CN106462064B - Positive type photosensitive organic compound - Google Patents

Positive type photosensitive organic compound Download PDF

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CN106462064B
CN106462064B CN201580031678.9A CN201580031678A CN106462064B CN 106462064 B CN106462064 B CN 106462064B CN 201580031678 A CN201580031678 A CN 201580031678A CN 106462064 B CN106462064 B CN 106462064B
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formula
carbon atom
atom number
positive type
type photosensitive
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CN106462064A (en
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古江健太郎
大野由起
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Nippon Paint Co Ltd
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Showa Ltd
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

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  • Polymers & Plastics (AREA)
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  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
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Abstract

The present invention provides a kind of positive type photosensitive organic compound that the film releasing gas after heating firing is few.A kind of positive type photosensitive organic compound, polyene-based phenol resin, alkali soluble resin and quinone di-azido compound containing the structure with formula (1), in formula (1), R1、R2And R3Separately indicate the alkoxy or hydroxyl of hydrogen atom, the alkyl of carbon atom number 1~5, alkenyl, carbon atom number 1~2 represented by formula (2), and R1、R2And R3In at least one be formula (2) represented by alkenyl.Q separately expression-CR4R5The alkylidene that indicates, the cycloalkylidene of carbon atom number 5~10, the bivalent organic group with aromatic rings, the bivalent organic group with ester ring type condensed ring or by bivalent group made of these moiety combinations.Wherein, the alkali soluble resin does not include the polyene-based phenol resin with the structure of formula (1).

Description

Positive type photosensitive organic compound
Technical field
The present invention relates to a kind of positive type photosensitive organic compounds characterized by releasing gas less.More specifically, it relates to And a kind of photosensitive polymer combination for forming insulating film, the composition is for insulating films such as organic electroluminescent devices In the case of, few to the releasing gas that insulating film pattern generate after hot firing is formed by, can inhibit as organic The generation that the blackspot or image of the degradation phenomena of electroluminescent cell are shunk.
Background technique
Photosensitive polymer combination is widely used in passing through radioactive ray in the production such as substrate of semiconductor or liquid crystal display panel Photoetching process forms fine structure.As photosensitive polymer combination, the resin combination of novolac resin system is in semiconductor system Make with etc. in be widely used (referring for example to patent document 1,2.), but existing novolac resin system photoresist group The gas that conjunction object is released after heating firing from film is more, becomes problem to the pollution of light-emitting component etc..
Photosensitive polymer combination is applied not only to semiconductors manufacture, and is made as the constituent element of light-emitting component With.For example, organic electroluminescent device identification due to self-luminous is high, and it is complete solid-state components, therefore, there is impact resistance The features such as excellent, so, it is concerned as the light-emitting component in display device, wherein including the works such as insulating film.? The insulating film or fine structure object of organic electroluminescent device are formed on the way, are required photosensitive resin film: (1) cross sectional shape For along conical by its shape；(2) gas released from the resin film after heating firing is few.
In order to improve the releasing gas from the resin film after heating firing, can illustrate novolac resin and benzo The photonasty tree that piperazine compound, carbodiimide compound, triazine thiol compound or bismaleimide compound are combined into Lipid resin combination (such as patent document 3).But in the technology, the low novolac resin of heat resistance is principal component, The viewpoint aspect for reducing releasing gas is insufficient.
In addition, the resin high as heat resistance, proposes containing polyimides, polyphenyl simultaneouslyAzoles or their precursor and Novolac resin, crosslinking agent, naphthalene quinone di-azido compound photosensitive polymer combination (patent document 4~6).But this In a little technologies, due to the reduction of the heat resistance due to novolac resin, release the reduction of gas and insufficient.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 62-260147 bulletin
Patent document 2: Japanese Unexamined Patent Publication 5-94013 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2009-222923 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2005-250160 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2008-268788 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2009-198957 bulletin
Summary of the invention
Problems to be solved by the invention
In view of above-mentioned status, the gas released the object of the present invention is to provide the film after a kind of firing from heating is few Positive type photosensitive organic compound.
Means for solving the problems
The inventors of the present invention have made intensive studies, as a result, it has been found that: the normal Photosensitive resin group containing polyene-based phenol resin The heat resistance for closing object is good, so containing polyene-based phenol resin, alkali soluble resin, quinone di-azido compound composition can be with Pattern is formed by photoetching process, and it is few that releasing gas after being burnt into the pattern may be implemented.
The present invention is a kind of positive type photosensitive organic compound, polyene-based phenol resin, alkali containing the structure with formula (1) Soluble resin (wherein, not including the polyene-based phenol resin with the structure of formula (1)) and quinone di-azido compound,
(in formula (1), R1、R2And R3Separately indicate that hydrogen atom, the alkyl of carbon atom number 1~5, formula (2) indicate The alkoxy or hydroxyl of alkenyl, carbon atom number 1~2, and R1、R2And R3In at least one be formula (2) indicate alkenyl.Q difference Independently expression-CR4R5Cycloalkylidene, the divalent organic base with aromatic rings of the alkylidene, carbon atom number 5~10 that indicate Group, the bivalent organic group with ester ring type condensed ring or by bivalent group made of these moiety combinations, R4And R5Independently Ground indicates hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~6, the naphthenic base of carbon atom number 5~10 or carbon The aryl of atomicity 6~12.
In formula (2), R6、R7、R8、R9And R10Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, carbon atom The naphthenic base of number 5~10 or the aryl of carbon atom number 6~12.* in formula (2) indicates the key with the carbon atom for constituting aromatic rings Conjunction portion.).
The present invention includes aspect below.
[1] a kind of positive type photosensitive organic compound, polyene-based phenol resin, alkali containing the structure with formula (1) are solvable Property resin (wherein, not including the polyene-based phenol resin with the structure of formula (1)) and quinone di-azido compound,
(in formula (1), R1、R2And R3Separately indicate that hydrogen atom, the alkyl of carbon atom number 1~5, formula (2) indicate The alkoxy or hydroxyl of alkenyl, carbon atom number 1~2, and R1、R2And R3In at least one be formula (2) indicate alkenyl.Q difference Independently expression-CR4R5Cycloalkylidene, the divalent organic base with aromatic rings of the alkylidene, carbon atom number 5~10 that indicate Group, the bivalent organic group with ester ring type condensed ring or by bivalent group made of these moiety combinations, R4And R5Independently Ground indicates hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~6, the naphthenic base of carbon atom number 5~10 or carbon The aryl of atomicity 6~12.
In formula (2), R6、R7、R8、R9And R10Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, carbon atom The naphthenic base of number 5~10 or the aryl of carbon atom number 6~12.* in formula (2) indicates the key with the carbon atom for constituting aromatic rings Conjunction portion.).
[2] positive type photosensitive organic compound according to [1], which is characterized in that the structure of formula (1) is formula (3) Structure,
(in formula (3), R1、R2And R3It indicates and the R in formula (1)1、R2And R3The identical meaning.).
[3] positive type photosensitive organic compound according to [2], which is characterized in that the polyenoid of the structure with formula (3) Base phenol resin contains the structure of formula (4),
(in formula (4), R1、R2And R3It indicates and the R in formula (1)1、R2And R3The identical meaning.The integer that P is 0~50.).
[4] positive type photosensitive organic compound according to any one of [1]~[3], which is characterized in that formula (2) table The alkenyl shown is allyl.
[5] positive type photosensitive organic compound according to any one of [1]~[4], which is characterized in that alkali-soluble Resin is polyimide precursor.
[6] positive type photosensitive organic compound according to any one of [1]~[5], which is characterized in that the polyamides Formula (5) expression of imines precursor,
(in formula (5), R11Indicate the bivalent organic group of 2 or more carbon atom number, R12Indicate the trivalent of 2 or more carbon atom number Or the organic group of tetravalence, R13Indicate the organic group of hydrogen atom or carbon atom number 1~20, R14Indicate hydrogen atom or carbon atom The organic group of number 1~50, m indicate 1 or 2, and n indicates 5~200 integer.).
[7] positive type photosensitive organic compound according to [6], which is characterized in that the R of formula (5)14Contain unsaturated group Group.
[8] positive type photosensitive organic compound according to [7], which is characterized in that the unsaturated group is Malaysia Imide.
[9] positive type photosensitive organic compound according to [8], which is characterized in that the polyimide precursor passes through Following methods manufacture, and the method includes the following process:
Process (i): acid compound the rubbing with 1:0.8~0.95 that the diamine compound that formula (6) indicates is indicated with formula (7) You obtain the polyamic acid that end has amino than carrying out reaction；
H2N-R11-NH2 (6)
(wherein, x, y indicate 0 or 1, and z indicates 0~4 integer.)
And
Process (ii): amino and bismaleimide amine compounds by making the end of polyamic acid obtained in process (i) Object reacts to obtain the polyimide precursor that end has dimaleoyl imino.
[10] positive type photosensitive organic compound according to any one of [1]~[9], which is characterized in that containing more 20~70 mass parts of 20~50 mass parts of alkenyl phenol resin, 100 mass parts of alkali soluble resin and quinone di-azido compound.
[11] positive type photosensitive organic compound according to any one of [6]~[10], which is characterized in that formula (5) The solid component acid value of the polyimide precursor of expression is 110~210mgKOH/g.
[12] a kind of radioactive ray photolithographic structures object, obtains, the method includes the following process by the following method:
(1) positive type photosensitive organic compound described in any one of [1]~[11] painting process: is coated on substrate；
(2) drying process: the solvent in the positive type photosensitive organic compound after coating is removed；
(3) exposure process: radioactive ray are irradiated across photomask；
(4) pattern developing procedure: is formed by alkali development；And
(5) heating treatment step: 150~350 DEG C at a temperature of heated.
[13] the radioactive ray photolithographic structures object according to [12], which is characterized in that temperature when thermal weight loss is 5 mass % It is 350 DEG C or more.
Invention effect
According to the present invention it is possible to provide the few positive-type photolithography of the gas released from the film after heat firing with photonasty tree Oil/fat composition.It uses, can be manufactured there is no concern that causing because gas is released especially by organic electroluminescent device Performance deterioration element.
Specific embodiment
Hereinafter, being described in detail to the present invention.
(polyene-based phenol resin)
Polyene-based phenol resin can be by making phenol resol resins, cresol novolac resin, triphenyl methane type Phenol well known to phenol resin, phenol aralkyl resin, xenyl aralkyl-phenol resin, phenol-dicyclopentadiene copolymer resin etc. Alkenyl etherificate occurs for the hydroxyl of resin, and then makes alkenyl ether that Claisen rearangement occur and obtain.
Polyene-based phenol resin used in photosensitive polymer combination of the invention has the structure of formula (1).By containing There is this resin, the developing property for the photosensitive polymer combination that can be improved, and also contribute to releasing subtracting for gas It is few.The substitution of phenol resol resins, cresol novolac resin, more vinyl phenol resins can be especially work perfectly well as Product and use.
(in formula (1), R1、R2And R3Separately indicate that hydrogen atom, the alkyl of carbon atom number 1~5, formula (2) indicate The alkoxy or hydroxyl of alkenyl, carbon atom number 1~2, and R1、R2And R3In at least one be formula (2) indicate alkenyl.Q difference It independently is formula-CR4R5Cycloalkylidene, the divalent organic base with aromatic rings of the alkylidene, carbon atom number 5~10 that indicate Group, the bivalent organic group with ester ring type condensed ring or by bivalent group made of these moiety combinations, R4And R5Independently Ground indicates hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~6, the naphthenic base of carbon atom number 5~10 or carbon The aryl of atomicity 6~12.
In formula (2), R6、R7、R8、R9And R10Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, carbon atom The naphthenic base of number 3~10 or the aryl of carbon atom number 6~12.* in formula (2) indicates the key with the carbon atom for constituting aromatic rings Conjunction portion.)
R in formula (1)1、R2And R3Indicate hydrogen atom, the alkyl of carbon atom number 1~5, alkenyl, carbon atom shown in formula (2) The alkoxy or hydroxyl of number 1~2, and R1、R2And R3In at least one be formula (2) indicate alkenyl.
R in formula (1)1、R2And R3In, the concrete example of the alkyl as carbon atom number 1~5 can be enumerated: methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl etc..Alkoxy as carbon atom number 1~2 it is specific Example, can enumerate methoxyl group, ethyoxyl.
In the alkenyl that formula (2) indicates, R6、R7、R8、R9And R10Separately indicate the alkane of hydrogen atom, carbon atom number 1~5 The aryl of base, the naphthenic base of carbon atom number 5~10 or carbon atom number 6~12.The concrete example of alkyl as carbon atom number 1~5, It can enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl etc..As carbon atom number 5 ~10 naphthenic base can be enumerated: cyclopenta, cyclohexyl, methylcyclohexyl, suberyl etc..Virtue as carbon atom number 6~12 The concrete example of base can be enumerated: phenyl, aminomethyl phenyl, ethylphenyl, xenyl, naphthalene etc..As R6、R7、R8、R9And R10, It is preferred that being separately hydrogen atom or the alkyl of carbon atom number 1~5.As the alkenyl that preferred formula (2) indicate, from reactivity From the aspect of, allyl, methacrylic, more preferably allyl can be enumerated.Moreover, R1、R2And R3In, most preferably one For allyl or methacrylic, other 2 are hydrogen atom.
Q is separately formula-CR4R5The cycloalkylidene of the alkylidene, carbon atom number 5~10 that indicate has aromatic rings Bivalent organic group, the bivalent organic group with ester ring type condensed ring or by bivalent group made of these moiety combinations. R4And R5Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~6, carbon atom number 5~10 Naphthenic base or carbon atom number 6~12 aryl.R4And R5In, the concrete example of the alkyl as carbon atom number 1~5, Ke Yiju Out: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl etc..Alkene as carbon atom number 2~6 The concrete example of base can be enumerated: vinyl, allyl, cyclobutenyl, pentenyl, hexenyl etc..As carbon atom number 5~10 Naphthenic base can be enumerated: cyclopenta, cyclohexyl, methylcyclohexyl, suberyl etc..The tool of aryl as carbon atom number 6~12 Body example can be enumerated: phenyl, aminomethyl phenyl, ethylphenyl, xenyl, naphthalene etc..R4And R5It is separately preferably that hydrogen is former The alkyl of son or carbon atom number 1~3, most preferably hydrogen atom.
The concrete example of cycloalkylidene as the Q carbon atom number 5~10 indicated, can enumerate: cyclopentylene, sub- hexamethylene Base, methylcyclohexylidene, cycloheptylidene etc..It as the concrete example of the bivalent organic group with aromatic rings, can enumerate: sub- benzene Base, xylene, naphthylene, biphenylene, fluorenylidene, anthrylene, xylylene, 4,4- methylene diphenylene, formula (8) The base etc. of expression.
As the concrete example of the bivalent organic group with ester ring type condensed ring, sub- dicyclopentadienyl etc. can be enumerated.
In polyene-based phenol resin used in photosensitive polymer combination of the invention, from alkali-developable, gas is released From the aspect of, as particularly preferred polyene-based phenol resin, the polyene-based phenol tree of the structure indicated with formula (3) can be enumerated Rouge.
(in formula (3), R1、R2And R3It indicates and the R in formula (1)1、R2And R3The identical meaning.)
Preferred R1、R2And R3With the preferred R in formula (1)1、R2And R3Equally.
Phenolic hydroxyl group ionizes in the presence of alkali compounds, can be dissolved in water, therefore, from alkali-developable Viewpoint is set out, and phenolic hydroxyl group needs for more than a certain amount of.Therefore, the structure that formula (1) or formula (3) indicate is in polyene-based phenol resin Preferably 50~100 mass %, more preferably 70~100 mass %.The polyene-based phenol resin of structure containing formula (3) is further The particularly preferably polyene-based phenol resin of formula (4) expression.
(in formula (4), R1、R2And R3It indicates and the R in formula (1)1、R2And R3The identical meaning.In addition, p be 0~50 it is whole Number.)
In addition, the number-average molecular weight of polyene-based phenol resin used in the present invention is preferably 800~5000, more preferably 1000~3000.If number-average molecular weight is lower than 800, the quantitative change for releasing gas is more, when more than 5000, alkali-developable drop It is low.
It should be noted that the number-average molecular weight and weight average molecular weight in the application are the polyphenyl measured by GPC The value of ethylene conversion.
(manufacturing method of polyene-based phenol resin)
The polyene-based phenol resin of structure used in the present invention with formula (1) is the phenol resin by that will become raw material Hydroxyl carry out Claisen rearangement reaction occurs after alkenyl etherificate and alkenyl made to reset ortho position to original hydroxyl or contraposition Obtained from resin.
The raw material phenol resin of polyene-based phenol resin as the structure with formula (1), can be used the structure with formula (9) Well known phenol resin.
(in formula (9), X1、X2And X3Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, carbon atom number 1~2 Alkoxy or hydroxyl, and the carbon atom for the phenyl ring being bonded with relative to hydroxyl is taking for the carbon atom bonding of ortho position or contraposition At least one of Dai Jizhong is hydrogen atom.Q indicates the meaning identical with the Q in formula (1).)
X in formula (9)1、X2And X3In, the concrete example of the alkyl as carbon atom number 1~5 can be enumerated: methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl etc..Alkoxy as carbon atom number 1~2 it is specific Example, can enumerate methoxyl group, ethyoxyl.In addition, Q, R4And R5Respectively with Q, R in formula (1)4And R5It is identical.
As the concrete example for the phenol resin that formula (9) indicate, can enumerate: phenol resol resins, cresol novolak Resin, triphenyl methane type phenol resin, phenol aralkyl resin, xenyl aralkyl-phenol resin, phenol-dicyclopentadiene copolymerization Resin etc., from the viewpoint of alkali-developable it is preferable to use Q be-CR4R5The alkylidene and R indicated4And R5For hydrogen original Phenol resol resins, the cresol novolac resin of son.
(the alkenyl etherification reaction of phenol resin)
The alkenyl etherification reaction of phenol resin may be exemplified the following two kinds method: (i) make allyl chloride, methallyl chloride, The well known method that the halogenations such as allyl bromide, bromoallylene alkenyl compound is reacted with phenol resin；(ii) make the carboxylic acid alkene of allyl acetate etc The method that based compound is reacted with phenol resin.
It can be used in such as Japanese Unexamined Patent Publication 2-91113 bulletin using the alkenyl etherification reaction of halogenation alkenyl compound The method of record.In addition, such as Japanese Unexamined Patent Publication 2011- can be used in the method for reacting carboxylic acid alkenyl compound with phenol resin The method recorded in No. 26253 bulletins.From the aspect of requiring long-term insulation performance, photosensitive polymer combination of the invention is excellent Choosing, which will not be mixed into, to be possible to bring the upper of the dysgenic halogen compound from halogenation alkenyl compound to long-term insulation performance The method for stating (ii).
Halogenation alkenyl compound or alkenyl carboxylate are preferably 0.3~1.0 equivalent relative to the addition amount of phenolic hydroxyl group, more Preferably 0.5~1.0 equivalent.If be lower than 0.3 equivalent, there are react after Claisen rearangement with bismaleimide Property reduce the case where.
(Claisen rearangement of polyene-based ether resin is reacted)
Target polyene-based phenol resin can be by making to utilize the method recorded in above-mentioned " the alkenyl etherification reaction of phenol resin " Manufactured polyene-based ether resin occurs Claisen rearangement and reacts to obtain.Claisen rearangement reaction can be by being heated to 100 ~250 DEG C of temperature reacts 1~20 hour to obtain.High boiling solvent can be used in Claisen rearangement reaction, can also not Use solvent.In addition, the inorganic salts such as sodium thiosulfate, sodium carbonate can be added in order to promote rearrangement reaction.Specifically, remember It is loaded in Japanese Unexamined Patent Publication 2-91113 bulletin.
By the reaction of phenol resol resins → alkenyl ether resin → (Claisen rearangement reaction) → polyene-based phenol resin The example of formula is shown in reaction equation 1 below.
(content of polyene-based phenol resin)
As for the content of the polyene-based phenol resin in photosensitive polymer combination, it is with 100 mass parts of alkali soluble resin Benchmark, preferably 20~50 mass parts, more preferably 30~40 mass parts.More than 20 mass parts, 300~400 DEG C Heat resistance when firing becomes well, if it is 50 below the mass, patternability when alkali development becomes good.
(alkali soluble resin)
It (wherein, does not include the structure with formula (1) that photosensitive polymer combination of the invention, which contains alkali soluble resin, Polyene-based phenol resin.).Alkali soluble resin makes favorable solubility of the composition in aqueous slkali.
As alkali soluble resin, preferably there is hydroxy or carboxy, can enumerate: phenol resol resins, cresol novolac Varnish gum, acrylic acid series polymeric compounds carboxylic-containing acid, the acrylic acid series polymeric compounds containing phenylol, contains carboxylic at more vinyl phenol resins Acid silicone resin, the silicone resin containing phenylol, polyphenyl simultaneouslyAzoles precursor, polyimide precursor, the polyamides containing phenylol are sub- Amine etc..
Here, the characteristic as alkali soluble resin, preferably makes 2 μm of resin coating film on a glass, is impregnated in When 2.38% tetramethylammonium hydroxide aqueous solution, it is completely dissolved within 60 seconds.
(polyimide precursor)
It is required that, it is preferable to use polyimide precursor is as alkali soluble resin in the case where higher heat resistance.The present invention Photosensitive polymer combination preferably comprise formula (5) expression polyimide precursor.
(in formula (5), R11Indicate the bivalent organic group of 2 or more carbon atom number, R12Indicate the trivalent of 2 or more carbon atom number Or the organic group of tetravalence, R13Indicate the organic group of hydrogen atom or carbon atom number 1~20, R14Indicate hydrogen atom or carbon atom The organic group of number 1~50, m indicate 1 or 2, and n indicates 5~200 integer.)
In formula (5), R11And R12It is preferred that having aromatic ring, preferred above-mentioned aromatic ring is phenyl ring and naphthalene nucleus.As R11 Example, can enumerate:
Deng.As R12Example, can enumerate:
Deng.In addition, as R13Carbon atom number 1~20 organic group example, can enumerate: methyl, ethyl, propyl, Butyl, amyl, hexyl, trimethyl silyl, phenyl, hydroxy phenyl, carboxyl phenyl, methyl carboxyl phenyl etc..It is shown to alkali From the aspect of the dissolubility of shadow liquid, preferably hydrogen atom, hydroxy phenyl or carboxyl phenyl.As R14Carbon atom number 1~50 have The example of machine group, the residue after reacting for carboxylic acid compound, carboxylic acid anhydrides or maleimide with amino are aobvious to alkali in order to adjust The dissolubility of shadow liquid and suitably select.At this point, it is preferred that the solid component acid value of the compound of formula (5) is set as 110~ 210mgKOH/g.If the solid component acid value of the compound of formula (5) is 110mgKOH/g or more, polyene-based phenol tree is cooperated When rouge and quinone di-azido compound, to the dissolubility of alkaline developer become well, if its be 210mgKOH/g hereinafter, if alkali it is aobvious The pattern form of movie queen becomes good.In addition, R14Preferably comprise unsaturated group.It as unsaturated group, does not limit, can lift Out: dimaleoyl imino, vinyl, allyl, acryloyl group, methylacryloyl etc., wherein preferred dimaleoyl imino. Here, dimaleoyl imino is the form for occurring to be detached from and become associative key with the hydrogen atom of the nitrogen atom bonding of maleimide Monovalent organic group.R14When containing dimaleoyl imino, with polyene-based phenol resin carry out cross-linking reaction, therefore, heat resistance into One step improves, so it is preferred that.The preferred number-average molecular weight of the compound of formula (5) is 5000~20000.
The polyimide precursor that formula (5) indicates can be by making diamine compound or derivatives thereof and tricarboxylic acids, tetrabasic carboxylic acid Equal acid compounds or derivatives thereof are dissolved in such as n-methyl-2-pyrrolidone, gamma-butyrolacton, N, N- dimethyl sulfoxide, N, N- Dimethyl acetamide, N,N-dimethylformamide, propylene carbonate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, butyl In cellosolve, ethyl cellosolve equal solvent, and is reacted and obtained in the range of -30 DEG C~300 DEG C.
At this point, it is preferred that make acid compounds such as diamines or derivatives thereof and tricarboxylic acids, tetrabasic carboxylic acid or derivatives thereof with 1:0.8~ 0.95 molar ratio is reacted, so that end be made to become amino.Can also further make end amino and carboxylic acid compound, The reaction such as carboxylic acid anhydrides or maleimide.
Preferred diamines formula (6) for manufacturing the compound of formula (5) indicates.
H2N-R11-NH2 (6)
In formula (6), R11With the R of formula (5)11It is identical.
As the concrete example of the diamine compound used, can enumerate: Isosorbide-5-Nitrae-phenylenediamine, 1,3- phenylenediamine, 4, 4 '-diamino-diphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfones, 4,4 '-diamino-diphenyls Thioether etc., these substances can be used alone or mix two or more and use.
Preferred acid compound formula (7) for manufacturing the compound of formula (5) indicates.
(wherein, x, y indicate 0 or 1, and z indicates 0~4 integer.And then be x+y+z > 0, xy=1 when, z=0, xy=0 and It is z=3 or 4 when z=1 or 2, x=0 and y=0 when x+y=1.)
It should be noted that in formula (7), R12With the R of formula (5)12It is identical.
As the concrete example of the acid compound used, can enumerate: Pyromellitic Acid, 3,3 ', 4,4 '-biphenyltetracarboxylic acids, 2,3,3 ', 4 '-biphenyltetracarboxylic acids, 3,3 ', 4,4 '-benzophenone tetracarboxylics, 4,4 '-oxygroup, two phthalic acid, 3,3 ', 4, 4 '-diphenyl sulfone tetracarboxylic acids, 2,2 '-bis- (3,4- dicarboxyphenyi) hexafluoropropane, 2,3,6,7- naphthalenetetracarbacidic acidic, 1,2,5,6- naphthalene Tetracarboxylic acid, 1,4,5,8 naphthalenetetracarboxylic acid, 1,2,3,4- cyclobutanetetracarboxylic, 1,2,3,4- ethylene-dimalonic acid, 1,2,4,5- ring penta Alkane tetracarboxylic acid, 1,2,4,5- cyclohexanetetracarboxylic acid, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic acids, 2,3,5- tricarboxylic cyclopentyl acetic acid Deng or their acid anhydrides, these substances can be used alone or mix two or more and use.
It as the maleimide compound that the amino with end reacts, can enumerate: N-phenylmaleimide, to hydroxyl Phenyl maleimide, hydroxyphenyl-maleimides, to carboxyl phenyl maleimide, N- dodecyl maleimide Equal simple functions maleimide compound, bis- (4- maleimidophenyl) methane, 4- methyl-1,3- dimaleimide base The dimaleoyl iminos compounds, the three (Malaysia 4- acyls such as benzene, bis- (3- ethyl -5- methyl -4- maleimidophenyl) methane Imido grpup phenyl) four Malaysias such as three maleimide based compounds, bis- (3,4- dimaleimide base phenyl) methane such as methane Polymaleimides based compound, these substances such as imide compound and poly- (4- dimaleoyl imino styrene) can be single Solely uses or mix two or more and use.
(quinone di-azido compound)
Positive type photosensitive organic compound of the invention contains quinone di-azido compound as radiation-sensitive compound. It as quinone di-azido compound, can enumerate: obtained from the sulfonic acid of two nitrine of quinone is bonded in the form of ester with polyol Compound；Compound obtained from the sulfonic acid of two nitrine of quinone is bonded in a manner of sulfonamide with multiamino compound；Two nitrine of quinone Sulfonic acid be bonded in a manner of ester and/or sulfonamide with polyhydroxy multiamino compound obtained from compound etc..From exposure portion From the perspective of the contrast in unexposed portion, the preferably functional group of these polyols or multiamino compound is whole 50 moles of % or more are by two azide substitution of quinone.It is available as Conventional UV by using this quinone di-azido compound The photoresist of photosensitive eurymeric is carried out under the i ray (365nm) of the mercury lamp of line, h ray (405nm), g ray (436nm) Composition.
As polyol, can enumerate: Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA、TrisOCR-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、 BisRS-2P、BisRS-3P、BisP-OCHP、メチレントリス-FR-CR、BisRS-26X、DML-MBPC、DML-MBOC、 DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、ジメチロール-BisOC- P、DML-PFP、DML-PSBP、DML-MTrisPC、TriML-P、TriML-35XL、TML-BP、TML-HQ、TML-pp-BPF、 TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade name, Honshu Chemical Ind's systems), BIR-OC、BIP-PC、BIR-PC、BIR-PTBP、BIR-PCHP、BIP-BIOC-F、4PC、BIR-BIPC-F、TEP-BIP-A、 46DMOC, 46DMOEP, TM-BIP-A (the above are trade name, rising sun organic material Industrial Co., Ltd systems), 2,6- dimethoxy first Base -4-TBP, 2,6- dimethoxy-methyl-paracresol, 2,6- diacetoxy methyl-paracresol, naphthols, tetrahydroxy (the above are trade name, Honshu chemistry works by benzophenone, gallic acid methyl esters, bisphenol-A, bis-phenol E, methylene bis-phenol, BisP-AP Industry Co. Ltd. system) etc., but it is not limited to these.
It as the example of quinone di-azido compound, can enumerate: 1,2- naphthoquinones, the two nitrine -4- sulphur of above-mentioned polyol Two nitrine -5- sulphonic acid ester of acid esters or 1,2- naphthoquinones.
Quinone di-azido compound generates carboxyl by reacting shown in following reaction equations 2 when being exposed with ultraviolet light etc.. By generating carboxyl, the part being exposed (epithelium) becomes to be dissolvable in water aqueous slkali, shows alkali-developable.
The content of quinone di-azido compound in photosensitive polymer combination is different due to the quinone di-azido compound used, On the basis of 100 mass parts of alkali soluble resin, preferably 20~70 mass parts, more preferably 30~60 mass parts.For 20 matter When measuring part or more, alkali-developable is good.In addition, below the mass if it is 70,300 DEG C or more of thermal weight loss is not easy to become larger.
Photosensitive polymer combination of the invention can be dissolved in solvent and be used with solution state.For example, by polyene-based phenol Resin, alkali soluble resin are dissolved in solvent, mixed in certain proportion in the solution quinone di-azido compound, as needed Thermal curing agents, surfactant or dyestuff, the colorants such as pigment, it is possible thereby to prepare the photosensitive resin composition of solution state Object.
It as solvent, can enumerate for example: glycol monoethyl ether, glycol dimethyl ether, Ethylene Glycol Methyl ethylether, ethylene glycol The ethylene glycol alkyl ethers such as the glycol ethers such as single ether, methylcellosolve acetate, ethyl cellosolve acetate acetic acid esters, diethylene glycol Monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethyl two The propylene glycol alkyls ether acetic acid such as the diethylene glycols such as alcohol monobutyl ether class, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters esters, Toluene, dimethylbenzene etc. is aromatic hydrocarbon, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4- hydroxy-4-methyl-2-pentanone, ring The ketones such as hexanone, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyl methyl propionate, 2- hydroxy-2-methyl ethyl propionate, ethyoxyl Ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-2-methyl methyl butyrate, 3- methoxy methyl propionate, 3- methoxypropionic acid second Ester, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ- The amides such as the esters such as butyrolactone, n-methyl-2-pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.These Solvent can be used alone, and can also combine two or more.
Hot radical producing agent can be used as heat as any ingredient in positive type photosensitive organic compound of the invention Curing agent.As preferred hot radical producing agent, organic peroxide can be enumerated specifically, diamyl peroxide can be enumerated Compound, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, t-butyl amyl peroxide, di-tert-butyl peroxide, 10 hours half life temperatures such as 1,1,3,3- tetramethyl butyl hydroperoxide, isopropyl benzene hydroperoxide are 100~170 DEG C organic Peroxide etc..
It, can with polyene-based phenol resin, alkali as the preferred content of the thermal curing agents in positive type photosensitive organic compound On the basis of 100 mass parts of total amount of soluble resin, preferably 0.1~5 mass parts, more preferably 0.5~3 mass parts.
Positive type photosensitive organic compound of the invention is further used as any ingredient, for example, in order to improve coating or In order to improve the developability of film, surfactant can be contained.
As this surfactant, can enumerate for example: polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxy The polyoxyethylene alkyl ethers class such as ethylene oleyl ether；The polyoxyethylene such as NONIN HS 240, ethylene nonyl phenyl ether Aryl ethers；The nonionic systems such as the polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate Surfactant；メガファックF-251,メガファックF-281,メガファックF-430,メガファックF- 444, メ ガ Off ァ ッ Network R-40 (more than, trade name, Dainippon Ink Chemicals), サ ー Off ロ Application S-242, サ ー Off ロ Application S- 243, サ ー Off ロ Application S-420, サ ー Off ロ Application S-611 (the above are trade name, ACG セ イ ミ ケ ミ カ Le Co. Ltd. systems) etc. Fluorine system surfactant；(the above are trade name, SHIN-ETSU HANTOTAI's chemical industry strains by organic siloxane polymer KP323, KP326, KP341 Formula commercial firm system) etc..Two or more also can be used in these substances.As for the amount of this surfactant, with polyene-based phenol resin, On the basis of 100 mass parts of total amount of alkali soluble resin, below the mass, preferably 1 below the mass for cooperation 2.
In turn, positive type photosensitive organic compound of the invention can contain the coloring such as dyestuff, pigment as any ingredient Material.The coloured materials such as this dyestuff or pigment can be inorganic pigment, or organic pigment.As this coloured material Concrete example, can enumerate: black pigments or the C.I. such as carbon black, carbon nanotube, acetylene black, graphite, iron oxide black, nigrosine, titanium are black Pigment yellow 20,24,86,93,109,110,117,125,137,138,147,148,153,154,166, C.I. pigment orange 36, 43,51,55,59,61, C.I. Pigment Red 9,97,122,123,149,168,177,180,192,215,216,217,220, 223,224,226,227,228,240, C.I. pigment violet 19,23,29,30,37,40,50, C.I. pigment blue 15,15:1,15: 4,22,60, the 64, coloring pigments such as C.I. pigment Green 7, C.I. pigment brown 23,25,26.
(preparation method)
Positive type photosensitive organic compound of the invention is by by above-mentioned polyene-based phenol resin, alkali soluble resin, quinone Two azido compounds and other ingredients as needed are dissolved or dispersed in above-mentioned solvent and mix and prepare, and are made according to it With purpose, solid component concentration appropriate can be used, such as can be set to 10~60 mass % of solid component concentration.In addition, The combination thing liquid prepared as described above is usually filtered before use.As the method for filtering, such as aperture can be enumerated 0.05~1.0 μm of millipore filter etc..
Prepared positive type photosensitive organic compound of the invention, long-standing storage-stable are also excellent in this way.
(pattern forming method and curing method)
When radioactive ray photoetching process is with positive type photosensitive organic compound of the invention is used on the way, firstly, by of the invention Positive type photosensitive organic compound be coated on substrate surface, solvent can be removed by dry etc. by the methods of heating It goes, forms film.The coating method of the positive type photosensitive organic compound of substrate surface is not particularly limited, example can be used Such as various methods of spray-on process, rolling method, Narrow slit, method of spin coating.
After positive type photosensitive organic compound of the invention is coated on substrate surface, usually pass through heating (prebake conditions) Solvent seasoning is made to film.Heating condition is also different due tos the type of each ingredient, mixing ratio etc., usually 70~120 Heat the stipulated time at DEG C, for example, if then heating 1~20 minute on electric hot plate, heating 3 in an oven ~60 minutes, it is hereby achieved that film.
Then, it is (such as luminous ray, ultraviolet that radioactive ray are irradiated via the mask of predetermined pattern to the film through prebake conditions Line, far ultraviolet, X-ray, electron beam, gamma-rays, synchrotron radioactive ray etc.) etc. (exposure process) utilize development thereafter Liquid develops, and removes unwanted part, is formed predetermined pattern shape film (developing procedure).As for eurymeric sense of the invention Preferred radioactive ray for photosensitive resin composition, since it is preferable to use naphthalene quinone di-azide sulfonic acid esters as positive light sensitivity chemical combination Object, so being ultraviolet light~luminous ray of the wavelength with 250~450nm.As developer solution, it can be used for example: hydrogen-oxygen Change the inorganic bases such as sodium, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammonium hydroxide；The primary amine classes such as ethylamine, n-propyl amine； The secondary amine class such as diethylamide, two-n-propyl amine；The tertiary amines such as triethylamine, methyidiethylamine；Dimethylethanolamine, three second The alcamines such as hydramine；The quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline；Pyrroles, piperidines, 1,8- diaza The aqueous solution of the bases such as the cyclic amines such as bicyclic [5.4.0] -7- endecatylene, 1,5- diazabicyclo [4.3.0] -5- nonane. Alternatively, it is also possible to use the water-miscible organic solvents, surface-active such as the methanol, the ethyl alcohol that add appropriate amount in above-mentioned aqueous alkali The aqueous solution of agent etc. is as developer solution.Developing time is usually 30~180 seconds, in addition, the method for development can be liquid pool method, spray Leaching method, infusion process etc. are any.After development, carry out flowing water and clean 30~90 seconds, remove unwanted part, with compressed air or Compressed nitrogen carries out air-dried, and pattern is consequently formed.Thereafter, by the pattern using heating devices such as electric hot plate, baking ovens, in predetermined temperature Such as heat 20~200 minutes at 150~350 DEG C, it is hereby achieved that film, can also periodically improve temperature (heating treatment step).
The radioactive ray photolithographic structures object of the positive type photosensitive organic compound of the invention made in aforementioned manners is used Volatile ingredient can also be removed and being further burnt under conditions of 350~450 DEG C, temperature when 5% Mass lost is made Spend high radioactive ray photolithographic structures object.If firing temperature be 450 DEG C hereinafter, if radioactive ray photolithographic structures object be not susceptible to heat it is bad Change.The atmosphere of firing can be any in air or under the inert gas atmospheres such as nitrogen.In addition, firing time also depends on firing Temperature, preferably 5~60 minutes, more preferably 10~40 minutes.If firing time is lower than 5 minutes, effect can't see sometimes, When it is more than 60 minutes, productivity is reduced sometimes.
Embodiment
Hereinafter, being based on Examples and Comparative Examples, the present invention is concretely demonstrated, but the present invention is not limited to these realities Apply example.
(1) resins synthesis
The manufacture of [Production Example 1] polyenoid propyl phenoxy Resin A -1
It is packed into 3 shape of the mouth as one speaks flasks of 1000mL potassium carbonate (Tso Tat Co., Ltd., Japan's system) 201g (1.45mol) is molten Solution that solution is formed in pure water 150g, phenol resol resins " シ ョ ウ ノ ー Le " (trade mark) BRG-556 (Showa electrician Co. Ltd. system) 150.0g, reactor is subjected to nitrogen displacement and is heated to 85 DEG C.It is put into allyl acetate under nitrogen flowing (Showa Denko K. K's system) 204g (2.04mol), containing 50% water 5%-Pd/C-STD type (by Metal Palladium in active carbon with The content of 5 mass % is dispersed, and by above-mentioned Metal Palladium and active carbon dispersion in a manner of becoming 50 mass % hydrous water And the catalyst of stabilized allylation reaction, エ ヌ イ ー ケ system キ ャ ッ ト Co. Ltd. system) 0.62g (0.291mmol) and triphenylphosphine (use the activator of the allylation reaction catalyst of above-mentioned palladium, the emerging chemical industry strain formula in north Commercial firm's system) 3.82g (14.6mmol), it is warming up in nitrogen atmosphere after 105 DEG C, reaction 4 hours, chases after and add allyl acetate 29g (0.291mol) continues heating 10 hours.Thereafter stop stirring, stand, be thus separated into two layers of organic layer and water layer.Addition Then until the salt dissolution being precipitated, toluene 200g is added in pure water (200g), confirm that the temperature for being maintained at 80 DEG C or more does not have After white precipitate is precipitated, by filtering, (1 μm of membrane filter (passes through pressurization using ADVANTEC society KST-142-JA (0.3MPa)) recycling Pd/C.The filter residue is cleaned with toluene 100g, its cleaning solution is merged with filtrate.By the water layer of the filtrate It is separated, organic layer is cleaned 2 times with water 200g, confirm its cleaning solution for neutrality.Separate organic layer after, under reduced pressure into Row concentration, obtains the polyallyl ethers resin of the phenol novolak type of brown oil.The substance is carried out1H-NMR measurement Result confirmation: contain the polyallyl ethers resin of phenol novolak type as principal component.The following institute of the determination data of feature It states.1H-NMR (400MHz, CDCl3, 27 DEG C), δ 3.6-4.0 (m ,-Ph-CH2 - Ph-) δ 4.4-4.8 (2H, m ,-CH2 CH=CH2), δ 5.1-5.3 (1H, m ,-CH2CH=CHH), δ 5.3-5.5 (1H, m ,-CH2CH=CHH), δ 5.8-6.2 (1H, m ,-CH2CH= CH2), δ 6.6-7.3 (m, phenyl ring).
In addition, measuring the hydroxyl value of the substance, but it is nearly no detectable.
Then, the polyallyl ethers resin of phenol novolak type is put into the burning for being fixed with the 500mL of mechanical agitator In bottle.It is stirred on one side with 300rpm, is warming up to 190 degree on one side, it is small to carry out Claisen rearangement reaction 10 in this state When, obtain the polyenoid propyl phenoxy Resin A -1 of phenol novolak type.The hydroxyl equivalent of polyenoid propyl phenoxy Resin A -1 is 165, can To confirm the generation of hydroxyl.In addition, number-average molecular weight is 1000, weight average molecular weight 2400.The substance is carried out1H-NMR The result of measurement confirms: the polyenoid propyl phenoxy Resin A -1 containing phenol novolak type is used as principal component.The determination data of feature As described below, it can be confirmed that the chemical shift of the hydrogen atom of allyl is moved after Claisen rearangement reaction.1H-NMR (400MHz, CDCl3, 27 DEG C), δ 3.2-3.4 (2H, m ,-CH2 CH=CH2), δ 3.6-4.0 (m ,-Ph-CH2- Ph- ,-OH), δ 4.6-5.0 (1H, m ,-CH2CH=CHH), δ 5.0-5.3 (1H, m ,-CH2CH=CHH), δ 5.8-6.1 (1H, m ,-CH2CH= CH2), δ 6.6-7.2 (m, phenyl ring).
For the resin, in formula (4), R1、R2、R3In 1 be allyl, other expression hydrogen atoms.
The manufacture of [Production Example 2] polyimide precursor 1
By 4,4 '-diamino-diphenyl ethers (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " ODA ".)10.00g (0.05 mole) is dissolved in N-Methyl pyrrolidone (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " NMP ".) 70g, add Enter 3,3 ', 4,4 '-biphenyltetracarboxylic acid acid anhydrides (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " BPDA ".)13.22g (0.045 mole) stirs 5 hours at 40 DEG C.Thereafter, bis- (3- ethyl -5- methyl -4- maleimidophenyl) first are added (ケ イ ア イ is melted into Co. Ltd. system, hereinafter referred to as " BMI-70 " to alkane.) 4.42g (0.01 mole), further at 90 DEG C Lower stirring 3 hours.It after reaction solution is returned to room temperature, devotes in acetone 1500mL, recycles sediment, obtain faint yellow Solid.Further obtained solid is cleaned with water 1500mL, it is 10 hours dry with 50 DEG C of vacuum drier thereafter, gathered The pale yellow powder of imide precursor 1.The solid component acid value of polyimide precursor 1 is 175mgKOH/g.
The manufacture of [Production Example 3] polyimide precursor 2
ODA (Wako Pure Chemical Industries, Ltd.'s system) 10.00g (0.05 mole) is dissolved in NMP (and Wako Pure Chemical Industries strain Formula commercial firm system) 70g, BPDA (Wako Pure Chemical Industries, Ltd.'s system) 13.22g (0.045 mole) is added, stirs 5 at 40 DEG C Hour.Thereafter, it is added to hydroxy-benzyl alcohol (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " p-HBzOH ".)5.58g (0.045 mole) further stirs 3 hours at 100 DEG C.After reaction solution is returned to room temperature, acetone is devoted In 1500mL, sediment is recycled, faint yellow solid is obtained.Further obtained solid is cleaned with water 1500mL, thereafter, with 50 DEG C vacuum drier dry 10 hours, obtain the pale yellow powder of polyimide precursor 2.The solid of polyimide precursor 2 at Dividing acid value is 150mgKOH/g.
The manufacture of [Production Example 4] polyimide precursor 3
ODA (Wako Pure Chemical Industries, Ltd.'s system) 10.00g (0.05 mole) is dissolved in NMP (and Wako Pure Chemical Industries strain Formula commercial firm system) 70g, BPDA (Wako Pure Chemical Industries, Ltd.'s system) 13.22g (0.045 mole) is added, stirs 5 at 40 DEG C Hour.Thereafter, BMI-70 (ケ イ ア イ is melted into Co. Ltd. system) 4.42g (0.01 mole) is added, further at 90 DEG C P-HBzOH (Wako Pure Chemical Industries, Ltd.'s system) 5.58g (0.045 mole) is added, further at 100 DEG C in stirring 3 hours Stirring 3 hours.It after reaction solution is returned to room temperature, devotes in acetone 1500mL, recycles sediment, obtain pale yellow colored solid Body.Further obtained solid is cleaned with water 1500mL, it is 10 hours dry with 50 DEG C of vacuum drier thereafter, obtain polyamides The pale yellow powder of imines precursor 3.The solid component acid value of polyimide precursor 3 is 115mgKOH/g.
The manufacture of [Production Example 5] polyimide precursor 4
ODA (Wako Pure Chemical Industries, Ltd.'s system) 10.00g (0.05 mole) is dissolved in NMP (and Wako Pure Chemical Industries strain Formula commercial firm system) 70g, BPDA (Wako Pure Chemical Industries, Ltd.'s system) 13.22g (0.045 mole) is added, stirs 5 at 40 DEG C Hour.Reaction solution is devoted in acetone 1500mL, sediment is recycled, obtains faint yellow solid.Further consolidate what is obtained Body is cleaned with water 1500mL, 10 hours dry with 50 DEG C of vacuum drier thereafter, obtains the yellowish toner of polyimide precursor 4 End.The solid component acid value of polyimide precursor 4 is 210mgKOH/g.
(2) preparation and evaluation of positive type photosensitive organic compound
Embodiment 1
6 mass parts polyenoid propyl phenoxy Resin As -1 and 20 mass parts are molten as the polyimide precursor 1 of alkali soluble resin TS-200A (Japan conjunction of 9 mass parts as quinone di-azido compound is added in 100 mass parts of n-methyl-2-pyrrolidone in solution At Industrial Co., Ltd's system, α, 1,2- naphthoquinones, the two nitrine -5- sulphur of α, α-three (4- hydroxy phenyl) -1- ethyl -4- cumene Acid esters).It after visual confirmation dissolution, is filtered with 1 μm of the millipore filter in aperture, prepares normal Photosensitive resin combination Object.
Embodiment 2
Polyimide precursor 1 is changed to polyimide precursor 2, in addition to this, is prepared similarly to Example 1.
Embodiment 3
Polyimide precursor 1 is changed to polyimide precursor 3, in addition to this, is prepared similarly to Example 1.
Embodiment 4
Polyimide precursor 1 is changed to polyimide precursor 4, in addition to this, is prepared similarly to Example 1.
Embodiment 5
Polyimide precursor 1 is changed to phenol resol resins " シ ョ ウ ノ ー Le " (trade mark) BRG-556 (Showa Electrician's Co. Ltd. system), in addition to this, prepare similarly to Example 1.
Embodiment 6
Polyimide precursor 1 is changed to cresol novolac resin " シ ョ ウ ノ ー Le " (trade mark) CRG-951 " (Showa Electrician's Co. Ltd. system), in addition to this, prepare similarly to Example 1.
Comparative example 1
It is (clear that polyene-based phenol resin A-1 is changed to cresol novolac resin " シ ョ ウ ノ ー Le " (trade mark) CRG-951 With electrician's Co. Ltd. system), in addition to this, prepare similarly to Example 1.
Comparative example 2
Polyimide precursor 1 and polyene-based phenol resin A-1 are all changed to phenol resol resins " シ ョ ウ ノ ー Le " (trade mark) BRG-556 (Showa Denko K. K's system), in addition to this, prepares similarly to Example 1.
Comparative example 3
Polyimide precursor 1 and polyene-based phenol resin A-1 are all changed to cresol novolac resin " シ ョ ウ ノ ー Le " (trade mark) CRG-591 (Showa Denko K. K's system), in addition to this, prepares similarly to Example 1.
Acid value is measured to polyimide precursor used in each embodiment and each comparative example, to each embodiment and each comparative example The positive type photosensitive organic compound of middle preparation, evaluation pattern generating formation, release gas at alkali-developable.Show the result in table 1.
The measuring method and pattern of acid value formed, alkali-developable and release gas evaluation method is as follows described.
[acid value]
It is measured according to JIS K0070.
[patternability and alkali-developable]
On glass substrate (size 100mm × 100mm × 1mm) by dry film thickness become about 2 μm in a manner of each reality of spin coating The positive type photosensitive organic compound for applying example and each comparative example, by solvent seasoning 2 minutes at 110 DEG C.Further with equipped with super The exposure device (trade name マ Le チ ラ イ ト ML-251A/B, ウ シ オ Electric Co., Ltd system) of high-pressure sodium lamp, via quartz The photomask of system is with 600mJ/cm2It is exposed.Use ultraviolet light accumulated light meter (trade name UIT-150, acceptance part UVD- S365, ウ シ オ Electric Co., Ltd system) measurement light exposure.The film of exposure further uses 2.38% tetramethylammonium hydroxide water Solution carries out alkali development, and the line width for measuring pattern becomes the alkali development time roughly the same with the line width of photomask, evaluation pattern generating Formative.The alkali development time was 30~100 seconds and is determined as zero the case where can carrying out pattern formation, by 100~180 seconds The case where situation is determined as △, will deviate from the range be determined as ×.The photomask of evaluation object as patternability The line width of pattern is 50 μm.
Alkali development is carried out using rotary developing device (AD-1200, Long Ze Industry Co., Ltd system), line width measurement uses light It learns microscope (VH-Z250, Co., Ltd.'s Keyemce system).In addition, the line width in pattern becomes the line width substantially phase with photomask With the presence or absence of the development residue of optical microscopy observation exposure portion in the same alkali development time, alkali-developable is thus evaluated.To not have There is the case where residue to be determined as zero, will have the case where residue be determined as ×.
[releasing gas]
The positive type photosensitive organic compound of each Examples and Comparative Examples of coating on aluminium sheet, it is 30 points dry at 100 DEG C 10~20 μm of thickness of film is made in clock.Further in air at 130 DEG C after drying 30 minutes, under a nitrogen at 250 DEG C Lower solidification 60 minutes.Using its film, use differential thermogravimetric amount while measurement device TG/DTA7000 (Co., Ltd. Hitachi Ha イ テ Network サ イ エ Application ス system), it heats up under nitrogen atmosphere from room temperature with 10 DEG C/min, measurement heating reduction amount is as releasing gas. It will be denoted as Td1 from the temperature of the Mass lost 1% before heating, the temperature of Mass lost 5% is denoted as Td5, is 370 DEG C by Td5 The case where above situation is determined as zero, and by 350 DEG C more than or lower than 370 DEG C the case where is determined as △, will be less than 350 DEG C judgement For ×.
[table 1]
Industrial availability
Radiation-ray sensitive composition of the invention can be adapted for positive radiation linear light lithography.Especially it can be adapted for The formation of the insulating films such as organic electroluminescent device.

Claims (12)

1. a kind of positive type photosensitive organic compound, polyene-based phenol resin, alkali soluble resin containing the structure with formula (1) And quinone di-azido compound, wherein the alkali soluble resin does not include the polyene-based phenol resin with the structure of formula (1),
In formula (1), R1、R2And R3Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, alkene represented by formula (2) The alkoxy or hydroxyl of base, carbon atom number 1~2, and R1、R2And R3In at least one be formula (2) indicate alkenyl；Q difference is only On the spot expression-CR4R5Cycloalkylidene, the divalent organic base with aromatic rings of the alkylidene, carbon atom number 5~10 that indicate Group, the bivalent organic group with ester ring type condensed ring or by bivalent group made of these moiety combinations, R4And R5Independently Ground indicates hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~6, the naphthenic base of carbon atom number 5~10 or carbon The aryl of atomicity 6~12；
In formula (2), R6、R7、R8、R9And R10Separately indicate hydrogen atom, the alkyl of carbon atom number 1~5, carbon atom number 5~ 10 naphthenic base or the aryl of carbon atom number 6~12；* in formula (2) indicates the bonding part with the carbon atom for constituting aromatic rings,
The alkali soluble resin is polyimide precursor.
2. positive type photosensitive organic compound according to claim 1, which is characterized in that
The structure of formula (1) is the structure of formula (3),
In formula (3), R1、R2And R3It indicates and the R in formula (1)1、R2And R3The identical meaning.
3. positive type photosensitive organic compound according to claim 2, which is characterized in that have the more of the structure of formula (3) Alkenyl phenol resin contains the structure of formula (4),
In formula (4), R1、R2And R3It indicates and the R in formula (1)1、R2And R3The identical meaning, in addition, the integer that p is 0~50.
4. positive type photosensitive organic compound described in any one of claim 1 to 3, which is characterized in that formula (2) institute table The alkenyl shown is allyl.
5. positive type photosensitive organic compound according to claim 1, which is characterized in that
Polyimide precursor formula (5) expression,
In formula (5), R11Indicate the bivalent organic group of 2 or more carbon atom number, R12Indicate the trivalent or tetravalence of 2 or more carbon atom number Organic group, R13Indicate the organic group of hydrogen atom or carbon atom number 1~20, R14Indicate hydrogen atom or carbon atom number 1~50 Organic group, m indicate 1 or 2, n indicate 5~200 integer.
6. positive type photosensitive organic compound according to claim 5, which is characterized in that the R in formula (5)14Contain insatiable hunger And group.
7. positive type photosensitive organic compound according to claim 6, which is characterized in that the unsaturated group is Malaysia Imide.
8. positive type photosensitive organic compound according to claim 7, which is characterized in that the polyimide precursor passes through Following methods manufacture, and the method includes the following process:
Process (i): diamine compound represented by formula (6) and acid compound rubbing with 1:0.8~0.95 represented by formula (7) You than carry out reaction to obtain end have amino polyamic acid,
H2N-R11-NH2(6)
Wherein, x, y indicate 0 or 1, and z indicates 0~4 integer；And
Process (ii): anti-by the amino and bismaleimide compound that make the end of polyamic acid obtained in process (i) Should come obtain end have dimaleoyl imino polyimide precursor.
9. positive type photosensitive organic compound described in any one of according to claim 1~3 and 5 contains polyene-based phenol resin 20~70 mass parts of 20~50 mass parts, 100 mass parts of alkali soluble resin and quinone di-azido compound.
10. the positive type photosensitive organic compound according to any one of claim 5~8, which is characterized in that formula (5) institute The solid component acid value of the polyimide precursor of expression is 110~210mgKOH/g.
11. a kind of radioactive ray photolithographic structures object, obtains, the method includes the following process by the following method:
(1) positive type photosensitive organic compound according to any one of claims 1 to 10 painting process: is coated on substrate；
(2) drying process: the solvent in the positive type photosensitive organic compound after coating is removed；
(3) exposure process: radioactive ray are irradiated across photomask；
(4) pattern developing procedure: is formed by alkali development；And
(5) heating treatment step: 150~350 DEG C at a temperature of heated.
12. radioactive ray photolithographic structures object according to claim 11, which is characterized in that temperature when thermal weight loss is 5 mass % Degree is 350 DEG C or more.
CN201580031678.9A 2014-07-18 2015-07-16 Positive type photosensitive organic compound Active CN106462064B (en)

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