used to Cuticula or the thickness of the liquid crystal layer in liquid crystal display device to be remained to the spacer of fixed thickness or in solid-state image pickup It is located in element in lenticule of colorized optical filtering on piece etc..
Fig. 1 is the composition concept map of an example for indicating organic EL display device.Indicate the organic EL displays dress of bottom emission type The model utility sectional view of substrate in setting, including planarization film 4.
The TFT (Thin Film Transistor, thin film transistor (TFT)) 1 that bottom gate type is formed on glass substrate 6, in covering Formed in the state of the TFT1 includes Si3N4Insulating film 3.After forming the contact hole for explanations are omitted hering diagram on the insulating film 3, The wiring 2 (being highly 1.0 μm) being connect with TFT1 is formed on the insulating film 3 via the contact hole.Wiring 2 is to connect It is formed by the wiring that organic EL element is connect with TFT1 between TFT1 or by step thereafter.
In addition, in order to make the concave-convex planarization generated due to forming wiring 2, in the state of being embedded to the bumps of wiring 2 Planarization layer 4 is formed on the insulating film 3.
The organic EL element of bottom emission type is formed on planarization film 4.Also will include ITO that is, on planarization film 4 First electrode 5, be connected on wiring 2 and formed via contact hole 7.Moreover, first electrode 5 is equivalent to organic EL element Anode.
It is pre-formed the insulating film 8 of the shape at the edge of covering first electrode 5, by the way that the insulating film 8 is arranged, the can be prevented Short circuit between one electrode 5 and behind second electrode the step of formed in.
In addition, though it is in Fig. 1 and not shown, but setting hole transport is sequentially deposited via desired pattern mask Layer, organic luminous layer, electron transfer layer, the secondly comprehensively upper formation above substrate include the second electrode of Al, use sealing It is bonded and is sealed with ultraviolet ray hardening type epoxy resin with glass plate, acquisition connects useful in each organic EL element Active matric-type organic EL display device with the TFT1 driven to it.
Fig. 2 is the conceptual sectional view of an example for the liquid crystal display device 10 for indicating active-matrix mode.The color liquid crystal Display device 10 is overleaf to include the liquid crystal display panel of back light unit 12, and liquid crystal display panel is in 2 pieces of glass bases for being pasted with light polarizing film The element of TFT16 corresponding with all pixels configured is configured between plate 14, glass substrate 15.Institute's shape on the glass substrate At each element in, the ito transparent electrode 19 that pixel electrode is formed by contact hole 18 formed in cured film 17 is matched Line connects.RGB (RGB) colored filter of layer and configuration black matrix" in ITO transparent electrodes 19 equipped with liquid crystal 20 22。
[embodiment]
It is exemplified below embodiment and more specific description is subject to the present invention.Material, usage amount shown in following embodiment, Ratio, process content, processing sequence etc. can then be carried out without departing from the purport of the present invention suitable for change.Therefore, of the invention Range is not limited to concrete example as shown below.In addition, as long as no special instructions, then " part ", " % " are quality criterias.
In synthesis example below, symbol below indicates compound below respectively.
V-65：2,2 '-azos bis- (2,4- methyl pentane nitriles) (and the manufacture of Wako Pure Chemical Industries limited liability company)
V-601：Bis- (2 Methylpropionic acid) dimethyl esters of 2,2 '-azos (and the manufacture of Wako Pure Chemical Industries limited liability company)
MAEVE：Methacrylic acid -1- ethoxy ethyl esters
MATHF：Methacrylic acid tetrahydrofuran -2- base esters
MATHP：Methacrylic acid tetrahydrochysene -2H- pyrans -2- base esters
DCPMA：Methacrylic acid bicyclopentyl ester
GMA：Glycidyl methacrylate
OXE-30：(Osaka Organic Chemical Industry share is limited for methyl esters for methacrylic acid (3- Ethyloxetane -3- bases) Company manufactures)
NBMA：N-butoxy methyl acrylamide
HEMA：Methacrylic acid -2- hydroxy methacrylates
St：Styrene
MMA：Methyl methacrylate
MAA：Methacrylic acid
CHOEMA：Methacrylic acid cyclohexyloxy ethyl ester
StOEVE：4- (1- ethoxyethyl groups oxygroup) styrene
P-Ph-1：The 1- ethoxyethylethers of 4-HBA (3- methacryloxypropyls) ester
IBMAA：Isobutoxymethyl acrylamide (manufacture of Tokyo chemical conversion industry limited liability company)
MMAA：Methoxy acrylamide (manufacture of (mitsubishi rayon) MRC Unitec limited liability companies)
M100：Methacrylic acid -3,4- epoxycyclohexanecarboxylate (manufacture of Daicel chemical industry limited liability company)
THFFMA：Methacrylic acid tetrahydro furfuryl ester
PHS：4-Vinyl phenol
Ph-1：4-HBA (3- methacryloxypropyls) ester
EDM：Diethylene glycol ethylmethyl ether (manufacture of Dong Bang chemical industry limited liability company, high solvent EDM)
PGMEA：Propylene glycol methyl ether acetate
<The synthesis of polymer A-1>
Polymer A-1 of the synthesis as copolymer as described below.
0.5 part of phenthazine is added in 144.2 parts of ethyl vinyl ether (2 molar equivalent), is cooled to 10 DEG C or less on one side 86.1 parts of methacrylic acid (1 molar equivalent) is added dropwise in reaction system on one side, is then carried out under room temperature (25 DEG C) 4 hours Stirring.After adding 5.0 parts of p-methyl benzenesulfonic acid pyridine, stirring in 2 hours is carried out at room temperature, places a night at room temperature.In 5 parts of 5 parts of sodium bicarbonate and sodium sulphate are added in reaction solution, carry out stirring in 1 hour at room temperature, after insoluble matter is filtered, 40 DEG C or less are concentrated under reduced pressure, and the yellow oil of residue are evaporated under reduced pressure and are obtained the boiling point of colorless oil (bp.) 134.0 parts of the methacrylic acid -1- ethoxy ethyl esters (MAEVE) of 43 DEG C~45 DEG C/7mmHg fractions.
By methacrylic acid -1- ethoxy ethyl esters (63.28 parts (0.4 molar equivalent)), (42.65 part (0.3 of the GMA of gained Molar equivalent)), MAA (8.61 parts (0.1 molar equivalent)), HEMA (26.03 parts (0.2 molar equivalent)) and EDM (110.8 parts) Mixed solution be heated to 70 DEG C under nitrogen flowing.One is stirred one side in face of the mixed solution was added dropwise freely with 2.5 hours Base polymerization initiator V-65 (trade name and Wako Pure Chemical Industries limited liability company manufacture, 4 parts) and EDM (100.0 parts) mixing Solution.After dripping, reaction in 4 hours is carried out at 70 DEG C, thus to obtain the EDM solution (solid concentrations of polymer A-1 For 40%).
The weight average molecular weight of the polymer A-1 of gained measured using gel permeation chromatography (GPC) is 15, 000。
<The synthesis of CHOEMA>
The synthesis of CHOEMA is carried out by method same as the synthetic method of MAEVE in the synthesis of the polymer A-1.
<The synthesis of MATHF>
Methacrylic acid (86g, 1 mole) is cooled to 15 DEG C in advance, addition camphorsulfonic acid (4.6g, 0.02 mole). 2- dihydrofuran (71g, 1 mole, 1.0 equivalents) is added dropwise in the solution.After carrying out stirring in 1 hour, saturated sodium bicarbonate is added (500mL) is extracted with ethyl acetate (500mL), after being dried with magnesium sulfate, filter insoluble matter after 40 DEG C or less into Row is concentrated under reduced pressure, and the yellow oil of residue is evaporated under reduced pressure and is obtained the boiling point (bp.) 54 DEG C~56 of colorless oil DEG C/methacrylic acid tetrahydrofuran -2- base esters (MATHF) 125g (yield 80%) of 3.5mmHg fractions.
Moreover, synthesizing Ph-1 (4-HBAs (3- methacryloxypropyls) by method as shown below Ester).
<The synthesis of Ph-1>
In the acetonitrile 100ml solution of 4-HBA (3- hydroxypropyls) ester 23g, N- methyl pyrroles are added under stiring Methacrylic chloride 16g is further added in pyrrolidone 20ml.So that it is reacted 8 hours when stirring at 35 DEG C, then will Reaction mixture is poured into ice water, and the crystallization that leaching is precipitated is recrystallized from ethyl acetate/n-hexane, obtains 4- Hydroxybenzoic acid (3- methacryloxypropyls) ester.
<The synthesis of P-Ph-1>
P-Ph-1 can be obtained by being protected to Ph-1 with 1- ethoxyethylethers.The 1- ethoxyethylethers of Ph-1 are protected It can be implemented by same as method recorded in the synthesis example 1 method.
<The synthesis of polymer A-2~polymer A-20>
Used each monomer and its usage amount are changed to recorded person in following table 1, in addition to this with polymer A-1 Synthesis be carried out similarly and be respectively synthesized polymer A-2~polymer A-20 as copolymer.
[table 1]
(embodiment 1)
By as it is following form A in the way of by each ingredient dissolve mix, with aperture be 0.2 μm polytetrafluoroethylene (PTFE) system filter Device is filtered, and obtains the photosensitive polymer combination of embodiment 1.
<Form A>
Copolymer (ingredient A)：The EDM solution of polymer A-1
With for copolymer solids basis be 100.0 parts
(ingredient B) photoacid generator：2.0 parts of B-1 shown in following
Specific compound (ingredient C)：2.0 parts of C-1 shown in following
Epoxy resin (ingredient F)：2.0 parts of F-1 shown in following
Touch modifying agent (ingredient G)：0.5 part of G-1 shown in following
Alkali compounds (ingredient H)：0.1 part of H-1 shown in following
Alkali compounds (ingredient H)：0.01 part of H-2 shown in following
Surfactant (ingredient I)：0.1 part of I-1 shown in following
Surfactant (ingredient I)：0.01 part of I-2 shown in following
With relative to it is above-mentioned form A for, all solid contents of composition add as the mode of 27 mass % as molten The PGMEA of agent (ingredient D).
(2~embodiment of embodiment 26)
Each compound used in embodiment 1 is changed in table 2 to recorded compound, in addition to this with embodiment 1 same additive amount carries out dissolving mixing, the photosensitive polymer combination of 2~embodiment of modulation embodiment 26.In addition, though Record is omitted in table 2, but is added using capacity same as Example 1 as solvent in 2~embodiment of embodiment 26 PGMEA。
In addition, in the case of H-1 and H-2 in replacing embodiment 1 using H-3, the H-3 of 0.1 part of addition.Using I- In the case that 1 replaces I-1 and I-2 in embodiment 1, the I-1 of 0.1 part of addition.Moreover, in the feelings of use (ingredient E) sensitizer Under condition, the sensitizer E-1 of 2.0 parts of addition.
(comparative example 1)
The C-1 of embodiment 1 is not used, carries out and modulate the photonasty tree of comparative example 1 similarly to Example 1 in addition to this Oil/fat composition.
(comparative example 2)
The A-5 of embodiment 7 is changed to A-7, carries out and modulate the sense of comparative example 2 similarly to Example 7 in addition to this Photosensitive resin composition.
(comparative example 3)
The A-19 of embodiment 25 and A-10 are changed to A-6, carries out and modulates similarly to Example 25 in addition to this The photosensitive polymer combination of comparative example 3.
(comparative example 4)
Composition recorded in the embodiment 1 of Japanese Patent Laid-Open 2000-298344 bulletins is modulated, as comparative example 4 photosensitive polymer combination.
(comparative example 5)
The C-1 of embodiment 1 is changed to C-27, carries out and modulate the sense of comparative example 5 similarly to Example 1 in addition to this Photosensitive resin composition.
(comparative example 6)
The C-1 of embodiment 1 is changed to adipic acid, carries out similarly to Example 1 in addition to this and modulates comparative example 6 Photosensitive polymer combination.
(comparative example 7)
The C-1 of embodiment 1 is changed to contiguity modifying agent G-1, is carried out and modulation ratio similarly to Example 1 in addition to this Compared with the photosensitive polymer combination of example 7.
It is detailed to indicate that the contracting of each compound used in 1~embodiment of embodiment 26,1~comparative example of comparative example 7 claims As described below.
Moreover, C-1~C-26 is and the identical compounds of institute C-1~C-26 above-mentioned in the explanation of ingredient C.
B-1：CGI-1397 (trade name, following compounds represented, the manufacture of Ciba Co., Ltd)
B-2：PAI-101 (trade name, following compounds represented, the manufacture of Ciba Co., Ltd)
B-3：Following compounds represented (aftermentioned synthesis example)
B-4：Following compounds represented (aftermentioned synthesis example)
B-5：Following compounds represented (aftermentioned synthesis example)
B-6：Following compounds represented
C-27：Recorded varnish A in Japanese Patent Laid-Open 2000-298344 bulletins
E-1：(trade name, 9,10- dibutoxies anthracene, Kawasaki chemical conversion industry limited liability company manufacture, are following shown DBA Compound)
F-1：JER157S65 (trade name, phenol novolak type epoxy resin, Nippon Epoxy Resin Co., Ltd. Manufacture)
G-1：KBM-403 (trade name, 3- glycidoxypropyltrimewasxysilanes, it is following shown in structure, SHIN-ETSU HANTOTAI Chemical industry limited liability company manufactures)
H-1：1,5- diazabicyclo [4.3.0] -5- nonenes
H-2：Triphenylimidazolyl
H-3：Following compounds represented
I-1：The nonionic surfactant containing perfluoroalkyl represented by following structural formula
I-2：Silicone surfactant SH-8400 (manufacture of Dong Li DOW CORNINGs limited liability company)
[changing 32]
[changing 33]
[changing 34]
[changing 35]
[changing 36]
<The synthesis of B-3>
Synthesize compound (α-(tolysulfonyl oxygroup the imino group) -2- phenyl second for being expressed as B-3 in such a way Nitrile).
The synthesis of α-(oxyimino) -2- phenylacetonitriles
Phenylacetonitrile 5.85g (manufacture of Tokyo chemical conversion industry limited liability company) is set to be mixed in tetrahydrofuran 50ml (and light Chun Yao Industries, Incs manufacture) in, it is dipped in ice bath and reaction solution is cooled to 5 DEG C or less.Secondly, SM-28 (first is added dropwise 28% methanol solution of sodium alkoxide and the manufacture of Wako Pure Chemical Industries limited liability company) 11.6g, it carries out under ice bath stirring for 30 minutes It mixes and makes its reaction.Secondly, isoamyl nitrite 7.03g (Tokyo chemical conversion works are added dropwise when remaining 20 DEG C of interior temperature or less Industry limited liability company manufactures), so that reaction solution is changed reaction 1 hour at room temperature after completion of dropwise addition.The reaction solution of gained is thrown Enter into the water 150mL dissolved with sodium hydroxide 1g and make it completely dissolved, secondly adds ethyl acetate 100ml and carry out liquid separation, Obtain the water layer about 180ml with object.Ethyl acetate 100ml is further added again, so that water layer is become pH with concentrated hydrochloric acid For 3 acidity below, extracts product and concentrated.The coarse crystallization of gained is cleaned with hexane, with 63% yield Obtain α-(oxyimino) -2- phenylacetonitriles 4.6g.
α-(oxyimino) -2- phenylacetonitriles 11.5g is set to be dissolved in tetrahydrofuran 100ml (and Wako Pure Chemical Industries shares Co., Ltd manufactures) in, it is dipped in ice bath and reaction solution is cooled to 5 DEG C or less.Secondly paratoluensulfonyl chloride 16.5g is added dropwise (and the manufacture of Wako Pure Chemical Industries limited liability company), is secondly added dropwise triethylamine 9.55g when remaining 20 DEG C of interior temperature or less (and the manufacture of Wako Pure Chemical Industries limited liability company), carries out stirring in 1 hour under ice bath and makes its reaction.
The reaction solution of gained is added dropwise in water 500mL, carries out stirring in one hour at room temperature.To the powdered of gained Precipitate is filtered, and is made it dry and is obtained α-(tolysulfonyl oxygroup imino group) -2- phenylacetonitriles (compound B-3) 20g.The compound1H-NMR spectrum show that product is the mixture of oxime constitutional isomer (cis/trans, syn/anti), deposit Than being syn: anti=25/75.
<The synthesis of B-4>
The synthesis of 1-1. synthetic intermediates B-4A
It is dissolved in 2- aminothiophenols 31.3g (manufacture of Tokyo chemical conversion industry limited liability company) under room temperature (25 DEG C) In toluene 100mL (and the manufacture of Wako Pure Chemical Industries limited liability company).Secondly, phenylacetyl chlorine is added dropwise in the solution of gained 40.6g (manufacture of Tokyo chemical conversion industry limited liability company) carries out stirring in 1 hour, is inferior at 100 DEG C and carries out at room temperature Stirring in 2 hours and make its reaction.Water 500mL is added in the reaction solution of gained and salt be precipitated is made to dissolve, extracts toluene Oil makes extract liquor concentrate in a rotary evaporator, obtains synthetic intermediate B-4A.
The synthesis of 1-2.B-4
Make as described above and the synthetic intermediate B-4A2.25g of gained is mixed in tetrahydrofuran 10mL (and Wako Pure Chemical Industries Limited liability company manufactures) in, being then dipped in ice bath makes reaction solution be cooled to 5 DEG C or less.Secondly, four are added dropwise in reaction solution Ammonium hydroxide 4.37g (25 mass % methanol solutions, Alpha Arthur (Alfa Acer) company manufacture), under ice bath into Row stirring in 0.5 hour and make its reaction.Isoamyl nitrite further is added dropwise when remaining 20 DEG C of interior temperature or less 7.03g after reaction solution is warming up to room temperature after completion of dropwise addition, carries out stirring in 1 hour.
Secondly, after reaction solution is cooled to 5 DEG C or less, paratoluensulfonyl chloride (1.9g) (Tokyo chemical conversion industry share is put into Co., Ltd manufactures), stirring in 1 hour is carried out when remaining 10 DEG C or less.Thereafter put into water 80mL, at 0 DEG C into Row stirring in 1 hour.After being filtered to the precipitate of gained, isopropanol (IPA) 60mL is put into, 50 DEG C is heated to and carries out 1 The stirring of hour is filtered when carrying out heat, is made it dry, and obtains B-4 (structure above-mentioned) 1.8g therefrom.
The B-4's of gained1H-NMR spectrum (300MHz, deuterate DMSO ((D3C)2S=O)) be δ=8.2~8.17 (m, 1H), 8.03~8.00 (m, 1H), 7.95~7.9 (m, 2H), 7.6~7.45 (m, 9H), 2.45 (s, 3H).
According to above-mentioned1H-NMR measurement results, the B-4 that can estimate gained is a kind of individual geometric isomer.
<The synthesis of B-5>
Beta naphthal (10g), chlorobenzene (30mL) aaerosol solution in addition aluminium chloride (10.6g), 2- chlorpromazine chlorides Mixed liquor is heated to 40 DEG C and makes the reaction of its progress 2 hours by (10.1g).Under ice-cold, 4N is added dropwise in reaction solution HCl/water solution (60mL) adds ethyl acetate (50mL) and carries out liquid separation.Potassium carbonate (19.2g) is added in organic layer, in 40 After carrying out reaction in 1 hour at DEG C, adds 2N HCl/waters solution (60mL) and carry out liquid separation, it is different with two after organic layer is concentrated Propyl ether (10mL) carries out repulped (reslurry) to crystallization, is filtered, dries and obtain ketone compound (6.5g).
Acetic acid (7.3g), 50 mass % are added in the ketone compound (3.0g) of gained, the aaerosol solution of methanol (30mL) Hydroxylamine aqueous solution (8.0g) and be heated to reflux.After placing cooling, water (50mL) is added, filters the crystallization of precipitation, uses cold methanol After being subject to cleaning, it is dried and obtains oxime compound (2.4g).
The oxime compound (1.8g) of gained is set to be dissolved in acetone (20mL), in ice-cold lower addition triethylamine (1.5g), right Toluene sulfochloride (2.4g) is warming up to room temperature and carries out reaction in 1 hour.Water (50mL) is added in reaction solution, to being precipitated Crystallization be filtered after, carried out with methanol (20mL) repulped, be filtered, dry and obtain B-6 (structure above-mentioned) 2.3g。
In addition, B-51H-NMR spectrum (300MHz, CDCl3) it is δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H)。
<The synthesis of C-1>
Addition ethyl acetate 30.0g, 2,3- dihydro furans in adipic acid 50.0g (manufacture of Northeast chemistry limited liability company) Mutter 70.0g (manufacture of Tokyo chemical conversion industry limited liability company), carries out heating in 24 hours and makes its reflux.By reaction solution air After cooling, residual solvent is concentrated and is obtained the C-1 of 98.0g.
In addition, C-11H-NMR spectrum (300MHz, CDCl3) be δ=6.2 (d, 2H), 4.9 (dd, 2H), 4.8 (dd, 2H), 2.2 (t, 4H), 2.0~1.8 (m, 8H), 1.55~1.45 (m, 4H).
<The synthesis of C-2~C-26>
By the adipic acid of C-1 and/or 2,3-dihydrofuran be changed to respectively corresponding carboxylic acid compound, phenolic compounds and/ Or vinyl ether compound, it is carried out similarly in addition to this with C-1 and synthesizes C-2~C-26.
To the photosensitive polymer combination of 1~embodiment of embodiment 26 of gained and 1~comparative example of comparative example 7 by above Carry out each evaluation as shown below.It will be evaluation result is shown in table in 2.
<The evaluation of the substrate adhesion of cured film>
On the glass substrate for being formed with molybdenum evaporation film after each photosensitive polymer combination of rotary coating, in 90 DEG C of heat 120 seconds preliminary dryings are carried out on plate and solvent is made to volatilize, and form the photosensitive polymer combination layer that film thickness is 4.1 μm.
Secondly, the PLA-501F exposure machines (extra-high-pressure mercury vapour lamp) manufactured using Canon, Inc. are to add up irradiation Amount becomes 300mJ/cm2(illumination 20mW/cm2) mode the photosensitive polymer combination layer of gained is exposed, thereafter will The substrate in baking oven, carry out heating in 1 hour at 230 DEG C and obtain cured film.
For the cured film of gained, implement the experiment of 100 lattice cross-cuts according to gimmick recorded in JISK5600, it is right The lattice number of peeling is counted.Evaluation criteria is as described below." 1 " and " 2 " is the level of no problem in practicality.Show the result in table In 2.
1：0 lattice peel off
2：The lattice of 1 lattice~20 peel off
3：The lattice of 21 lattice~50 peel off
4：It more than 51 lattice peels off
<The evaluation of the heat flow of cured film>
Each photosensitive resin composition of slot coated on glass substrate (EAGLE XG, 0.7mm thickness (Corning Incorporated's manufacture)) It after object, carries out 120 seconds preliminary dryings on 90 DEG C of hot plate and solvent is made to volatilize, form the photoresist group that film thickness is 4.1 μm Close nitride layer.
Secondly, the PLA-501F exposure machines (extra-high-pressure mercury vapour lamp) manufactured using Canon, Inc., via regulation Mask, be suitble to each composition light exposure the photosensitive polymer combination layer of gained is exposed.It then, will be after exposure Photosensitive composition layer carried out at 23 DEG C 60 seconds with alkaline-based developer (tetramethylammonium hydroxide aqueous solution of 0.4 mass %) Development after, flushing in 20 seconds is carried out with ultra-pure water, 5.0 μm of sectional hole patterns are made.
PLA-501F is further used, 300mJ/cm is become with accumulative exposure2(illumination 20mW/cm2) mode to such as Photosensitive polymer combination layer after the upper pattern is exposed, and is carried out to the substrate in baking oven, at 230 DEG C thereafter Heating in 1 hour.
The hole shape after baking oven heating is observed by section SEM, measures the angle of taper in hole.Evaluation criteria is as described below. " 1 " and " 2 " is the level of no problem in practicality.It shows the result in table 2.
1：Angle of taper is 60 degree or more
2：Angle of taper is 45 degree less than 60 degree
3：Angle of taper is 30 degree less than 45 degree
4：Angle of taper is less than 30 degree
<The evaluation of sensitivity>
Each photosensitive resin composition of slot coated on glass substrate (healthy and free from worry 1737,0.7mm thick (Corning Incorporated's manufacture)) It after object, carries out 120 seconds preliminary dryings on 90 DEG C of hot plate and solvent is made to volatilize, form the photosensitive resin composition of 3.0 μm of film thickness Nitride layer.
Secondly, the PLA-501F exposure machines (extra-high-pressure mercury vapour lamp) manufactured using Canon, Inc., via regulation Mask the photosensitive polymer combination layer of gained is exposed.Then, by the photosensitive composition layer alkalinity after exposure After developer solution (tetramethylammonium hydroxide aqueous solution of 0.4 mass %) carries out development in 60 seconds at 23 DEG C, carried out with ultra-pure water Flushing in 20 seconds.
By the Optimum i line exposing amount (Eopt) by those are operated using the line of 1: 1 10 μm of parsing and when gap as feeling Luminosity.In addition, evaluation criteria is as described below." 1 " and " 2 " is the level of no problem in practicality.It shows the result in table 2.
1：Less than 20mJ/cm2
2：20mJ/cm2Less than 30mJ/cm2
3：30mJ/cm2Less than 40mJ/cm2
4：40mJ/cm2More than
<The evaluation of development film reduction>
Each photosensitive resin composition of rotary coating on glass substrate (healthy and free from worry 1737,0.7mm thick (Corning Incorporated's manufacture)) It after object, carries out 120 seconds preliminary dryings on 90 DEG C of hot plate and solvent is made to volatilize, form photosensitive polymer combination layer, measure it Film thickness.
Secondly, it is carried out at 23 DEG C 60 seconds with alkaline-based developer (tetramethylammonium hydroxide aqueous solution of 0.4 mass %) After development, film thickness is measured again.
Ratio of the film thickness measured at this time relative to the film thickness measured before development is calculated, evaluated for film is reduced.In addition, commenting Valence benchmark is as described below." 1 " and " 2 " is the level of no problem in practicality.It shows the result in table 2.
1：Residual film ratio is 97% or more
2：Residual film ratio is 95% less than 97%
3：Residual film ratio is 90% less than 95%
4：Residual film ratio is less than 90%
<The evaluation of liquid ageing stability (fluid preservation)>
The photosensitive polymer combination of modulation shortly after is measured with E types viscosimeter (Dong Ji industries limited liability company manufactures) Viscosity (initial viscosity), at 30 DEG C take care of 1 week after and keeping 2 weeks after photosensitive polymer combination viscosity (warp When viscosity).Evaluation criteria be will through when viscosity relative to initial viscosity (100%) carry out relative evaluation, will change 10% or more The case where be used as " 3 ", viscosity change is less than 10% and is used as " 2 " for 5% or more situation, viscosity change is less than 5% Situation is used as " 1 "." 1 " and " 2 " is the level of no problem in practicality.It shows the result in table 2.
As shown in 1~embodiment of embodiment 26, it is known that composition of the invention can be by the substrate as the cured film of project Adhesion and heat flow are improved to the level in practicality without a doubt.In addition, understand sensitivity or development film reduce, through when stablize Property is also excellent.
It understands in 1~comparative example of comparative example 3, if without using the bridging property unit of ingredient C and ingredient A, cured film Adhesion and heat flow deteriorate.
It understands in comparative example 4 and comparative example 5, if the molecular weight of ingredient C is excessive, the adhesion of cured film and heat flow Deteriorate.
Known in comparative example 6, if using unprotected low molecular acid compound replace ingredient C, cured film it is close Connecing property deteriorates.
It understands in comparative example 7, even if addition (increment) contiguity modifying agent replaces ingredient C, also fails to improve cured film Adhesion, and heat flow deteriorates.On the other hand, although in embodiment 3 be not used contiguity modifying agent G-1, cured film it is close Connecing property is very good.
The hardening of the composition of the present invention can be enlightened according to 1~embodiment of above example 26 and 1~comparative example of comparative example 7 The mechanism of improvement of film adhesion is different from previous contiguity modifying agent.Its detailed mechanism is still not clear, but can also be obtained by heat flow Infer its reason to inhibition and may is that：The ingredient C being partly deprotected in exposure can caused by holding low molecule Plasticity in the state of intermiscibility in resin entirety with the bridging property unit process in ingredient A and be crosslinked, therefore can one side It mitigates stress one side when hardening and forms extremely uniform and fine and close cross-linked structure.

Claims (11)

1. a kind of photosensitive polymer combination, it is characterised in that contain：
Ingredient A：Meet the ingredient of following (1) or (2)；
Ingredient B：Photoacid generator；
Ingredient C：The molecular weight of residue made of being protected by sour decomposability base with 1 or more acidic group is less than 1,000 compound, The content of the ingredient C is 0.01 matter of mass %~20 for all solid contents of the photosensitive polymer combination Measure %；And
Ingredient D：Solvent,
The ingredient C is protected by the base represented by following formula (c1) or formula (c2) with 1 or more carboxyl and/or phenolic hydroxyl group Made of residue molecular weight be less than 1,000 compound,
(1) structural unit of residue and (a2) are with bridging property base made of being protected by sour decomposability base with acidic group comprising (a1) Structural unit polymer,
(2) include (a1) with acidic group polymer of the structural unit of residue made of the protection of sour decomposability base and include (a2) The polymer of structural unit with bridging property base,
In formula (c1) and formula (c2), R1、R2、R4And R5Separately indicate hydrogen atom or alkyl, wherein R1With R2It is hydrogen original Except the situation of son, R3Indicate can also there is heteroatomic alkyl or aryl, R6Indicate can also there is heteroatomic alkylidene, Asia The divalent concatenating group that aryl or the base are composed, R1Or R2With R3Also it can link and form cyclic ether.
2. photosensitive polymer combination according to claim 1, it is characterised in that：
The photosensitive polymer combination is chemically amplified positive photosensitive polymer combination.
3. photosensitive polymer combination according to claim 1 or 2, it is characterised in that：
The ingredient C is the compound represented by following formula (c3) or formula (c4),
[changing 2]
In formula (c3) and formula (c4), R7It indicates also to may include the n valency alkyls that the carbon number of O atom or S atom is 1~16, R8And R9Point Not independently expression-COO- or-O-, R10It separately indicates also to may include 1 valence that the carbon number of O atom or S atom is 1~8 Alkyl, X1Separately indicate the base represented by the formula (c1), X2Indicate that the base represented by the formula (c2), n indicate 1~3 Integer, m indicate 2.
4. photosensitive polymer combination according to claim 1 or 2, it is characterised in that：
The ingredient C is that the molecular weight of residue made of being protected by sour decomposability base with 1 or more aliphatic carboxylic is less than 1, 000 compound.
5. photosensitive polymer combination according to claim 3, it is characterised in that：
The ingredient C is that the molecular weight of residue made of being protected by sour decomposability base with 1 or more aliphatic carboxylic is less than 1, 000 compound.
6. a kind of forming method of cured film, it is characterised in that include：
(1) photosensitive polymer combination according to claim 1 is coated on substrate by application step；
(2) solvent removal stage removes solvent from the photosensitive polymer combination being coated with；
(3) step of exposure is exposed the photosensitive polymer combination for removing the solvent using actinic ray；
(4) development step develops to the photosensitive polymer combination after exposure using aqueous developer；And
(5) post-baking step carries out thermmohardening to the photosensitive polymer combination after development.
7. the forming method of cured film according to claim 6, it is characterised in that include：
After the development step and before post-baking step, to comprising described in the photosensitive polymer combination after development Substrate carries out the step of blanket exposure.
8. a kind of cured film, it is characterised in that：
The cured film is formed using the forming method of cured film according to claim 6.
9. cured film according to claim 8, it is characterised in that：
The cured film is interlayer dielectric.
10. a kind of organic electroluminescence display device and method of manufacturing same, it is characterised in that include：
Cured film according to claim 8.
11. a kind of liquid crystal display device, it is characterised in that include：
Cured film according to claim 8.
CN201310037511.6A 2012-01-31 2013-01-30 Photosensitive polymer combination, the forming method of cured film, cured film, organic electroluminescence display device and method of manufacturing same and liquid crystal display device Expired - Fee Related CN103226290B (en)

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