CN103293858A - Photo-curable resin composition, method for manufacturing cured film, cured film, organic el device and liquid crystal display - Google Patents

Photo-curable resin composition, method for manufacturing cured film, cured film, organic el device and liquid crystal display Download PDF

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Publication number
CN103293858A
CN103293858A CN2013100614028A CN201310061402A CN103293858A CN 103293858 A CN103293858 A CN 103293858A CN 2013100614028 A CN2013100614028 A CN 2013100614028A CN 201310061402 A CN201310061402 A CN 201310061402A CN 103293858 A CN103293858 A CN 103293858A
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component units
alkyl
acid
mole
organic compound
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山﨑健太
米泽裕之
霜山达也
川岛敬史
下野胜弘
山田悟
汤本真敏
安藤豪
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Fujifilm Holdings Corp
Fujifilm Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

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  • Crystallography & Structural Chemistry (AREA)
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  • Materials For Photolithography (AREA)

Abstract

The invention provides a photo-curable resin composition, a method for manufacturing a cured film, the cured film, an organic EL device and a liquid display. The photo-curable resin composition is high in sensitivity and excellent in volume resistivity and resistance to solvent. The positive photo-curable resin composition comprises (A) a copolymer including a structure unit (a1) containing groups acid groups of which are protected by acid decomposing groups, and a structure unit (a2) containing a structure represented by -NH-CH2-O-R (R is alkyl carbon atom number of which is between 1 and 20); (B) a photoacid generator and (D) a solvent.

Description

The manufacture method of photosensitive polymer combination, cured film, cured film, organic electroluminescence display device and method of manufacturing same and liquid crystal indicator
Technical field
The present invention relates to a kind of positive type photosensitive organic compound.In addition, the present invention relates to a kind of manufacture method of the cured film of described positive type photosensitive organic compound, the cured film that the positive light sensitivity composition sclerosis is formed, various image displays that use described cured film of using.
More specifically; the present invention relates to a kind of positive type photosensitive organic compound that is suitable for forming planarization film, diaphragm or the interlayer dielectric of the electronic components such as liquid crystal indicator, organic electroluminescent (Electroluminescence, EL) display device, integrated circuit component, solid photographic element, and use the manufacture method of its cured film.
Background technology
Be provided with in organic EL display or liquid crystal indicator etc. and form figuratum interlayer dielectric.Few and can obtain with regard to sufficient flatness etc. with regard to the number of steps in order to obtain required pattern form, be widely used photosensitive polymer combination in the formation of this interlayer dielectric.
With regard to the viewpoint that reduces manufacturing cost, use photosensitive polymer combination as above and form figuratum interlayer dielectric or planarization film needs the photosensitive polymer combination that light sensitivity is high.In addition, recently because the mobile displays such as smart mobile phone are extensively universal, the high cured film of reliability that therefore especially need to be in temperature environment widely.
The known example (for example,, with reference to Japanese Patent Laid-Open 2011-221494 communique, Japanese Patent Laid-Open 2004-264623 communique, Japanese Patent Laid-Open 2005-15532 communique) that the photosensitive polymer combination that uses lifting storage stability, light sensitivity etc. is arranged.But light sensitivity is excellent and photosensitive polymer combination specific insulation and solvent resistance excellence is not known.
Summary of the invention
The present invention is the invention that solves described problem, and its purpose is to provide a kind of photosensitive polymer combination, and the light sensitivity of this photosensitive polymer combination is high, productivity is high and specific insulation and solvent resistance excellence.
The inventor makes great efforts the result of research in order to solve described problem; discovery contains acidic group by the polymkeric substance of the Component units (a1) of the base of sour decomposability base protection, (B) light acid producing agent, and (D) in the positive type photosensitive organic compound of solvent comprising that (A) has, and by comprising in described (A) polymkeric substance, has by-NH-CH 2The Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and should (a2) crosslinking group in addition, can realize described light sensitivity, specific insulation and solvent resistance and deposit, thus completed the present invention.
Particularly, by following<1 >, preferably by<2 >～<13 solve described problem.
<1 > a kind of positive type photosensitive organic compound is characterized in that comprising: (A) meet at least one component of polymer of following (1) and following (2),
(1) (A1) have contain acidic group by the Component units (a1) of the base of sour decomposability base protection, contain by-NH-CH 2The Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and multipolymer that should (a2) Component units that contains crosslinking group (a3) in addition,
(2) (A2) have and contain acidic group by the Component units (a1) of the base of sour decomposability base protection and contain by-NH-CH 2The multipolymer of the Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and the polymkeric substance that (C) there is this (a2) Component units that contains crosslinking group (c2) in addition;
(B) light acid producing agent; And
(D) solvent.
<2 > according to<1 > described positive type photosensitive organic compound, it is characterized in that: described Component units (a2) is by the represented Component units of following general formula (1).
General formula (1)
Figure BDA00002864124900021
(in described formula, R 1Mean hydrogen atom or methyl, R 2Mean the alkyl that carbon number is 1～20)
<3 > according to<1 > or<2 > described positive type photosensitive organic compound, it is characterized in that: described Component units (a1) is by the represented Component units of formula (A2 ').
Formula (A2 ')
Figure BDA00002864124900031
(in formula, R 1And R 2Mean respectively hydrogen atom, alkyl or aryl, at least R 1And R 2Any be alkyl or aryl, R 3Mean alkyl or aryl, R 1Or R 2With R 3Can link and form cyclic ether, R 4Mean hydrogen atom or methyl, X means singly-bound or arlydene)
<4 > according to<1 > to<3 > the middle described positive type photosensitive organic compound of any one, it is characterized in that: in described (A) component of polymer, any contained polymkeric substance comprises that the Component units that contains carboxylic acid is as other constituents (a4).
<5 > according to<1 > to<4 > the middle described positive type photosensitive organic compound of any one, it is characterized in that: described Component units (a2) or Component units (c2) Component units for containing epoxy radicals and/or oxa-cyclobutyl.
<6 > according to<1 > to<5 > the middle described positive type photosensitive organic compound of any one, it is characterized in that: comprise that oxime sulfonates compound or salt compound are as (B) acid producing agent.
<7 > according to<1 > to<6 > the middle described positive type photosensitive organic compound of any one, it is characterized in that: in positive light sensitivity composition, contained total polymer composition is described Component units (a2) more than 10 % by mole, the total polymer composition more than 20 % by mole, be described Component units (a3) and/or described Component units (c2).
<8 > according to<1 > to<7 > the middle described positive type photosensitive organic compound of any one, it is characterized in that: in positive type photosensitive organic compound, more than 30 quality % of contained polymkeric substance, be described (1) multipolymer.
<9 > a kind of manufacture method of cured film is characterized in that comprising:
(1) will be according to<1 > to<8 in the described positive type photosensitive organic compound of any one be applied to the step on substrate;
(2) remove the step of solvent from applied photosensitive polymer combination;
(3) step of utilizing active radioactive ray to be exposed;
(4) step of utilizing aqueous developer solution to be developed; And
(5) carry out the rear baking procedure of thermmohardening.
<10 > according to<9 > described cured film manufacture method, it is characterized in that: after described development step, before rear baking procedure, comprise the step of carrying out blanket exposure.
<11 > a kind of cured film is characterized in that: it is to make according to<1 > to<8 in the described positive type photosensitive organic compounds sclerosis of any one form.
<12 > according to<11 > described cured film, it is characterized in that: it is interlayer dielectric.
<13 > a kind of liquid crystal indicator or organic EL display is characterized in that: comprise according to<11 > or<12 > described cured film.
(effect of invention)
According to the present invention, can provide the photosensitive polymer combination of a kind of light sensitivity, specific insulation and solvent resistance excellence.
The accompanying drawing explanation
Fig. 1 means the formation concept map of an example of organic EL display.The constructed profile of the substrate in the organic EL display of expression bottom-emission type, and there is planarization film 4.
Fig. 2 means the formation concept map of an example of liquid crystal indicator.Mean the constructed profile of the active-matrix substrate in liquid crystal indicator, and there is the cured film 17 as interlayer dielectric.
[explanation of symbol]
1:TFT (thin film transistor (TFT))
2: distribution
3: dielectric film
4: planarization film
5: the first electrodes
6: glass substrate
7: contact hole
8: dielectric film
10: liquid crystal indicator
12: back light unit
14,15: glass substrate
16：TFT
17: cured film
18: contact hole
The 19:ITO transparency electrode
20: liquid crystal
22: colored filter
Embodiment
Below, content of the present invention is elaborated.The explanation of following put down in writing constitutive requirements is carried out based on representative embodiment of the present invention sometimes, but the present invention is not limited thereto kind of an embodiment.Moreover, in present specification, "～" comprises the numerical value of putting down in writing before and after it to use as the implication of lower limit and higher limit.
Moreover, in the statement of base in this manual (atomic group), the record statement that is not substituted and is unsubstituted comprises and do not have substituent base (atomic group), and also comprise and there is substituent base (atomic group).For example, so-called " alkyl ", not only comprise and do not have substituent alkyl in (alkyl be unsubstituted), also comprises and have substituent alkyl in (alkyl be substituted).
[photosensitive polymer combination]
Photosensitive polymer combination of the present invention is characterised in that and comprises: at least one component of polymer, (B) light acid producing agent and (D) solvent that (A) meets following (1) and following (2).
(1) (A1) have contain acidic group by the Component units (a1) of the base of sour decomposability base protection, contain by-NH-CH 2The Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and multipolymer that should (a2) Component units that contains crosslinking group (a3) in addition,
(2) (A2) have and contain acidic group by the Component units (a1) of the base of sour decomposability base protection and contain by-NH-CH 2The multipolymer of the Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and the polymkeric substance that (C) there is this (a2) Component units that contains crosslinking group (c2) in addition.
Photosensitive polymer combination of the present invention is positive type photosensitive organic compound.In addition, the positive type photosensitive organic compound of the preferred chemical amplification type of photosensitive polymer combination of the present invention (chemically amplified positive photosensitive polymer combination).
Below, for photosensitive polymer combination of the present invention, the preferred form of each composition is described successively.
<(A) composition >
In the first example; photosensitive polymer combination of the present invention is characterised in that and comprises that (A1) multipolymer is as (A) composition, described (A1) multipolymer have contain acidic group by the Component units (a1) of the base of sour decomposability base protection, contain by-NH-CH 2The Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and should (a2) Component units that contains crosslinking group (a3) in addition.In the second example, comprise following 2 kinds of polymkeric substance, (A2) has and contains acidic group by the Component units (a1) of the base of sour decomposability base protection and contain by-NH-CH 2The multipolymer of the Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and the polymkeric substance that (C) there is this (a2) Component units that contains crosslinking group (c2) in addition.Certainly, in the present invention, also comprise the form that meets the first example and the second example or the form that further comprises (C) polymkeric substance in the first example, this point is self-evident.Below, (A1) multipolymer, (A2) multipolymer, (C) polymkeric substance are described.
In addition, in this manual, sometimes (A1) multipolymer and (A2) multipolymer are called to " (A) composition " or " (A) multipolymer " in the lump.
Herein, (A) resin of the preferred addition polymerization type of composition, more preferably contain the polymkeric substance of the Component units that is derived from (methyl) acrylic acid and/or its ester.Moreover, also can there is the Component units beyond the Component units that is derived from (methyl) acrylic acid and/or its ester, such as the Component units that is derived from cinnamic Component units or derived from ethylene based compound etc.
Described (A) composition is with respect to the total Component units in polymkeric substance, the Component units that preferably contains (methyl) acrylic acid of being derived from more than 50 % by mole and/or its ester, be derived from cinnamic Component units, be derived from the Component units of maleimide compound, Alpha-Methyl-4-Vinyl phenol, and 4-Vinyl phenol, more preferably contain more than 90 % by mole, and then more preferably contain more than 95 % by mole, particularly preferably only comprise the Component units that is derived from (methyl) acrylic acid and/or its ester, be derived from cinnamic Component units, be derived from the Component units of maleimide compound, Alpha-Methyl-4-Vinyl phenol, and the polymkeric substance of 4-Vinyl phenol.
Moreover, also will " be derived from the Component units of (methyl) acrylic acid and/or its ester " and be called " acrylic acid series Component units ".In addition, " (methyl) acrylic acid " refers to " methacrylic acid and/or acrylic acid ".
Described (A) multipolymer also can have the structure that contains carboxyl described later, be derived from carboxylic acid anhydrides and/or other Component units of phenol hydroxyl etc.But, when importing acidic groups, preferably described (A) multipolymer integral body is being remained to importing in the insoluble scope of alkali.
(A1) multipolymer
The first example in the present invention is for to be contained in by Component units (a1), Component units (a2) and Component units (a3) form that is used as component of polymer in 1 polymkeric substance.
<Component units (a1) >
Polymkeric substance (A1) at least has (a1) and contains the Component units of acidic group by the base of sour decomposability base protection.There is Component units (a1) by (A1) composition, can be made into the high photosensitive polymer combination of light sensitivity.
" acidic group is by the base of sour decomposability base protection " in the present invention can be used as acidic group and sour decomposability base and known base is not particularly limited.As concrete acidic group, can preferably enumerate carboxyl, reach the phenol hydroxyl.In addition, as sour decomposability base, can use than being easier to by the base (acetals such as ester structure, oxinane ester group or tetrahydrofuran ester group such as the base represented by formula described later (A1) are the functional group) that decomposes of acid or relatively being difficult to by the sour base decomposed (three grades of alkyl ester groups of carbonic acid such as three grades of alkyl such as tert-butyl ester base, carbonic acid tert-butyl ester base).
(a1) containing acidic group is preferably contained by the Component units of the protection carboxyl of sour decomposability base protection or is contained the Component units by the protection phenol hydroxyl of sour decomposability base protection by the Component units of the base of sour decomposability base protection.
Below, successively the Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base and the Component units (a1-2) that contains the protection phenol hydroxyl of being protected by sour decomposability base are described respectively.
The Component units that the protection carboxyl of being protected by sour decomposability base (a1-1) is contained in<<<> > >
The described Component units (a1-1) contained by the protection carboxyl of sour decomposability base protection is the Component units that the Component units that contains carboxyl has the following protection carboxyl of being protected by sour decomposability base that will describe.
The described Component units that contains carboxyl as can be used for the described Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base, can be used known Component units with no particular limitation.Such as enumerating: be derived from the Component units (a1-1-1) of the unsaturated carboxylic acid that there is at least 1 carboxyl in unsaturated monocarboxylic acid, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular etc., or there is ethene unsaturated group and the Component units (a1-1-2) that is derived from the structure of acid anhydrides simultaneously.
Below, successively to (a1-1-1) that can be used as the described Component units that contains carboxyl be derived from molecule unsaturated carboxylic acid with at least 1 carboxyl etc. Component units, and (a1-1-2) there is the ethene unsaturated group simultaneously and describe respectively with the Component units that is derived from the structure of acid anhydrides.
<<<<(a1-1-1) is derived from molecule the Component units of unsaturated carboxylic acid with at least 1 carboxyl etc. > > > >
As the described Component units (a1-1-1) that is derived from molecule unsaturated carboxylic acid with at least 1 carboxyl etc., can use the unsaturated carboxylic acid of lifting as listed below as the unsaturated carboxylic acid used in the present invention.That is, as unsaturated monocarboxylic acid, such as enumerating: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc.In addition, as unsaturated dicarboxylic, such as enumerating: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.The unsaturated polybasic carboxylic acid of the Component units that in addition, for acquisition, contains carboxyl can be also its acid anhydrides.Particularly, can enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc.In addition, unsaturated polybasic carboxylic acid can be also list (the 2-methacryloxy alkyl) ester of polybasic carboxylic acid, such as enumerating: succinic acid list (2-acryloxy ethyl) ester, succinic acid list (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.And then unsaturated polybasic carboxylic acid can be also list (methyl) acrylate of its two ends dicarboxyl polymkeric substance, such as enumerating ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates etc.In addition, as unsaturated carboxylic acid, also can use acrylic acid-2-carboxyl ethyl ester, methacrylic acid-2-carboxyl ethyl ester, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, 4-carboxyl styrene etc.
Wherein, with regard to the viewpoint of developability, in order to form the described Component units (a1-1-1) that is derived from molecule unsaturated carboxylic acid with at least 1 carboxyl etc., preferably use the acid anhydride of acrylic acid, methacrylic acid or unsaturated polybasic carboxylic acid etc., more preferably use acrylic or methacrylic acid.
The described Component units (a1-1-1) that is derived from molecule unsaturated carboxylic acid with at least 1 carboxyl etc. can comprise separately a kind, also can comprise two or more.
<<<<(a1-1-2) has ethene unsaturated group and the Component units that is derived from the structure of acid anhydrides simultaneously > > > >
Have that the ethene unsaturated group is reacted with acid anhydrides with Component units (a1-1-2) preferred source existing hydroxyl in making the Component units that contains the ethene unsaturated group of the structure that is derived from acid anhydrides and the unit of the monomer that obtains simultaneously.
As described acid anhydrides, can use known acid anhydrides, particularly, can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; The acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Among these acid anhydrides, with regard to the viewpoint of developability, preferred phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.
With regard to the viewpoint of developability, described acid anhydrides is for preferably 10 % by mole～100 % by mole of the reaction rates of hydroxyl, more preferably 30 % by mole～100 % by mole.
<<<<the can be used for sour decomposability base of Component units (a1-1) > > > >
Described sour decomposability base as can be used for the described Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base, can be used described sour decomposability base.
Among these sour decomposability bases; basic physical properties with regard to photosensitive polymer combination; the viewpoint of the storage stability of the formative of light sensitivity or pattern form, contact hole, photosensitive polymer combination particularly, preferably carboxyl is by the protection carboxyl of the form protection of acetal.And then, among sour decomposability base, with regard to the viewpoint of light sensitivity, more preferably carboxyl is by the protection carboxyl of the form protection of the acetal represented with following general formula (a1-1).Moreover, in the situation that carboxyl is by the protection carboxyl of the form protection of the acetal represented with following general formula (a1-1) or ketal, become-(the C=O)-O-CR of integral body of protection carboxyl 101R 102(OR 103) structure.
General formula (a1-1)
Figure BDA00002864124900091
(in formula (a1-1), R 101And R 102Mean independently respectively hydrogen atom or alkyl, wherein, get rid of R 101With R 102Be the situation of hydrogen atom.R 103Mean alkyl.R 101Or R 102With R 103Can link and form cyclic ether)
In described general formula (a1-1), R 101～R 103Mean independently respectively hydrogen atom or alkyl, described alkyl can be any of straight chain shape, chain, ring-type.There do not is R herein, 101And R 102The situation that all means hydrogen atom, R 101And R 102At least one mean alkyl.
In described general formula (a1-1), work as R 101, R 102And R 103While meaning alkyl, described alkyl can be any of straight chain shape, a chain or ring-type.
As the alkyl of described straight chain shape or a chain, preferably carbon number is 1～12, and more preferably carbon number is 1～6, and then more preferably carbon number is 1～4.Particularly, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.
As described cyclic alkyl, preferably carbon number is 3～12, and more preferably carbon number is 4～8, and then more preferably carbon number is 4～6.As described cyclic alkyl, such as enumerating: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc.
Described alkyl also can have substituting group, as substituting group, but illustration halogen atom, aryl, alkoxy.When having halogen atom as substituting group, R 101, R 102, R 103Become haloalkyl, when having aryl as substituting group, R 101, R 102, R 103Become aralkyl.
As described halogen atom, but illustration fluorine atom, chlorine atom, bromine atoms, iodine atom, among these halogen atoms, preferably fluorine atom or chlorine atom.
In addition, as described aryl, the aryl that preferably carbon number is 6～20, the aryl that more preferably carbon number is 6～12, particularly, but illustration phenyl, Alpha-Methyl phenyl, naphthyl etc., as the alkyl integral body replaced by aryl, be aralkyl, but illustration benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc.
As described alkoxy, the alkoxy that preferably carbon number is 1～6, the alkoxy that more preferably carbon number is 1～4, and then more preferably methoxy or ethoxy.
In addition, when described alkyl is naphthenic base, described naphthenic base can have the alkyl of straight chain shape that carbon number is 1～10 or a chain as substituting group, and when alkyl that alkyl is straight chain shape or a chain, the naphthenic base that can to have carbon number be 3～12 is as substituting group.
These substituting groups also can further be replaced by described substituting group.
In described general formula (a1-1), work as R 101, R 102And R 103While meaning aryl, the preferred carbon number of described aryl is 6～12, and more preferably carbon number is 6～10.Described aryl can have substituting group, as described substituting group, and the alkyl that preferably the illustration carbon number is 1～6.As aryl, but such as illustration phenyl, tolyl, silylation (silyl), cumenyl, 1-naphthyl etc.
In addition, R 101, R 102And R 103Bond mutually, and together form ring with the carbon atom of their institute's bonds.As R 101With R 102, R 101With R 103Or R 102With R 103Ring structure during bond, such as enumerating: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.
Moreover, in described general formula (a1-1), preferred R 101And R 102Any be hydrogen atom or methyl.
The free radical polymerization monomer that is used to form the Component units that contains the protection carboxyl represented by described general formula (a1-1) can be used commercially available free radical polymerization monomer, also can use by the free radical polymerization monomer of known method synthesized.The synthetic methods of for example, putting down in writing in, can the paragraph 0037～paragraph 0040 by Japanese Patent Laid-Open 2011-221494 communique etc. are come synthetic.
The first preferred form of the described Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base is by the represented Component units of formula (A2 ').
Formula (A2 ')
Figure BDA00002864124900111
(in formula, R 1And R 2Mean respectively hydrogen atom, alkyl or aryl, at least R 1And R 2Any be alkyl or aryl, R 3Mean alkyl or aryl, R 1Or R 2With R 3Can link and form cyclic ether, R 4Mean hydrogen atom or methyl, X means singly-bound or arlydene)
Work as R 1And R 2During for alkyl, the alkyl that preferably carbon number is 1～10.Work as R 1And R 2During for aryl, preferred phenyl.R 1And R 2The alkyl that preferably hydrogen atom or carbon number are 1～4 respectively.
R 3Mean alkyl or aryl, the alkyl that preferably carbon number is 1～10, the alkyl that more preferably carbon number is 1～6.
X means singly-bound or arlydene, preferably singly-bound.
The structural unit that the second preferred form of the described Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base is following general formula.
Figure BDA00002864124900121
(in formula, R 121Mean the alkyl that hydrogen atom or carbon number are 1～4, L 1Mean carbonyl or phenylene, R 122～R 128Mean independently respectively the alkyl that hydrogen atom or carbon number are 1～4)
R 121Preferred hydrogen atom or methyl.
L 1Preferred carbonyl.
R 122～R 128Preferred hydrogen atom.
As the preferred concrete example of the described Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base, but the following Component units of illustration.Moreover R means hydrogen atom or methyl.
Figure BDA00002864124900122
The Component units that the protection phenol hydroxyl of being protected by sour decomposability base (a1-2) is contained in<<<> > >
The described Component units (a1-2) contained by the protection phenol hydroxyl of sour decomposability base protection is the Component units that the Component units that contains the phenol hydroxyl has the following protection phenol hydroxyl of being protected by sour decomposability base that will describe.
The Component units of<<<<(a1-2-1) contain the phenol hydroxyl > > > >
As the described Component units that contains the phenol hydroxyl, can enumerate hydroxy styrenes and be the Component units in the resin of Component units or novolaks system, among these Component units, with regard to transparent viewpoint, preferred source is from the Component units of hydroxy styrenes or Alpha-Methyl hydroxy styrenes.Among the Component units that contains the phenol hydroxyl, with regard to the viewpoint of the transparency, light sensitivity, preferably by the represented Component units of following general formula (a1-2).
General formula (a1-2)
Figure BDA00002864124900131
(in general formula (a1-2), R 220Mean hydrogen atom or methyl, R 221The concatenating group that means singly-bound or divalence, R 222Mean the alkyl of the straight or branched that halogen atom or carbon number are 1～5, a means 1～5 integer, and b means 0～4 integer, and a+b is below 5.Moreover, as the R existed more than 2 222The time, these R 222Mutually can be different, also can be identical)
In described general formula (a1-2), R 220Mean hydrogen atom or methyl, preferable methyl.
In addition, R 221The concatenating group that means singly-bound or divalence.Work as R 221During for singly-bound, but promotion feeling luminosity, and then can promote the transparency of cured film, therefore preferably.As R 221The concatenating group of divalence, but the illustration alkylidene, as R 221For the concrete example of alkylidene, can enumerate: methylene, ethylidene, propylidene, isopropylidene, positive butylidene, isobutylene, tertiary butylidene, pentylidene (pentylene), isopentylidene, new pentylidene, hexylidene etc.Wherein, R 221Preferred singly-bound, methylene, ethylidene.In addition, the concatenating group of described divalence can have substituting group, as substituting group, can enumerate halogen atom, hydroxyl, alkoxy etc.In addition, a means 1～5 integer, but with regard to the viewpoint of effect of the present invention or easily manufacture with regard to this viewpoint, preferably a is 1 or 2, and more preferably a is 1.
In addition, when will with R 221The carbon atom that carries out bond is during as benchmark (1), and the bond location optimization bond of the hydroxyl in phenyl ring is on 4.
R 222Alkyl for halogen atom or the carbon number straight or branched that is 1～5.
Particularly, can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl etc.Wherein, with regard to this viewpoint of easy manufacture, preferred chlorine atom, bromine atoms, methyl or ethyl.
In addition, b means 0 or 1～4 integer.
<<<<the can be used for sour decomposability base of Component units (a1-2) > > > >
As the described sour decomposability base that can be used for the described Component units (a1-2) that contains the protection phenol hydroxyl of being protected by sour decomposability base; with can be used for described containing by the described sour decomposability base of the Component units (a1-1) of the protection carboxyl of sour decomposability base protection similarly; can use known sour decomposability base, be not particularly limited.Among acid decomposability base; basic physical properties with regard to photosensitive polymer combination; the viewpoint of the formative of the storage stability of light sensitivity or pattern form, photosensitive polymer combination, contact hole particularly, preferably contain the Component units by the protection phenol hydroxyl of ketal protection by the protection phenol hydroxyl of acetal protection or phenol hydroxyl.And then, among sour decomposability base, with regard to the viewpoint of light sensitivity, more preferably the phenol hydroxyl is by the protection phenol hydroxyl of the acetal represented with described general formula (a1-1) or ketal protection.Moreover, in the situation that the phenol hydroxyl, by the protection phenol hydroxyl of the acetal represented with described general formula (a1-1) or ketal protection, is protected the become-Ar-O-CR of integral body of phenol hydroxyl 101R 102(OR 103) structure.Moreover Ar means arlydene.
But the preference illustration R of the acetal ester structure of phenol hydroxyl 101=R 102=R 103=methyl or R 101=R 102=methyl and R 103The combination of=benzyl.
In addition; contain the free radical polymerization monomer of phenol hydroxyl by the Component units of the protection phenol hydroxyl of the form of acetal or ketal protection as being used to form, such as the free radical polymerization monomer of putting down in writing in the paragraph 0042 that can enumerate Japanese Patent Laid-Open 2011-215590 communique etc.
Among these free radical polymerization monomers; with regard to transparent viewpoint, the 1-alkoxyalkyl protective of preferable methyl acrylic acid 4-hydroxylphenyl ester (4-hydroxy phenyl methacrylate), the THP trtrahydropyranyl protective of methacrylic acid 4-hydroxylphenyl ester.
As the acetal protecting group of phenol hydroxyl and ketal protected concrete example; can enumerate the 1-alkoxyalkyl; such as enumerating 1-ethoxyethyl group, 1-methoxy ethyl, 1-n-butoxy ethyl, 1-isobutoxy ethyl, 1-(2-chloroethoxy) ethyl, 1-(2-ethyl hexyl oxy) ethyl, 1-positive propoxy ethyl, 1-cyclohexyloxy ethyl, 1-(2-cyclohexyl ethoxy) ethyl, 1-benzyloxy ethyl etc., these bases can be used alone or two or more is used in combination.
The free radical polymerization monomer that is used to form the described Component units (a1-2) that contains the protection phenol hydroxyl of being protected by sour decomposability base can be used commercially available free radical polymerization monomer, also can use by the free radical polymerization monomer of known method synthesized.For example, can with vinyl ether, be reacted by the compound that makes to contain the phenol hydroxyl under the existence of sour catalyst to synthesize.Described synthesizing also can make the monomer and other monomers that contain the phenol hydroxyl carry out copolymerization in advance, then under the existence of sour catalyst, with vinyl ether, reacted.
As the preferred concrete example of the described Component units (a1-2) that contains the protection phenol hydroxyl of being protected by sour decomposability base, but the following Component units of illustration, but the present invention is not limited to these Component units.
Figure BDA00002864124900151
The preferred form of<<<Component units (a1) > > >
Form in the Component units of multipolymer (A1), with regard to the viewpoint of light sensitivity, by polymkeric substance as a whole, preferably 1 % by mole～95 % by mole of the containing ratios of Component units (a1), more preferably 10 % by mole～80 % by mole, and then more preferably 20 % by mole～70 % by mole, particularly preferably 20 % by mole～50 % by mole.In addition; especially in the situation that can be used for the described sour decomposability base of described Component units (a1) be contain carboxyl by the protection carboxyl of acetal protection or carboxyl the Component units by the protection carboxyl of ketal protection; more preferably 20 % by mole～60 % by mole of the containing ratios of the Component units (a1) in the Component units of the polymkeric substance that formation contains Component units (a1), particularly preferably 20 % by mole～50 % by mole.
With the described Component units (a1-2) that contains the protection phenol hydroxyl of being protected by sour decomposability base, compare, the described Component units (a1-1) that contains the protection carboxyl of being protected by sour decomposability base has fast this feature of developing.Therefore, in the situation that want rapid development, preferably contain the Component units (a1-1) by the protection carboxyl of sour decomposability base protection.On the contrary, in the situation that it is slack-off to want to make to develop, preferably use the Component units (a1-2) contained by the protection phenol hydroxyl of sour decomposability base protection.
<<(a2) contained by-NH-CH 2The Component units of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented>>
(A1) multipolymer used in the present invention has and contains by-NH-CH 2The Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented (below, also referred to as " Component units (a2) ").By thering is Component units (a2), can utilize the heat treated of mitigation to produce sclerous reaction, and can obtain the cured film of various characteristics excellence.Herein, the alkyl that the preferred carbon number of R is 1～9, the alkyl that more preferably carbon number is 1～4.In addition, alkyl can be any of alkyl of straight chain, branch or ring-type, but the preferred alkyl of straight chain or branch.Component units (a2) more preferably has the Component units of the base represented by following general formula (1).
General formula (1)
Figure BDA00002864124900161
(in described formula, R 1Mean hydrogen atom or methyl, R 2Mean the alkyl that carbon number is 1～20)
R 2The alkyl that preferably carbon number is 1～9, the alkyl that more preferably carbon number is 1～4.In addition, alkyl can be any of alkyl of straight chain, branch or ring-type, but the preferred alkyl of straight chain or branch.
As R 2Concrete example, can enumerate: methyl, ethyl, normal-butyl, isobutyl, cyclohexyl, and n-hexyl.Wherein, preferred isobutyl, normal-butyl, methyl.
Form in the Component units of (A1) multipolymer, preferably 1 % by mole～95 % by mole of the containing ratios of Component units (a2), more preferably 1 % by mole～60 % by mole, and then more preferably 1 % by mole～40 % by mole, and then more preferably 1 % by mole～30 % by mole, particularly preferably 3 % by mole～30 % by mole.If in the scope of described numerical value, it is good that the various characteristics of the cured film obtained by photosensitive polymer combination becomes.
The Component units that<<(a3) contained crosslinking group > >
(A1) multipolymer will contain the Component units (a3) of crosslinking group as essential composition.Described crosslinking group so long as pass through the base that heat treated produces sclerous reaction, is not particularly limited (still, being equivalent to except (a2) person).By containing crosslinking group, the mechanical property of cured film promotes.As the form of the Component units that preferably contains crosslinking group, can enumerate contain select free epoxy radicals, oxa-cyclobutyl, and the group that forms of ethene unsaturated group in the Component units of at least 1, more preferably epoxy radicals and/or oxa-cyclobutyl.
More specifically, can enumerate following person.
<<<(a3-1) has a Component units of epoxy radicals and/or oxa-cyclobutyl > > >
Described (A1) multipolymer can contain the Component units (Component units (a3-1)) with epoxy radicals and/or oxa-cyclobutyl.
Concrete example as the free radical polymerization monomer that is used to form the Component units with epoxy radicals, for example can enumerate glycidyl acrylate, glycidyl methacrylate, the α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid-3, 4-epoxy radicals butyl ester, methacrylic acid-3, 4-epoxy radicals butyl ester, acrylic acid-3, 4-epoxycyclohexyl methyl esters, methacrylic acid-3, 4-epoxycyclohexyl methyl esters, α-ethylacrylate-3, 4-epoxycyclohexyl methyl esters, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether, the compound that contains ester ring type epoxy radicals skeleton of putting down in writing in the paragraph 0031～paragraph 0035 of No. 4168443 communique of Jap.P. etc.
As the concrete example of the free radical polymerization monomer that is used to form the Component units with oxa-cyclobutyl, such as (methyl) acrylate with oxa-cyclobutyl of putting down in writing in the paragraph 0011～paragraph 0016 that can enumerate Japanese Patent Laid-Open 2001-330953 communique etc.
Concrete example as the free radical polymerization monomer that is used to form the described Component units (a3-1) with epoxy radicals and/or oxa-cyclobutyl, preferably contain the monomer of metacrylic acid ester structure, the monomer that contains acrylate structural.
Among these monomers, the compound that contains ester ring type epoxy radicals skeleton of putting down in writing in paragraph 0034～paragraph 0035 that preferred monomer is No. 4168443 communique of Jap.P., and the paragraph 0011～paragraph 0016 of Japanese Patent Laid-Open 2001-330953 communique in (methyl) acrylate with oxa-cyclobutyl of putting down in writing, (methyl) acrylate with oxa-cyclobutyl of putting down in writing in paragraph 0011～paragraph 0016 that monomer particularly preferably is Japanese Patent Laid-Open 2001-330953 communique.Among these monomers, preferable methyl glycidyl acrylate, acrylic acid 3,4-epoxycyclohexyl methyl esters, methacrylic acid 3,4-epoxycyclohexyl methyl esters, acrylic acid (3-Ethyloxetane-3-yl) methyl esters, and methacrylic acid (3-Ethyloxetane-3-yl) methyl esters, most preferably acrylic acid (3-Ethyloxetane-3-yl) methyl esters, and methacrylic acid (3-Ethyloxetane-3-yl) methyl esters.These Component units can be used alone a kind or two or more is used in combination.
The described Component units (a3-1) with epoxy radicals and/or oxa-cyclobutyl preferably has the structure in the group that selects free following formula (a2-1-1) and formula (a2-1-2) to form.
Figure BDA00002864124900181
The so-called described Component units (a3-1) with epoxy radicals and/or oxa-cyclobutyl has any of the 3 kind structures represented by described formula (a2-1-1), refers to have to remove the base that the hydrogen atom more than 1 forms from the structure represented by formula (a2-1-1).
The described Component units (a3-1) with epoxy radicals and/or oxa-cyclobutyl more preferably has 3,4-epoxycyclohexyl, 2,3-epoxycyclohexyl, 2,3-epoxide ring amyl group.
Figure BDA00002864124900182
(in general formula (a2-1-2), R 1bAnd R 6bMean independently respectively hydrogen atom or alkyl, R 2b, R 3b, R 4b, R 5b, R 7b, R 8b, R 9b, R 10bMean independently respectively hydrogen atom, halogen atom, alkyl or aryl)
In described general formula (a2-1-2), R 1bAnd R 6bMean independently respectively hydrogen atom or alkyl, the alkyl that preferably hydrogen atom or carbon number are 1～8, the alkyl that more preferably hydrogen atom or carbon number are 1～5 (below, also referred to as " low alkyl group ").
R 2b, R 3b, R 4b, R 5b, R 7b, R 8b, R 9b, R 10bMean independently respectively hydrogen atom, halogen atom, alkyl or aryl.
As described halogen atom, but illustration fluorine atom, chlorine atom, bromine atoms, iodine atom, more preferably fluorine atom and chlorine atom, and then more preferably fluorine atom.
Described alkyl can be any of straight chain shape, chain, ring-type, in addition, also can have substituting group.As the alkyl of straight chain shape and a chain, preferably carbon number is 1～8, and more preferably carbon number is 1～6, and then more preferably carbon number is 1～4.As described cyclic alkyl, preferably carbon number is 3～10, and more preferably carbon number is 4～8, and then more preferably carbon number is 5～7.Moreover the alkyl of straight chain shape and a chain can be replaced by cyclic alkyl, cyclic alkyl also can be replaced by straight chain shape and/or branched-chain alkyl.
As described aryl, the aryl that preferably carbon number is 6～20, the aryl that more preferably carbon number is 6～10.
Described alkyl, aryl can further have substituting group, the substituting group that can have as alkyl, but illustration halogen atom, aryl, the substituting group that can have as aryl, but illustration halogen atom, alkyl.Among these, more preferably R 2b, R 3b, R 4b, R 5b, R 7b, R 8b, R 9b, R 10bThe perfluoroalkyl that alkyl, phenyl or the carbon number that is independently 1～4 for hydrogen atom, fluorine atom, carbon number respectively is 1～4.
As the base with structure represented by described general formula (a2-1-2), preferred illustration (3-Ethyloxetane-3-yl) methyl.
As the described preferred concrete example with Component units (a3-1) of epoxy radicals and/or oxa-cyclobutyl, but the following Component units of illustration.Moreover R means hydrogen atom or methyl.
Figure BDA00002864124900191
<<<(a3-2) has a Component units of ethene unsaturated group > > >
As a kind of the described Component units that contains crosslinking group (a3), can enumerate Component units (a3-2) with ethene unsaturated group (below, also referred to as " Component units (a3-2) ").As the described Component units (a3-2) with ethene unsaturated group, preferably on side chain, there is the Component units of ethene unsaturated group, more preferably end has the ethene unsaturated group and has the Component units of the side chain that carbon number is 3～16, and then more preferably has the Component units of the side chain represented by following general formula (a3-2-1).
General formula (a3-2-1)
Figure BDA00002864124900201
(in general formula (a3-2-1), R 301The concatenating group that means the divalence that carbon number is 1～13, R 302Mean hydrogen atom or methyl, * means the position that the main chain with the Component units that contains crosslinking group (a3) links)
R 301For the concatenating group of the carbon number divalence that is 1～13, the base that comprises thiazolinyl, cycloalkenyl group, arlydene or they are combined, also can contain the keys such as ester bond, ehter bond, amido link, urethane bonds.In addition, the concatenating group of divalence can have the substituting groups such as hydroxyl, carboxyl on position arbitrarily.As R 301Concrete example, can enumerate the concatenating group of following divalence.
Figure BDA00002864124900202
By described general formula (a3-2-1), among represented side chain, preferably comprised by described R 301The aliphatic side chain of the concatenating group of represented divalence.
In addition, preferably with respect to the total of described polymkeric substance (A) or the total 150g of polymkeric substance (A) and polymkeric substance (C)～2,000g, comprise contained ethene unsaturated group in 1 mole of side chain represented by described general formula (a3-2-1), more preferably with respect to the total of described polymkeric substance (A) or the total 200g of polymkeric substance (A) and polymkeric substance (C)～1,300g, comprise contained ethene unsaturated group in 1 mole of side chain represented by described general formula (a3-2-1).
In the present invention, described have the Component units (a3-2) of ethene unsaturated group preferably by the represented Component units of following general formula (a3-2-2).
General formula (a3-2-2)
Figure BDA00002864124900211
(in general formula (a3-2-2), R 311Implication and the R in described general formula (a3-2-1) 301Identical, preferred scope is also identical.R 312, R 313Mean independently respectively hydrogen atom or methyl)
The method that acquisition has the Component units (a3-2) of the side chain represented by described general formula (a3-2-1) is not particularly limited, for example, can be in advance by polymerizations such as free radical polymerizations, and generation has the polymkeric substance of particular functional base, then make this polymkeric substance with have the compound that the base that reacted with its particular functional base and end have the ethene unsaturated group (below, be called specific compound) reacted, make thus the multipolymer that contains the Component units (a3-2) with side chain represented by described general formula (a3-2-1).
Herein, as described particular functional base, can enumerate: carboxyl, epoxy radicals, hydroxyl, the amino that contains reactive hydrogen, phenol hydroxyl, isocyanate group etc.In order to the monomer with particular functional base of the synthetic polymkeric substance with particular functional base by aftermentioned.
The combination of the base reacted with the particular functional base had with described specific compound as described particular functional base, can enumerate: the combination of combination, hydroxyl and the acyl chlorides of the combination of combination, carboxyl and the isocyanate group of the combination of combination, hydroxyl and the isocyanate group of the combination of carboxyl and epoxy radicals, carboxyl and oxa-cyclobutyl, phenol hydroxyl and epoxy radicals, amino and isocyanate group etc.
In addition, as described specific compound, can enumerate: glycidyl methacrylate, glycidyl acrylate, methacrylic acid 3,4-epoxycyclohexyl methyl esters, acrylic acid 3,4-epoxycyclohexyl methyl esters, methacrylic acid isocyanate group ethyl ester, acrylic acid isocyanate group ethyl ester, methacrylic chloride, acryloyl chloride, methacrylic acid, acrylic acid etc.
As the combination of preferred described particular functional base and described specific compound, can enumerate: as the combination of the carboxyl of described particular functional base and glycidyl methacrylate as described specific compound, and the combination with methacrylic acid isocyanate group ethyl ester as described specific compound as the hydroxyl of described particular functional base.
Below, enumerate the needed concrete example with monomer of described particular functional base of polymkeric substance that there is described particular functional base in order to acquisition, but be not limited to these concrete examples.
As the monomer with described carboxyl, such as enumerating: acrylic acid, methacrylic acid, crotonic acid, phthalic acid list (2-(acryloxy) ethyl) ester, phthalic acid list (2-(methacryloxy) ethyl) ester, N-(carboxyl phenyl) maleimide, N-(carboxyl phenyl) Methacrylamide, N-(carboxyl phenyl) acrylamide etc.
As the monomer with described epoxy radicals, for example can enumerate: glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy radicals-5-hexene, 1,7-octadiene monoepoxide, methacrylic acid 3,4-epoxycyclohexyl methyl esters, acrylic acid 3,4-epoxycyclohexyl methyl esters etc.
As the monomer with described hydroxyl, for example can enumerate: acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, acrylic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, acrylic acid 2, 3-dihydroxy propyl ester, methacrylic acid 2, 3-dihydroxy propyl ester, diethylene glycol monoacrylate, the diethylene glycol monomethacrylates, caprolactone 2-(acryloxy) ethyl ester, caprolactone 2-(methacryloxy) ethyl ester, PEG ether acrylate, PEG ether methacrylate, 5-acryloxy-6-hydroxyl norborene-2-carboxylic acid-6-lactone, 5-methacryloxy-6-hydroxyl norborene-2-carboxylic acid-6-lactone etc.
As the monomer with described amino that contains reactive hydrogen, can enumerate: acrylic acid 2-amino ethyl ester, methacrylic acid 2-amino methyl etc.
As the monomer with described phenol hydroxyl, such as enumerating: hydroxy styrenes, N-(hydroxyphenyl) acrylamide, N-(hydroxyphenyl) Methacrylamide, N-(hydroxyphenyl) maleimide etc.
And then, as the monomer with described isocyanate group, such as enumerating: tetramethyl xylene ester etc. between isocyanic acid acryloyl group ethyl ester (acryloyl ethyl isocyanate), isocyanic acid methacryl ethyl ester, isocyanic acid.
In addition, in the present invention, in the time will obtaining the polymkeric substance with described particular functional base, and with Component units (a2) with become (a1) and contain the monomer by the Component units of the base of sour decomposability base protection.And then, can and use other monomers.
The method that obtains the polymkeric substance with described particular functional base used in the present invention is not particularly limited, in the solvent that can coexist by the monomer making to have the particular functional base, the monomer beyond it and the polymerization initiator depended on the needs etc., carry out polyreaction and obtain at the temperature of 50 ℃～110 ℃.Now, the solvent used so long as dissolve to form the monomer of the polymkeric substance with particular functional base and have the solvent of the polymkeric substance of particular functional base, is not particularly limited.As concrete example, can enumerate the solvent of putting down in writing in (D) described later solvent.The polymkeric substance with particular functional base obtained in this way is generally the state that is dissolved in the solution in solvent.
Then, can make the obtained polymkeric substance with particular functional base be reacted with specific compound, and the end of acquisition side chain have the Component units (a3-2) of ethene unsaturated group.Now, usually will there is the solution of polymkeric substance of particular functional base in reaction.For example, under the existence of the catalyst such as benzyltriethylammoinium chloride, the solution that makes to have the acrylate copolymer of carboxyl with the temperature of 80 ℃～150 ℃ is reacted with glycidyl methacrylate, can obtain thus Component units (a3-2).
In addition, in order to form Component units (a3-2), except utilizing high molecular weight reactive as above, also can be by allyl methacrylate, allyl acrylate etc. as free radical polymerization monomer.These Component units can be used alone or two or more is used in combination.
In the situation that Component units (a3) and described Component units (a1) and Component units (a2) are contained in to the first form of same polymkeric substance, form in the Component units of multipolymer (A1), the containing ratio of Component units (a3) is 5 % by mole～70 % by mole of all repetitives preferably, more preferably 10 % by mole～50 % by mole.
If in the scope of described numerical value, it is good that the various characteristics of the cured film obtained by photosensitive polymer combination becomes.
Other Component units of<<(a4) > >
In the present invention, (A1) composition, except described Component units (a1), Component units (a2) and Component units (a3), also can have these Component units other Component units (a4) in addition.As the monomer that becomes other Component units (a4), there is no particular restriction.For example can enumerate: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) acrylic acid aryl ester, unsaturated dicarboxylic diester, dicyclo unsaturated compound class, maleimide compounds, unsaturated aromatics, conjugated diolefine based compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.
Particularly, can enumerate the Component units formed by following compound: styrene, methyl styrene, hydroxy styrenes, α-methyl styrene, acetoxy-styrene, methoxy styrene, ethoxybenzene ethene, chlorostyrene, the vinyl benzoic acid methyl esters, the vinyl benzoic acid ethyl ester, 4-HBA (3-methacryloxypropyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, vinyl cyanide, glycol monomethyl acetoacetate list (methyl) acrylate etc.In addition, can enumerate the compound of putting down in writing in the paragraph 0021～paragraph 0024 of Japanese Patent Laid-Open 2004-264623 communique.
In the present invention, with regard to the viewpoint of light sensitivity, particularly preferably contain the Component units with carboxyl or there is the Component units of phenol hydroxyl.Preferably 1 % by mole～50 % by mole of content, more preferably 2 % by mole～30 % by mole, and then more preferably 5 % by mole～20 % by mole, particularly preferably 5 % by mole～15 % by mole.As the Component units with carboxyl or phenol hydroxyl, can enumerate the monomer with known acidic groups, wherein, preferably hydroxy styrenes class or (methyl) acrylic acid, following long-chain carboxylic acid.
As the Component units with long-chain carboxylic acid, the preferred represented Component units by following formula.
(in described formula, R 1For hydrogen atom or methyl, R 2For the organic group of n+1 valency, the integer that n is 1～4)
R 2Preferably carbon number is 2～15 and the heteroatoms number organic group that is 0～6 (more preferably the heteroatoms number is 1～6).
Component units with long-chain carboxylic acid is the represented Component units by following formula more preferably.
Figure BDA00002864124900242
(in described formula, R 1For hydrogen atom or methyl, R 3For carbon number be 1～10 alkylidene, R 4For the carbon number alkylidene that is 1～10)
R 3And R 4Can be respectively any of straight chain, branch, ring-type.R 3And R 4The alkylidene that preferably carbon number is 2～8 respectively.
In addition, as other Component units (a4), with regard to the viewpoint of electrical characteristics, the optimization styrene class, there is the base of aliphatics ring type skeleton.Particularly, can enumerate: styrene, methyl styrene, hydroxy styrenes, α-methyl styrene, (methyl) acrylic acid two ring pentyl esters, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate etc.
And then, as other Component units (a4), with regard to the viewpoint of adhesion, preferred (methyl) alkyl acrylate.Particularly, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate etc., more preferably (methyl) methyl acrylate.
The described monomer that becomes other Component units (a4) can be used alone or two or more is used in combination.
Form in the Component units of multipolymer (A1), the containing ratio of Component units (a4) is preferably below 60 % by mole, more preferably below 50 % by mole, and then more preferably below 40 % by mole.Lower limit can be 0 % by mole, but for example can be made as more than 1 % by mole, and then can be made as more than 5 % by mole.If in the scope of described numerical value, it is good that the various characteristics of the cured film obtained by photosensitive polymer combination becomes.
The molecular weight of the multipolymer of<<(A1) > >
(A1) molecular weight of multipolymer is in the polystyrene conversion weight average molecular weight, and preferably 1,000～200,000, more preferably 2,000～50,000 scope.If, in the scope of described numerical value, various characteristics is good.The ratio (dispersion degree) of number average molecular weight and weight average molecular weight preferably 1.0～5.0, more preferably 1.5～3.5.
The manufacture method of the multipolymer of<<(A1) > >
In addition, synthetic method about (A1) composition, also known have a whole bag of tricks, if enumerate an example, can be by utilizing the free radical polymerization initiator, the free radical polymerization monomer potpourri that makes at least to contain the free radical polymerization monomer that is used to form the Component units represented by described (a1) and described (a2) carries out polymerization and synthesizes in organic solvent.In addition, also can synthesize by so-called high molecular weight reactive.
In addition, (A) composition to have endways a carboxyl also preferred.
[end has the synthetic method of the resin of carboxyl]
End has the resin of carboxyl and can manufacture by utilizing free radical polymerization, anionic polymerisation, group transfer polymerization (Group Transfer Polymerization, GTP) etc. to make corresponding monomer carry out copolymerization.The manufacture method that end of the present invention has the resin of carboxyl is not particularly limited, and for example can enumerate the method for (I)～(VIII) of Japanese Patent Laid-Open 2005-122035 communique 0099 paragraph～0117 paragraph record.
Wherein, preferred (I) and method (II).
(I) there is the method for the polymerization initiator of carboxyl as use, when polymerization, use and there is the polymerization initiator of carboxyl as initiator.
As the example that is widely used as the polymerization initiator with carboxyl, can enumerate VA-057 (manufacturing with the pure pharmaceutical worker's industry of light company), V-501 (manufacturing with the pure pharmaceutical worker's industry of light company).
Figure BDA00002864124900261
With respect to 100 moles of polymerizable monomers, the preferred 0.05mol%～10mol% of this polymerization initiator, more preferably 0.1mol%～5mol%.
Preferably 50 ℃～100 ℃ of the temperature of reaction of copolyreaction, more preferably 60 ℃～100 ℃.
(II) use when polymerization in the method for the chain-transferring agent with carboxyl, also use the mercaptan compound with at least one carboxyl when polymerization.As the mercaptan compound with at least one carboxyl, following example is arranged.
With respect to initial dose, preferably, with the ratio allotment chain-transferring agent of 1/100 mole～2/3 mole, more preferably with the ratio of 1/20 mole～1/3 mole, allocate chain-transferring agent.
Summation by initial dose and chain-transferring agent is adjusted molecular weight, but with respect to total mole of all monomer, preferred 0.05mol%～10mol%, more preferably 0.1mol%～5mol%.
Preferably 50 ℃～100 ℃ of the temperature of reaction of copolyreaction, more preferably 60 ℃～95 ℃.
(A2) multipolymer
The second example in the present invention for the multipolymer that comprises there is Component units (a1) and Component units (a2), and (C) there is the form of the polymkeric substance of this (a2) Component units that contains crosslinking group (c2) in addition as component of polymer.
With the homomorphosis of described (A1), preferred scope is also identical beyond the item of the following stated.
The preferred form of<<<Component units (a1) > > >
Form in the Component units of multipolymer (A2), with regard to the viewpoint of light sensitivity, by polymkeric substance as a whole, preferably 1 % by mole～95 % by mole of the containing ratios of Component units (a1), more preferably 10 % by mole～80 % by mole, and then more preferably 20 % by mole～70 % by mole, particularly preferably 30 % by mole～60 % by mole.In addition; especially in the situation that can be used for the described sour decomposability base of described Component units (a1) be contain carboxyl by the protection carboxyl of acetal protection or carboxyl the Component units by the protection carboxyl of ketal protection; more preferably 20 % by mole～70 % by mole of the containing ratios of the Component units (a1) in the Component units of the polymkeric substance that formation contains Component units (a1), particularly preferably 30 % by mole～60 % by mole.
The preferred form of<<<Component units (a2) > > >
Form in the Component units of multipolymer (A2), preferably 1 % by mole～95 % by mole of the containing ratios of Component units (a2), more preferably 1 % by mole～70 % by mole, and then more preferably 1 % by mole～50 % by mole, and then more preferably 5 % by mole～50 % by mole, particularly preferably 6 % by mole～50 % by mole.If in the scope of described numerical value, it is good that the various characteristics of the cured film obtained by photosensitive polymer combination becomes.
The preferred form of<<<Component units (a4) > > >
In the second example, (A2) multipolymer also can contain other Component units (a4) Component units of (still, be equivalent to described (a3) except).
Form in the Component units of multipolymer (A2), the containing ratio of Component units (a4) is preferably below 60 % by mole, more preferably below 50 % by mole, and then more preferably below 40 % by mole.Lower limit can be 0 % by mole, but for example can be made as more than 1 % by mole, and then can be made as more than 5 % by mole.If in the scope of described numerical value, it is good that the various characteristics of the cured film obtained by photosensitive polymer combination becomes.
The molecular weight of the multipolymer of<<(A2) > >
(A2) molecular weight of multipolymer is in the polystyrene conversion weight average molecular weight, and preferably 1,000～200,000, more preferably 2,000～50,000 scope.If, in the scope of described numerical value, various characteristics is good.The ratio (dispersion degree) of number average molecular weight and weight average molecular weight preferably 1.0～5.0, more preferably 1.5～3.5.
<(C) composition >
Photosensitive polymer combination of the present invention, not containing (A1) multipolymer the time, comprises (A2) multipolymer and (C) at least has the polymkeric substance of (c2) crosslinking group as component of polymer.In addition, photosensitive polymer combination of the present invention, when comprising (A1) multipolymer, also can comprise (C) composition as component of polymer.
(C) resin of the preferred addition polymerization type of composition, more preferably contain the polymkeric substance of the Component units that is derived from (methyl) acrylic acid and/or its ester.Moreover, also can there is the Component units beyond the Component units that is derived from (methyl) acrylic acid and/or its ester, such as the Component units that is derived from cinnamic Component units or derived from ethylene based compound etc.
(C) composition is preferably with respect to the total Component units in polymkeric substance, the Component units that contains (methyl) acrylic acid of being derived from more than 50 % by mole and/or its ester, be derived from cinnamic Component units, be derived from the Component units of maleimide compound, Alpha-Methyl-4-Vinyl phenol, and 4-Vinyl phenol, more preferably contain more than 90 % by mole, and then more preferably contain more than 95 % by mole, particularly preferably only comprise the Component units that is derived from (methyl) acrylic acid and/or its ester, be derived from cinnamic Component units, be derived from the Component units of maleimide compound, Alpha-Methyl-4-Vinyl phenol, and the polymkeric substance of 4-Vinyl phenol.
(C) composition can further comprise (c1) and contain the Component units of acidic group by the base of sour decomposability base protection.Contain (c1) by (C) composition, light sensitivity promotes, and by (C) composition, contains (c2), and the permanent film characteristic promotes.In addition, (C) composition does not preferably comprise in fact and contains by-NH-CH 2The Component units of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented.By being made as this kind of formation, the tendency that exists effect of the present invention more effectively to bring into play.Herein, what is called does not comprise in fact, does not refer to and adds with the level that effect of the present invention is impacted, and for example can enumerate below 4 % by mole of total Component units that are made as (C) composition, and then be made as below 1 % by mole.
As (c1) of (C) composition, can use with described<<(a1) contain the Component units of acidic group by the base of sour decomposability base protection identical base.Form in the Component units of multipolymer (C), with regard to the viewpoint of light sensitivity, 0 % by mole～95 % by mole of the containing ratio preferred polymers integral body of Component units (c1), more preferably 5 % by mole～90 % by mole, particularly preferably 20 % by mole～70 % by mole.
As (c2) of (C) composition, can use with described<<Component units that (a3) contains crosslinking group identical base.Preferred form is also identical.Form in the Component units of multipolymer (C), with regard to the viewpoint of light sensitivity, by polymkeric substance as a whole, preferably 1 % by mole～95 % by mole of the containing ratios of Component units (c2), more preferably 5 % by mole～90 % by mole, particularly preferably 30 % by mole～70 % by mole.
(C) composition, except (c1), (c2) reach (a2), also can have other Component units (c3).There is no particular restriction to become the monomer of other Component units (c3).Can use aptly with described<<(a4) other Component units identical base.Preferred form is also identical.Preferred scope is also identical.
The molecular weight of the composition of<<(C) > >
(C) molecular weight of composition is in the polystyrene conversion weight average molecular weight, and preferably 1,000～200,000, more preferably 2,000～50,000 scope.If, in the scope of described numerical value, various characteristics is good.The ratio (dispersion degree) of number average molecular weight and weight average molecular weight preferably 1.0～5.0, more preferably 1.5～3.5.
The manufacture method of the composition of<<(C) > >
Synthetic method about (C) composition, also known have a whole bag of tricks, if enumerate an example, can be by utilizing the free radical polymerization initiator, the free radical polymerization monomer potpourri that makes to contain the free radical polymerization monomer that is used to form the Component units represented by described (c1) and described (c2) carries out polymerization and synthesizes in organic solvent.In addition, also can synthesize by so-called high molecular weight reactive.
With (A) composition similarly, it is also preferred that end has carboxyl.
As the example of (C) composition, can enumerate:
Methacrylic acid-3,4-epoxycyclohexyl methyl esters/acrylic acid/hydroxystyrene/methyl methacrylate multipolymer (mol ratio is that 30/40/15/15, Mw is 7000)
Glycidyl methacrylate/methacrylic acid/styrene/methacrylic acid two ring pentyl ester multipolymers (mol ratio is that 70/10/10/10, Mw is 15000)
To vinyl benzyl glycidol ether/methacrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters/maleic acid/cyclohexyl methacrylate multipolymer (mol ratio is that 25/25/30/20, Mw is 27000)
Methacrylic acid 1-ethoxy ethyl ester/methacrylic acid/methacrylic acid (3-Ethyloxetane-3-yl) methyl esters/2-hydroxyethyl methacrylate/methylmethacrylate copolymer (mol ratio is that 38/7/35/15/5, Mw is 35000)
Methacrylic acid 1-cyclohexyloxy ethyl ester/methacrylic acid/methoxy polyethylene glycol methacrylate-styrene polymer (Blemmer PME-400, day oil (share) multipolymer (mol ratio is that 70/10/10, Mw is 45000)
Acrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters/methacrylic acid/N-phenyl maleimide copolymer (mol ratio is that 30/30/, Mw is 57000).
When with described (A2) multipolymer used time, (C) 10 quality % of the preferred total polymer composition of the content of composition～80 quality %, more preferably 20 quality %～70 quality %, and then more preferably 30 quality %～65 quality %, particularly preferably 30 quality %～60 quality %.
When with described (A1) multipolymer used time, (C) 0 quality % of the preferred total polymer composition of the content of composition～80 quality %, more preferably 8 quality %～70 quality %, and then more preferably 10 quality %～60 quality %, particularly preferably 10 quality %～50 quality %.
During (C) of more than two kinds when containing composition, its total amount becomes described scope.
<each Component units is for the ratio of total polymer composition >
99 quality % of photosensitive polymer combination preferred polymers composition of the present invention are above is (A) composition or (C) composition.
In addition, in the present invention, preferably 1 % by mole～50 % by mole of the ratios of the Component units in the total polymer composition (a2), more preferably 1 % by mole～40 % by mole, and then more preferably 1 % by mole～30 % by mole.
In addition, in the present invention, preferably 1 % by mole～50 % by mole of the ratios of the total of the Component units in the total polymer composition (a3) and Component units (c2), more preferably 10 % by mole～50 % by mole, and then more preferably 15 % by mole～50 % by mole.
The allotment amount of the multipolymer of<<(A) > >
Photosensitive polymer combination of the present invention is preferably with the ratio more than the 80 quality % that add up to the total solid composition, comprises (A1) multipolymer, (A2) multipolymer and (C) polymkeric substance.
<(B) light acid producing agent >
Photosensitive polymer combination of the present invention contains (B) light acid producing agent.As the light acid producing agent used in the present invention (also referred to as " (B) composition "), the induction wavelength is 300nm is above, optimal wavelength is 300nm～450nm actinic ray and acidic compound for preferably, but not limited by its chemical constitution.In addition, about directly not responding to wavelength, be the photoactinic smooth acid producing agent more than 300nm, if by with sensitizer and to be used for responding to wavelength be actinic ray more than 300nm and acidic compound, also can with the sensitizer combination after preferably use.As the light acid producing agent used in the present invention, preferably producing pKa is the light acid producing agent of the acid below 4, and more preferably producing pKa is the light acid producing agent of the acid below 3, and most preferably producing pKa is the light acid producing agent of the acid below 2.
As the example of light acid producing agent, can enumerate: trichloromethyl-s-triazine, sulfonium salt or salt compounded of iodine, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound, and oxime sulfonates compound etc.Among these light acid producing agents, with regard to the viewpoint of insulativity, preferably use the oxime sulfonates compound.These light acid producing agents can be used alone a kind or two or more is used in combination.As trichloromethyl-s-triazine, diaryl group iodized salt class, triaryl matte salt, quarternary ammonium salt class, and the concrete example of diazomethane derivative, but the compound of putting down in writing in the paragraph 0083～paragraph 0088 of illustration Japanese Patent Laid-Open 2011-221494 communique.
As the oxime sulfonates compound, there is the compound of oxime sulfonates structure, the compound that preferably illustration contains the oxime sulfonates structure represented by following general formula (B1).
General formula (B1)
Figure BDA00002864124900311
(in general formula (B1), R 21Mean alkyl or aryl.Wave-like line means the bond with other bases)
Any base all can be substituted, R 21In alkyl can be the straight chain shape, can be also branch-like, can be also ring-type.The substituting group that below explanation is allowed.
As R 21Alkyl, straight chain shape alkyl or branch-like alkyl that preferably carbon number is 1～10.R 21The alkyl aryl that can be 6～11 by carbon number, alkoxy that carbon number is 1～10 or naphthenic base (comprise 7,7-dimethyl-endocyclic alicyclic groups such as 2-oxo norborny, preferably bicyclic alkyl etc.) replace.
As R 21Aryl, the aryl that preferably carbon number is 6～11, more preferably phenyl or naphthyl.R 21Aryl can be replaced by low alkyl group, alkoxy or halogen atom.
The described compound that contains the oxime sulfonates structure represented by described general formula (B1) is also preferred for the oxime sulfonates compound represented by following general formula (B2).
Figure BDA00002864124900321
(in formula (B2), R 42Mean alkyl or aryl, X means alkyl, alkoxy or halogen atom, and m4 means 0～3 integer, and when m4 is 2 or 3, a plurality of X can be identical, also can be different)
R 42Preferred scope and described R 21Preferred scope identical.
The straight chain shape alkyl that is 1～4 as the preferred carbon number of the alkyl of X or branch-like alkyl.
The straight chain shape alkoxy that is 1～4 as the preferred carbon number of the alkoxy of X or branch-like alkoxy.
As the preferred chlorine atom of the halogen atom of X or fluorine atom.
M4 preferably 0 or 1.
In described general formula (B2), particularly preferably m4 is that 1, X is methyl, and the position of substitution of X is ortho position, R 42For the carbon number straight chain shape alkyl, 7 that is 1～10,7-dimethyl-2-oxo norborny methyl or to the compound of toluyl groups.
The compound that contains the oxime sulfonates structure represented by described general formula (B1) is for by following general formula (B3), represented oxime sulfonates compound is also more preferably.
(in formula (B3), R 43Implication and the R in formula (b1) 42Identical, X 1Mean the alkyl that halogen atom, hydroxyl, carbon number are 1～4, alkoxy, cyano group or the nitro that carbon number is 1～4, n4 means 0～5 integer)
As the R in described general formula (B3) 43, preferable methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor-n-pro-pyl, perfluor-normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, particularly preferably n-octyl.
X 1The alkoxy that preferably carbon number is 1～5, more preferably methoxyl.
N4 preferably 0～2, and particularly preferably 0～1.
Concrete example as the compound represented by described general formula (B3), can enumerate: α-(sulfonyloxy methyl oxygen base imino group) benzyl cyanide, α-(ethyl sulfonyloxy imino group) benzyl cyanide, α-(n-pro-pyl sulfonyloxy imino group) benzyl cyanide, α-(normal-butyl sulfonyloxy imino group) benzyl cyanide, α-(4-tosyloxy imino group) benzyl cyanide, α-[(sulfonyloxy methyl oxygen base imino group)-4-methoxyphenyl] acetonitrile, α-[(ethyl sulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(n-pro-pyl sulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(normal-butyl sulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(4-tosyloxy imino group)-4-methoxyphenyl] acetonitrile.
As the concrete example of preferred oxime sulfonates compound, can enumerate following compound (i)～compound (viii) etc., these compounds can be used alone a kind, or and use two or more.Compound (i)～compound (viii) can be used as commercially available product and obtains.In addition, also can be used in combination with (B) light acid producing agent of other kinds.
Figure BDA00002864124900341
As the compound that contains the oxime sulfonates structure represented by described general formula (B1), the compound represented by following general formula (OS-1) is also preferred.
Figure BDA00002864124900342
In described general formula (OS-1), R 101Mean hydrogen atom, alkyl, thiazolinyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl (carbamoyl), sulfamoyl, sulfo group, cyano group, aryl or heteroaryl.R 102Mean alkyl or aryl.
X 101Expression-O-,-S-,-NH-,-NR 105-,-CH 2-,-CR 106H-or-CR 105R 107-, R 105～R 107Mean alkyl or aryl.
R 121～R 124Mean independently respectively hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxy, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide group, sulfo group, cyano group or aryl.R 121～R 124In 2 can distinguish mutual bond and form ring.
As R 121～R 124, preferably hydrogen atom, halogen atom, and alkyl, in addition, also can preferably enumerate R 121～R 124In at least 2 mutual bonds and form the form of aryl.Wherein, with regard to the viewpoint of light sensitivity, preferred R 121～R 124Be the form of hydrogen atom.
Already described functional group all can further have substituting group.
The compound represented by described general formula (OS-1) is more preferably by the represented compound of following general formula (OS-2).
Figure BDA00002864124900351
In described general formula (OS-2), R 101, R 102, R 121～R 124Implication respectively with formula (OS-1) in R 101, R 102, R 121～R 124Identical, in addition, preference is also identical.
Among these compounds, the more preferably R in described general formula (OS-1) and described general formula (OS-2) 101For the form of cyano group or aryl, most preferably by described general formula (OS-2), meaned, and R 101Form for cyano group, phenyl or naphthyl.
In addition, in described oxime sulfonates compound, the spatial structure (E, Z etc.) about oxime or benzothiazole ring, can be respectively any spatial structure, can be also potpourri.
As can be aptly for of the present invention by described general formula (OS-1) concrete example of represented compound, can enumerate the compound (exemplary compounds b-1～exemplary compounds b-34) of putting down in writing in the paragraph 0128～paragraph 0132 of Japanese Patent Laid-Open 2011-221494 communique, but the present invention is not limited thereto.
In the present invention, as the compound that contains the oxime sulfonates structure represented by described general formula (B1), preferably by following general formula (OS-3), following general formula (OS-4) or the represented oxime sulfonates compound of following general formula (OS-5).
Figure BDA00002864124900361
(in general formula (OS-3)～general formula (OS-5), R 22, R 25And R 28Mean independently respectively alkyl, aryl or heteroaryl, R 23, R 26And R 29Mean independently respectively hydrogen atom, alkyl, aryl or halogen atom, R 24, R 27And R 30Mean independently respectively halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkoxy sulfonyl, X 1～X 3Mean independently respectively oxygen atom or sulphur atom, n 1～n 3Mean independently respectively 1 or 2, m 1～m 3Mean independently respectively 0～6 integer)
In described general formula (OS-3)～general formula (OS-5), R 22, R 25And R 28In alkyl, aryl or heteroaryl can there is substituting group.
In described formula (OS-3)～formula (OS-5), as R 22, R 25And R 28In alkyl, preferably can there is the alkyl that substituent total carbon number is 1～30.
In addition, in described general formula (OS-3)～general formula (OS-5), as R 22, R 25And R 28In aryl, preferably can there is the aryl that substituent total carbon number is 6～30.
In addition, in described general formula (OS-3)～general formula (OS-5), as R 1In heteroaryl, preferably can there is the heteroaryl that substituent total carbon number is 4～30.
In described general formula (OS-3)～general formula (OS-5), R 22, R 25And R 28In heteroaryl as long as at least 1 ring is assorted aromatic rings, for example mix aromatic rings and the phenyl ring ring that also can contract.
In described general formula (OS-3)～general formula (OS-5), R 23, R 26And R 29Preferred hydrogen atom, alkyl or aryl, more preferably hydrogen atom or alkyl.
In described general formula (OS-3)～general formula (OS-5), preferably in compound, there is the R more than 2 23, R 26And R 29In 1 or 2 be alkyl, aryl or halogen atom, more preferably 1 is alkyl, aryl or halogen atom, particularly preferably 1 is that alkyl and residue are for hydrogen atom.
As R 23, R 26And R 29In alkyl, preferably can there is the alkyl that substituent total carbon number is 1～12, more preferably can there is the alkyl that substituent total carbon number is 1～6.
As R 23, R 26And R 29In aryl, preferably can there is the aryl that substituent total carbon number is 6～30.
In described general formula (OS-3)～general formula (OS-5), X 1～X 3Mean independently respectively O or S, preferably O.
In described general formula (OS-3)～general formula (OS-5), contain X 1～X 3Ring as ring person is 5 Yuans rings or 6 Yuans rings.
In described general formula (OS-3)～general formula (OS-5), n 1～n 3Mean independently respectively 1 or 2, work as X 1～X 3During for O, preferred n 1～n 3Be independently 1 respectively, in addition, work as X 1～X 3During for S, preferred n 1～n 3Be independently respectively 2.
In described general formula (OS-3)～general formula (OS-5), R 24, R 27And R 30Mean independently respectively halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkoxy sulfonyl.Wherein, preferred R 24, R 27And R 30Independent respectively is alkyl or alkoxy.
R 24, R 27And R 30In alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkoxy sulfonyl can there is substituting group.
In described general formula (OS-3)～general formula (OS-5), as R 24, R 27And R 30In alkyl, preferably can there is the alkyl that substituent total carbon number is 1～30.
In described general formula (OS-3)～general formula (OS-5), as R 24, R 27And R 30In alkoxy, preferably can there is the alkoxy that substituent total carbon number is 1～30.
In addition, in described general formula (OS-3)～general formula (OS-5), m 1～m 3Mean independently respectively 0～6 integer, preferred 0～2 integer, more preferably 0 or 1, particularly preferably 0.
In addition, about each substituting group of described (OS-3)～(OS-5), the substituent preferred scope of (OS-3)～(OS-5) put down in writing in the paragraph 0092～paragraph 0109 of Japanese Patent Laid-Open 2011-221494 communique is preferred too.
In addition, the compound that contains the oxime sulfonates structure represented by described general formula (B1) is particularly preferably by any represented oxime sulfonates compound of following general formula (OS-6)～general formula (OS-11).
Figure BDA00002864124900381
(in formula (OS-6)～formula (OS-11), R 301～R 306Mean alkyl, aryl or heteroaryl, R 307Mean hydrogen atom or bromine atoms, R 308～R 310, R 313, R 316And R 318Mean independently respectively alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl that hydrogen atom, carbon number are 1～8, R 311And R 314Mean independently respectively hydrogen atom, halogen atom, methyl or methoxy, R 312, R 315, R 317And R 319Mean independently respectively hydrogen atom or methyl)
Preferred scope in described general formula (OS-6)～general formula (OS-11) is identical with the preferred scope of (OS-6)～(OS-11) that put down in writing in the paragraph 0110～paragraph 0112 of Japanese Patent Laid-Open 2011-221494 communique.
Concrete example as the oxime sulfonates compound represented by described general formula (OS-3)～described general formula (OS-5), can enumerate the compound of putting down in writing in the paragraph 0114～paragraph 0120 of Japanese Patent Laid-Open 2011-221494 communique, but the present invention is not limited to these compounds.
In photosensitive polymer combination of the present invention, with respect to (the preferred solid constituent of all resinous principles in photosensitive polymer combination, the more preferably total of multipolymer) 100 mass parts, (B) the light acid producing agent is preferably used 0.1 mass parts～10 mass parts, more preferably uses 0.5 mass parts～10 mass parts.Also two or more kinds may be used.
<(D) solvent >
Photosensitive polymer combination of the present invention contains (D) solvent.Preferably prepared as following solution by photosensitive polymer combination of the present invention: will be as the composition of described (C) composition that must composition～(D), as the composition of (E) described later composition of preferred composition～(I) and composition arbitrarily described later, be dissolved in the solution formed in (D) solvent.
As (D) solvent used in photosensitive polymer combination of the present invention, can use known solvent, but illustration: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetates, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetates, diethylene glycol dialkyl ether class, diethylene glycol monoalky lether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ether, dipropylene glycol monoalky lether acetates, ester class, ketone, amide-type, lactone etc.In addition, as the concrete example of (D) solvent used in photosensitive polymer combination of the present invention, also can enumerate the solvent of putting down in writing in the paragraph 0174～paragraph 0178 of Japanese Patent Laid-Open 2011-221494 communique.
In addition, optionally also can be to further adding benzylisoeugenol (benzyl ethyl ether), two hexyl ethers (dihexyl ether), ethyleneglycol monophenylether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, anisole, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, carbonic allyl ester equal solvent in these solvents.These solvents can be used alone a kind or two or more mix is used.Can be used for solvent of the present invention preferably separately use a kind or and with 2 kinds, more preferably also with 2 kinds, and then more preferably also by propylene-glycol monoalky lether acetates or dialkyl ether, diacetate class and diethylene glycol dialkyl ether class, or ester class and butylene glycol alkyl ether acetates.
In addition, as components D, preferably boiling point is more than 130 ℃, less than the solvents of 160 ℃, boiling point is the solvent more than 160 ℃, or the potpourri of these solvents, more preferably boiling point is more than 130 ℃, less than the solvents of 160 ℃, boiling point is the solvent more than 160 ℃, below 200 ℃, or the potpourri of these solvents, and then more preferably boiling point be more than 130 ℃, the potpourri that is the solvent more than 160 ℃, below 200 ℃ less than the solvents of 160 ℃ and boiling point.
As boiling point, be more than 130 ℃, less than the solvents of 160 ℃, but illustration: propylene glycol monomethyl ether acetate (boiling point is 146 ℃), dihydroxypropane single-ether acetate (boiling point is 158 ℃), propylene glycol methyl-n-butyl ether (methyl-n-buthyl ether) (boiling point is 155 ℃), propylene glycol methyl-positive propyl ether (boiling point is 131 ℃).
As boiling point, it is the solvent more than 160 ℃, but illustration: 3-ethoxyl ethyl propionate (boiling point is 170 ℃), diethylene glycol methyl ethyl ether (boiling point is 176 ℃), propylene glycol monomethyl ether propionate (boiling point is 160 ℃), dipropylene glycol methyl ether acetate (boiling point is 213 ℃), 3-methoxyl monobutyl ether acetate (boiling point is 171 ℃), diethylene glycol diethyl ether (boiling point is 189 ℃), diethylene glycol dimethyl ether (boiling point is 162 ℃), PGDA (boiling point is 190 ℃), diethylene glycol ether acetate alone (boiling point is 220 ℃), dipropylene glycol dimethyl ether (boiling point is 175 ℃), 1, 3-butylene glycol diacetate (boiling point is 232 ℃).
With respect to (the preferred solid constituent of all resinous principles in photosensitive polymer combination, more preferably described (C) multipolymer) 100 mass parts, the content of (D) solvent in photosensitive polymer combination of the present invention is 50 mass parts～3 preferably, 000 mass parts, more preferably 100 mass parts～2,000 mass parts, and then more preferably 150 mass parts～1,500 mass parts.
<other compositions >
In positive type photosensitive organic compound of the present invention, except described composition, optionally can preferably add (E) sensitizer, (F) crosslinking chemical, (G) and connect airtight modifying agent, (H) alkali compounds, (I) interfacial agent.And then, in positive type photosensitive organic compound of the present invention, can add plasticiser, hot radical and produce agent, antioxidant, thermal acid generator, ultraviolet light absorber, tackifier, development accelerant, and the known adjuvants such as antisettling agent of organic or inorganic.
(E) sensitizer
Photosensitive polymer combination of the present invention preferably contains sensitizer in the combination with (B) light acid producing agent, to promote the decomposition of (B) light acid producing agent.Sensitizer absorbs actinic ray or radioactive ray and becomes the electron excitation state.The sensitizer that becomes the electron excitation state contacts with the light acid producing agent, and produce, electronics moves, the effects such as energy moves, heating.Thus, the light acid producing agent produces chemical change and decomposes, and generates acid.As the example of preferred sensitizer, the compound that can enumerate the compounds that belongs to following and there is absorbing wavelength in any one of the wave band of 350nm～450nm.
The polynuclear aromatic same clan (pyrene for example, perylene, triphenylene, anthracene, 9,10-dibutoxy anthracene, 9,10-diethoxy anthracene, 3,7-dimethoxy anthracene, 9,10-dipropoxy anthracene), oxa anthracenes (fluorescein for example, eosin, erythrosine, rhodamine B, rose bengal), xanthone (xanthone for example, thioxanthone, dimethyl thia anthrone, diethyl thioxanthone), cyanine class (thia-carbonyl cyanine for example, the oxa-carbocyanine), merocyanine element class (merocyanine element for example, carbonyl merocyanine element), if red cyanines class, the oxonols class, thiazide (thionine for example, methylene blue, toluidine blue), acridine (acridine orange for example, chloroflavin, acridine yellow), acridine ketone (acridone for example, 10-butyl-2-chloro-acridine ketone), Anthraquinones (for example anthraquinone), class in side's acid (for example, in side's acid), the styrene base class, the basicity styrene base class (for example 2-[2-[4-(dimethylamino) phenyl] vinyl] benzoxazoles), Coumarins (7-lignocaine 4-methylcoumarin for example, 7-hydroxyl 4-methylcoumarin, 2,3,6,7-tetrahydrochysene-9-methyl isophthalic acid H, 5H, 11H[1] chromene [6,7,8-ij] quinolizine-11-ketone also).
Among these sensitizers, preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, Coumarins, more preferably the polynuclear aromatic same clan.Among the polynuclear aromatic same clan, anthracene derivant most preferably.
Light acid producing agent 100 mass parts with respect to photosensitive polymer combination, the addition of the sensitizer in photosensitive polymer combination of the present invention is 0 mass parts～1000 mass parts preferably, more preferably 10 mass parts～500 mass parts, and then more preferably 50 mass parts～200 mass parts.
Also two or more kinds may be used.
(F) crosslinking chemical
Optionally, photosensitive polymer combination of the present invention preferably contains crosslinking chemical.By adding crosslinking chemical, can make the cured film obtained by photosensitive polymer combination of the present invention become more firmly film.
As crosslinking chemical, so long as produces cross-linking reaction by heat, and unrestrictedly (except the A composition).Such as the compound, the crosslinking chemical that contains alkoxy methyl that there is epoxy radicals more than 2 or oxa-cyclobutyl in the molecule that can add the following stated or there is compound, blocked isocyanate (blocked isocyanate) compound of at least 1 ethene unsaturated double-bond etc.
Total solid composition 100 mass parts with respect to photosensitive polymer combination, the addition of the crosslinking chemical in photosensitive polymer combination of the present invention is 0.01 mass parts～50 mass parts preferably, more preferably 0.1 mass parts～30 mass parts, and then more preferably 0.5 mass parts～20 mass parts.By being added, can obtain the cured film of physical strength and solvent resistance excellence in this scope.Crosslinking chemical also can be used together multiple, in the case, all crosslinking chemicals is added up to calculate content.
There is epoxy radicals more than 2 or the compound of oxa-cyclobutyl in<molecule >
As the concrete example of the compound that there is the epoxy radicals more than 2 in molecule, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, aliphatic epoxy resin etc.
These compounds can be used as commercially available product and obtain.Such as the commercially available product of putting down in writing in the paragraph 0189 that can enumerate the Japanese Patent Laid-Open 2011-221494 communiques such as JER157S70, JER157S65, JER1007 (Mitsubishi Chemical's holding (Mitsubishi Chemical Holdings) (share) manufactures) etc.
In addition, also can enumerate: ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (more than, Ai Dike (ADEKA) (share) manufactures), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (more than, Ai Dike (share) manufactures), 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 (more than, the long rapids manufacture that changes into), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (more than, Nippon Steel's chemistry is manufactured), Celloxide 2021P, 2081, 3000, EHPE3150, Epolead GT400, Celvenus B0134, B0177 (Daicel (Daicel) (share)) etc.
These compounds can be used alone a kind or two or more is used in combination.
Among these compounds, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin and aliphatic epoxy resin can be more preferably enumerated, bisphenol A type epoxy resin can be particularly preferably enumerated.
As the concrete example of the compound that there is the oxa-cyclobutyl more than 2 in molecule, can use ARON OXETANE OXT-121, OXT-221, OX-SQ, PNOX (more than, East Asia synthetic (share) manufactured).
In addition, the compound that contains the oxa-cyclobutyl is preferably used separately or uses with the compound that contains epoxy radicals.
In addition, as other crosslinking chemicals, also can preferably use the crosslinking chemical that contains alkoxy methyl of putting down in writing in the paragraph 0107～paragraph 0108 of Japanese Patent Laid-Open 2012-8223 communique and the compound with at least 1 ethene unsaturated double-bond etc.
<blocked isocyanate compound >
The blocked isocyanate compound is so long as have the compound of blocked isocyanate base, and there is no particular restriction, but, with regard to indurative viewpoint, preferably in 1 molecule, have the compound of the blocked isocyanate base more than 2.
Moreover the blocked isocyanate base in the present invention refers to can be by the hot base that generate isocyanate group, for example, preferably illustration makes sealer be reacted the base of protecting isocyanate group to form with isocyanate group.In addition, described blocked isocyanate base preferably can generate the base of isocyanate group by the 90 ℃～heat of 250 ℃.
In addition, as the blocked isocyanate compound, its skeleton is not particularly limited, so long as have the compound of 2 isocyanate group in 1 molecule, can be any compound, can be also aliphatics, alicyclic or aromatic polyisocyanate, for example can be used: 2,4-toluene diisocyanate aptly, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-, nine methylene diisocyanates, 1,10-decamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-the diethyl ether diisocyanate, diphenyl methane-4,4 '-diisocyanate, the o-xylene diisocyanate, m xylene diisocyanate, the P-xylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), cyclohexane-1, the 3-dimethylene diisocyanate, cyclohexane-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, 3,3 '-methylene dimethylbenzene-4,4 '-diisocyanate, 4,4 '-the diphenyl ether diisocyanate, the tetrachloro phenylene vulcabond, norbornene alkyl diisocyanate, hydrogenation 1,3-xylylene diisocyanate, hydrogenation Isosorbide-5-Nitrae-isocyanate compounds such as xylylene diisocyanate reach the compound of the skeleton of prepolymer (prepolymer) type gone out from these compound derivings.Among these compounds, toluene diisocyanate (Tolylene Diisocyanate particularly preferably, TDI) or methyl diphenylene diisocyanate (Diphenyl Methane Diisocyanate, MDI), hexamethylene diisocyanate (Hexamethylene Diisocyanate, HDI), isophorone diisocyanate (Isophorone Diisocyanate, IPDI).
As the parent structure of the blocked isocyanate compound in photosensitive polymer combination of the present invention, can enumerate: biuret type, isocyanuric acid ester (isocyanurate) type, adduct type, two functional prepolymer types etc.
As the sealer of the enclosed construction that forms described blocked isocyanate compound, can enumerate: oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazole compound, imide series compound etc.Among these sealers, particularly preferably be selected from the sealer in oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound.
As described oxime compound, can enumerate oxime, reach ketoxime, particularly, but illustration: acetoxime, formaldoxime, cyclohexane oxime (cyclohexane oxime), methyl ethyl ketone oxime, cyclohexanone-oxime, diphenyl-ketoxime etc.
As described lactam compound, but illustration: epsilon-caprolactams, butyrolactam etc.
As described phenolic compounds, but illustration: phenol, naphthols, cresols, xylenol, halogen-substituted phenol etc.
As described alcoholic compound, but illustration: methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, lactic acid alkyl ester etc.
As described amines, can enumerate primary amine and secondary amine, can be any of aromatic amine, fatty amine, cycloaliphatic amines, but illustration: aniline, diphenylamine, aziridine, polyethyleneimine etc.
As described activity methene compound, but illustration: diethyl malonate, dimethyl malenate, ethyl acetoacetate, methyl acetoacetate etc.
As described pyrazole compound, but illustration: pyrazoles, methylpyrazole, dimethyl pyrazole etc.
As described mercaptan compound, but illustration: alkyl sulfhydryl, aryl mercaptan etc.
The blocked isocyanate compound that can be used for photosensitive polymer combination of the present invention can be used as commercially available product and obtains, and for example can preferably use: Coronate AP Stable M, Coronate2503, 2515, 2507, 2513, 2555, Millionate MS-50 (more than, Japanese polyurethane industry (Nippon Polyurethane Industry) (share) is manufactured), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (more than, Mitsui Chemicals (share) is manufactured), Duranate17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (more than, Asahi Chemical Industry's chemistry (Asahi Kasei Chemicals) (share) is manufactured), Desmodur BL1100, BL1265MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Desmodur BL3175 (more than, firmly change Bayer polyurethane (Sumika Bayer Urethane) (share) manufacture) etc.
(G) connect airtight modifying agent
Photosensitive polymer combination of the present invention also can contain (G) and connect airtight modifying agent (also referred to as " (G) composition ").Connect airtight modifying agent if use, can promote the character by the formed film of photosensitive polymer combination of the present invention by the adhesion of the formed film of photosensitive polymer combination of the present invention and substrate or capable of regulating.As connecting airtight modifying agent, preferred dialkoxy silicane compound or trialkoxy silane compound, more preferably trialkoxy silane compound.The carbon number of the alkoxy that alkoxysilane compound containing trialkylsilyl group in molecular structure has preferably 1～5.
(G) that can be used for photosensitive polymer combination of the present invention connects airtight modifying agent and preferably promotes the inorganics that becomes substrate, silicon compounds such as silicon, monox, silicon nitride, the compound of the adhesion of the metal such as gold, copper, molybdenum, titanium, aluminium and dielectric film.Particularly, known silane coupling agent etc. is also effective.
As silane coupling agent, for example can enumerate: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyl trialkoxy silane, γ-glycidoxypropyl dialkoxy silicane, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-sulfydryl propyl trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyl trialkoxy silane, vinyl trialkyl oxysilane.Among these silane coupling agents, more preferably γ-glycidoxypropyl trialkoxy silane or γ-methacryloxypropyl trialkoxy silane, and then more preferably γ-glycidoxypropyl trialkoxy silane, and then more preferably 3-glycidoxypropyltrimewasxysilane.These connect airtight modifying agent and can be used alone a kind or two or more is used in combination.
In addition, also can preferably adopt following compound.
(R 1) 4-n-Si-(OR 2) n
In general formula, R 1For the carbon number that do not there is reactive base be 1～20 alkyl, R 2For carbon number be 1～3 alkyl or phenyl, the integer that n is 1～3.
As concrete example, can enumerate following compound.
Figure BDA00002864124900471
In described compound, Ph is phenyl.
With respect to total solid composition 100 mass parts in photosensitive polymer combination, the content that (G) in photosensitive polymer combination of the present invention connects airtight modifying agent is 0.1 mass parts～30 mass parts, more preferably 0.5 mass parts～10 mass parts preferably.
(H) alkali compounds
Photosensitive polymer combination of the present invention also can contain (H) alkali compounds.As (H) alkali compounds, in the alkali compounds that can use from the chemically amplified photo resist agent, at random select to use.Such as enumerating: the quarternary ammonium salt of fatty amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic acid etc.As the concrete example of these alkali compounds, can enumerate the compound of putting down in writing in the paragraph 0204～paragraph 0207 of Japanese Patent Laid-Open 2011-221494 communique.
Particularly, as fatty amine, such as enumerating: trimethylamine, diethylamine, triethylamine, two-n-propylamine, three-n-propylamine, two-n-amylamine, three-n-amylamine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexyl methylamine etc.
As aromatic amine, such as enumerating: aniline, benzylamine (benzylamine), DMA, diphenylamine (diphenylamine) etc.
As hetero ring type amine, for example can enumerate: pyridine, the 2-picoline, the 4-picoline, the 2-ethylpyridine, the 4-ethylpyridine, the 2-phenylpyridine, the 4-phenylpyridine, N-methyl 4-phenyl pyridine, DMAP, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenyl imidazoles, nicotine, niacin, Nicotinic Acid Amide, quinoline, oxine, pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, piperidines, piperazine, morpholine, the 4-methyl morpholine, N-cyclohexyl-N '-[2-(4-morpholinyl) ethyl] thiocarbamide, 1, 5-diazabicyclo [4.3.0]-5-nonene, 1, 8-diazabicyclo [5.3.0]-7-hendecene etc.
As hydroxide level Four ammonium, such as enumerating: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide four-normal-butyl ammonium, hydroxide four-n-hexyl ammonium etc.
As the quarternary ammonium salt of carboxylic acid, such as enumerating: acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid four-normal-butyl ammonium, benzoic acid four-normal-butyl ammonium etc.
Can be used for alkali compounds of the present invention and can be used alone a kind, also two or more kinds may be used, preferably also uses two or more, more preferably also with 2 kinds, and then more preferably also with 2 kinds of hetero ring type amine.
With respect to total solid composition 100 mass parts in photosensitive polymer combination, the content of (H) alkali compounds in photosensitive polymer combination of the present invention is 0.001 mass parts～1 mass parts preferably, more preferably 0.005 mass parts～0.2 mass parts.
(I) interfacial agent
Photosensitive polymer combination of the present invention also can contain (I) interfacial agent.As (I) interfacial agent, can use any of negative ion system, kation system, nonionic system or both sexes, but preferred interfacial agent is that nonionic is interfacial agent.
Be the example of interfacial agent as nonionic, can enumerate: polyoxyethylene senior alkyl ethers, polyoxyethylene senior alkyl phenylate class, the higher fatty acid diester class of polyoxyethylene glycol, silicone-based, fluorine are interfacial agent.In addition, can enumerate following trade name: KP (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), Polyflow (common prosperity society chemistry (share) is manufactured), Eftop (Mitsubishi Materials changes into company and manufactures), Megafac (Di Aisheng (DIC) (share) manufacture), Fluorad (Sumitomo 3M (share) manufacture), Asahi Guard, Surflon (Asahi Glass (share) manufacture), PolyFox (manufacture of Ou Nuofa (OMNOVA) company), each series such as SH-8400 (eastern beautiful DOW CORNING silicone (Dow Corning Toray Silicone)).
In addition, as interfacial agent, the multipolymer that can be listed below is as preference, this multipolymer contains the Component units A represented by following general formula (1) and Component units B, and by tetrahydrofuran (Tetrahydrofuran, the weight average molecular weight (Mw) of the polystyrene conversion of being measured by gel permeation chromatography (Gel Penetration Chromatography) during THF) as solvent is more than 1,000, below 10,000.
General formula (1)
Component units A Component units B
Figure BDA00002864124900491
(in formula (1), R 401And R 403Mean independently respectively hydrogen atom or methyl, R 402Mean that carbon number is the straight-chain alkyl-sub-more than 1, below 4, R 404Mean that hydrogen atom or carbon number are the alkyl more than 1, below 4, L means that carbon number is the alkylidene more than 3, below 6, p and q are for meaning the quality percentage of polymerization ratio, p means the numerical value that 10 quality % are above, 80 quality % are following, q means the numerical value that 20 quality % are above, 90 quality % are following, r means the integer more than 1, below 18, and s means the integer more than 1, below 10)
Described L is represented branch's alkylidene by following general formula (2) preferably.R in general formula (2) 405Mean that carbon number is the alkyl 1 or more, 4 below, with regard to compatibility and, for regard to the viewpoint of the wetting state of applied, preferred carbon number is the alkyl more than 1, below 3, the alkyl that more preferably carbon number is 2 or 3.P and q and (p+q) preferred p+q=100, be 100 quality %.
General formula (2)
Figure BDA00002864124900492
The weight average molecular weight of described multipolymer (Mw) more preferably more than 1,500, below 5,000.
These interfacial agents can be used alone a kind or two or more mix is used.
With respect to total solid composition 100 mass parts in photosensitive polymer combination, the addition of (I) interfacial agent in photosensitive polymer combination of the present invention is preferably below 10 mass parts, more preferably 0.001 mass parts～50 mass parts, and then more preferably 0.01 mass parts～10 mass parts.
[antioxidant]
Photosensitive polymer combination of the present invention also can contain antioxidant.Can contain known antioxidant as antioxidant.By adding antioxidant, have advantages of as follows: can prevent cured film painted, maybe can reduce by decomposing caused thickness and reduce, in addition, the heat-resisting transparency is excellent.
As this kind of antioxidant, such as enumerating: phosphorous antioxidant, amide-type, hydrazides class, hindered amine are that antioxidant, sulphur are that antioxidant, phenol are antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxylamine derivative etc.Among these antioxidants, with regard to the viewpoint that painted, the thickness of cured film reduces, particularly preferably phenol is that antioxidant, acid amides are that antioxidant, hydrazides are that antioxidant, sulphur are antioxidant.These antioxidants can be used alone a kind, also can mix two or more.
Be the commercially available product of antioxidant as phenol, for example can enumerate: Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO-50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A-613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, AdekastabCDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (more than, Ai Dike (share) manufactures), Irganox245FF, Irganox1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BASF (BASF) (share) manufacture), sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 (Sumitomo Chemical (share) manufacture), Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 (manufacture of (share) API company) etc.
Wherein, can use aptly Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098.
With respect to the total solid composition of photosensitive polymer combination, the content of antioxidant is 0.1 quality %～10 quality % preferably, more preferably 0.2 quality %～5 quality %, particularly preferably 0.5 quality %～4 quality %.By being made as in this scope, light sensitivity when formed film can obtain the sufficient transparency and pattern formation also becomes good.
In addition, adjuvant beyond also can be using the various ultraviolet light absorbers put down in writing in " new development of polymeric additive (Nikkan Kogyo Shimbun (share)) " or metal passivator etc. as antioxidant, be added in photosensitive polymer combination of the present invention.
In addition, in the present invention, use in fact and can not produce acid because of the irradiation of exposure light, and come acidic sulphonic acid ester also preferred by heat.
Can not produce acid because of the irradiation of exposure light in fact can be by the infrared ray (Infrared before and after the exposure according to compound, IR) spectrum or nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectroscopic assay, spectrum is unchanged to be judged.
The molecular weight of sulphonic acid ester preferably 230～1,000, more preferably 230～800.
Can be used for sulphonic acid ester of the present invention and can use commercially available sulphonic acid ester, also can use by the sulphonic acid ester of known method synthesized.Sulphonic acid ester for example can, by under alkali condition, make sulfonic acid chloride or sulphonic acid anhydride be reacted with corresponding polyvalent alcohol synthetic.
When the total content by (C) composition is made as 100 mass parts, the content of thermal acid generator in photosensitive polymer combination is 0.5 mass parts～20 mass parts preferably, more preferably 1 mass parts～15 mass parts.
[acid proliferation generator]
For promotion feeling luminosity, photosensitive polymer combination of the present invention can be used acid proliferation generator.
Can be used for acid proliferation generator of the present invention is to react and further to produce compound sour and that make the acid concentration in reactive system increase by sour catalyst, and is the compound stably existed under sour state in not existing.This kind of compound increases the acid more than a kind by 1 secondary response, therefore follow the progress of reaction, reaction is carried out post, but itself can bring out selfdecomposition the acid produced, the intensity of the acid that therefore this place produces is in acid ionization constant, pKa, preferably below 3, particularly preferably below 2.
As the concrete example of acid proliferation generator, can enumerate: the paragraph 0203～paragraph 0223 of Japanese patent laid-open 10-1508 communique, the paragraph 0016～paragraph 0055 of Japanese patent laid-open 10-282642 communique, and the 39th page of the 12nd row～47 of Jap.P. JP-A 9-512498 communique page the 2nd row in the compound put down in writing.
As can be used for acid proliferation generator of the present invention, the acid that can enumerate by producing from acid producing agent is decomposed, and produces the compound that the pKa such as dichloroacetic acid, trichloroacetic acid, methane-sulforic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid are the acid below 3.
Particularly, can enumerate following compound etc.
Figure BDA00002864124900521
With regard to the viewpoint of the dissolving contrast of exposure section and unexposed section, with respect to light acid producing agent 100 mass parts, content by acid proliferation generator in photosensitive polymer combination preferably is made as 10 mass parts～1,000 mass parts, more preferably is made as 20 mass parts～500 mass parts.
[development accelerant]
Photosensitive polymer combination of the present invention can contain development accelerant.
As development accelerant, can use the compound arbitrarily with development accelaration effect, but the compound that preferably there is at least one structure in the group that is selected from carboxyl, phenol hydroxyl, reaches alkylene oxide group, the compound that more preferably has carboxyl or phenol hydroxyl, most preferably have the compound of phenol hydroxyl.
In addition, as the molecular weight of (M) development accelerant, preferably 100～2000, more preferably 100～1000, most suitable is 100～800.
Example as development accelerant, as the development accelerant with alkylene oxide group, can enumerate: the monomethyl ether of polyglycol, polyglycol, the dimethyl ether of polyglycol, LABRAFIL M 1944CS, polypropylene glycol glyceride, polypropylene glycol two glyceride, polytetramethylene glycol, polyglycol-Bisphenol A Ether, polypropylene glycol-Bisphenol A Ether, polyoxyethylated alkyl ether, polyoxyethylated Arrcostab, and Japanese patent laid-open 9-222724 communique in the compound put down in writing etc.
As the development accelerant with carboxyl, can enumerate: maleic acid, fumaric acid, acetylene carboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, suberic acid, hexane diacid, citric acid, malic acid etc.In addition, can enumerate: the compound of putting down in writing in Japanese Patent Laid-Open 2000-66406 communique, Japanese patent laid-open 9-6001 communique, Japanese patent laid-open 10-20501 communique, Japanese patent laid-open 11-338150 communique etc.
As the development accelerant with phenol hydroxyl, can enumerate: the compound of putting down in writing in Japanese Patent Laid-Open 2005-346024 communique, Japanese patent laid-open 10-133366 communique, Japanese patent laid-open 9-194415 communique, Japanese patent laid-open 9-222724 communique, Japanese patent laid-open 11-171810 communique, Japanese Patent Laid-Open 2007-121766 communique, Japanese patent laid-open 9-297396 communique, Japanese Patent Laid-Open 2003-43679 communique etc.Among these, suitable is the phenolic compounds that the phenyl ring number is 2～10, is more suitably the phenolic compounds that the phenyl ring number is 2～5.As compound particularly preferably, can enumerate the phenoloid disclosed as dissolution accelerator in Japanese patent laid-open 10-133366 communique.
Development accelerant can be used alone a kind, and also two or more kinds may be used.
With regard to the viewpoint of light sensitivity and residual film ratio, when (A) become to be divided into 100 mass parts, the addition of the development accelerant in photosensitive polymer combination of the present invention is 0 mass parts～30 mass parts preferably, more preferably 0.1 mass parts～20 mass parts, most preferably 0.5 mass parts～10 mass parts.
In addition, also can use the hot radical of putting down in writing in the paragraph 0120～paragraph 0121 of Japanese Patent Laid-Open 2012-8223 communique to produce agent, reach the thermal acid generator as other adjuvants.
The preparation method of<photosensitive polymer combination >
With the ratio of regulation and with method arbitrarily, each composition is mixed, then carry out stirring and dissolving and prepare photosensitive polymer combination.For example, also can make in advance composition be dissolved in solvent respectively in and after making solution, by these compositions with the regulation ratio mix to prepare resin combination.As the composition solution of preparation as above also can be after being used filtrator that aperture be 0.2 μ m etc. to be filtered, in.
[manufacture method of cured film]
Secondly, the manufacture method of cured film of the present invention described.
The manufacture method of cured film of the present invention preferably includes the step of following (1)～(5).
(1) photosensitive polymer combination of the present invention is coated on to the step on substrate;
(2) remove the step of solvent from be coated with photosensitive polymer combination;
(3) step of utilizing actinic ray to be exposed to the photosensitive polymer combination of having removed solvent;
(4) step of utilizing aqueous developer solution to be developed to the photosensitive polymer combination through exposure;
(5) to the photosensitive polymer combination through developing carry out thermmohardening after baking procedure.
Next coming in order describe each step.
In the application step of (1), preferably photosensitive polymer combination of the present invention be coated on substrate and make the moistening film that contains solvent.Preferably photonasty is being set to resin combination and is being carried out before coating on substrate the cleaning of the substrates such as alkali cleaning or plasma cleaning, more preferably after base-plate cleaning and then utilize hexamethyldisilazane to be processed substrate surface.By carrying out this processing, there is the tendency of photosensitive polymer combination for the adhesion lifting of substrate.Method as utilizing hexamethyldisilazane to be processed substrate surface, be not particularly limited, and such as enumerating, first makes substrate expose method in the hexamethyldisilazane steam etc. to the open air.
As described substrate, can enumerate inorganic substrate, resin, resin composite materials etc.
As inorganic substrate, for example can enumerate: glass, quartz, silicone, silicon nitride, and the composite base plate that evaporation molybdenum, titanium, aluminium, copper etc. form on this kind of substrate.
As resin, can enumerate the substrate that comprises following synthetic resin: polybutylene terephthalate, polyethylene terephthalate, Polyethylene Naphthalate, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyethersulfone, polyarylate, allyl diglycol carbonates, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, poly-cycloolefin, norbornene resin, the fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acryl resin, epoxy resin, silicone resin, ionomer resin, cyanate ester resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic ether, maleimide-alkene, cellulose, episulfide compounds etc.
The situation that these substrates directly use with described form is few, usually according to the form of end article, and is formed with the multilayer laminated boards structure as thin film transistor (TFT) (Thin Film Transistor, TFT) element for example.
Coating process on substrate is not particularly limited, such as using: methods such as slot coated method, spray-on process, rolling method, method of spin coating, curtain coating rubbing method, slit and rotation (slit and spin) methods.And then, also can apply so-called prewetting (prewet) method as put down in writing in Japanese Patent Laid-Open 2009-145395 communique.
Wet-film thickness while having carried out coating is not particularly limited, and can be coated with the thickness corresponding to purposes, but usually use in the scope of 0.5 μ m～10 μ m.
In the solvent removal step of (2), remove solvent by decompression (vacuum) and/or heating from be coated with described film, thereby form Gan Zao Tu film on substrate.The heating condition of solvent removal step preferably heats about 30 seconds～300 seconds under 70 ℃～130 ℃.When temperature and time is described scope, there is the tendency that adhesion is better and residue also can further reduce of pattern.
In the step of exposure of (3), via the shade of the pattern with regulation, to being provided with the substrate of filming, irradiate actinic ray.In this step, the light acid producing agent decomposes and produces sour.Be coated with the catalysis of the acid that in film component, contained sour decomposability gene produces and be hydrolyzed, thereby generating carboxyl or phenol hydroxyl.
As utilizing photoactinic exposure light source, can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light emitting diode (Light Emitting Diode, LED) light source, excimer laser generation device etc., can preferably use g ray (436nm), i ray (365nm), h ray (405nm) etc. there is 300nm more than, the actinic ray of the following wavelength of 450nm.In addition, optionally also can adjust irradiation light by minute optical filter as long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter (band-pass filter).
As exposure device, can use mirror surface projection to aim at exposer (mirror projection aligner), stepper, scanner, the exposure machine of the variety of ways such as close induction type, contact, microlens array, laser explosure.
In generation, have in the zone of sour catalyst, in order to accelerate described hydrolysis reaction, the rear heat treated of can being exposed: postexposure bake (Post Exposure Bake) (below, also referred to as " PEB ").By PEB, can promote the generation from carboxyl or the phenol hydroxyl of sour decomposability base.Temperature while carrying out PEB preferably more than 30 ℃, below 130 ℃, more preferably more than 40 ℃, below 110 ℃, particularly preferably more than 50 ℃, below 100 ℃.
But the energy of activation that the sour decomposability base in the present invention decomposes due to acid is low, the acid that is derived from the light acid producing agent that easily the reason exposure produces and decomposing, and produce carboxyl or phenol hydroxyl, and therefore may not carry out PEB, also can form erect image by developing.
In the development step of (4), use alkaline-based developer to have Yi Swam from carboxyl or the polymkeric substance of phenol hydroxyl developed.Remove in the exposure section zone that will comprise the resin combination with the carboxyl that easily is dissolved in alkaline-based developer or phenol hydroxyl, forms thus erect image.
Contain alkali compounds in the developer solution preferably used in development step.As alkali compounds, such as using: alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide; The alkali carbonate such as sodium carbonate, sal tartari class; The alkaline metal bicarbonate such as sodium bicarbonate, potassium bicarbonate class; The ammonium hydroxide classes such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, bursine; The aqueous solution of sodium silicate, sodium metasilicate etc.In addition, also can will add aqueous solution that the water-miscible organic solvent such as appropriate amount methyl alcohol or ethanol or interfacial agent form in the aqueous solution to described bases as developer solution.
As preferred developer solution, can enumerate 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution, 2.38% aqueous solution of tetraethyl ammonium hydroxide.
The pH of developer solution preferably 10.0～14.0.
Development time preferably 30 seconds～500 seconds, in addition, the method for development can be any methods such as puddle formula (puddle) development method, infusion process.After development, the flowing water that usually can carry out 30 seconds～300 seconds cleans, and forms desired pattern.
After development, also can carry out the drip washing step.In the drip washing step, utilize pure water etc. to clean the substrate after developing, developer solution removal that thus will be accompanying, and the development residue is removed.ELUTION METHOD can be used known method.Such as enumerating spray drip washing or dipping drip washing etc.
In the rear baking procedure of (5), by the erect image to obtained, heated, can make sour decomposability base carry out thermal decomposition and generate carboxyl or phenol hydroxyl, and carry out crosslinkedly with bridging property base, crosslinking chemical etc., can form cured film thus.The heating arrangements such as heating plate or baking oven are preferably used in this heating, for example, in the temperature of regulation, under 180 ℃～250 ℃, with official hour, if for example on heating plate, carry out the heat treated of 5 minutes～90 minutes, if baking oven carries out the heat treated of 30 minutes～120 minutes.By carrying out this kind of cross-linking reaction, can form more excellent diaphragm or the interlayer dielectrics such as thermotolerance, hardness.In addition, when carrying out heat treated, also can under nitrogen environment, carry out, further promote thus the transparency.
Baking (appending of middle baking procedure) after carrying out after also can being toasted before rear baking, with lower temperature.When carrying out the centre baking, preferably under 90 ℃～150 ℃, heating, after 1 minute～60 minutes, is toasted after carrying out under the high temperature more than 200 ℃.In addition, also centre can be toasted, rear baking is divided into 3 multistages more than the stage and heated.By the design of baking, rear baking in the middle of this kind, the cone angle of capable of regulating pattern.Described heating can be used the known heating means such as heating plate, baking oven, infrared heater.
Moreover, can be before rear baking, utilize actinic ray to form figuratum substrate expose again (post-exposure) comprehensively, then carry out rear baking, produce thus acid in light acid producing agent from be present in unexposed portion, and make it as the catalyst performance function that promotes cross-linking step, thereby can promote the sclerous reaction of film.The preferred 100mJ/cm of preferred exposure while comprising the post-exposure step 2～3,000mJ/cm 2, 100mJ/cm particularly preferably 2～500mJ/cm 2.
And then the cured film obtained by photosensitive polymer combination of the present invention also can be used as dry etching resist (dry etching resist).In the time will being undertaken cured film that thermmohardening obtains as dry etching resist by rear baking procedure, can carry out the dry etch process such as ashing, plasma etching, ozone etching as etch processes.
[cured film]
Cured film of the present invention is to make photosensitive polymer combination sclerosis of the present invention and the cured film of acquisition.
Cured film of the present invention can be used as interlayer dielectric aptly.In addition, the cured film of the present invention cured film that preferably manufacture method by cured film of the present invention obtains.
By photosensitive polymer combination of the present invention, can obtain the insulativity excellence, also there is the interlayer dielectric of high transparent while at high temperature being toasted.The interlayer dielectric that uses photosensitive polymer combination of the present invention to form has high transparent and cured film physical properties excellent, therefore useful for the purposes of organic EL display or liquid crystal indicator.
[liquid crystal indicator]
Liquid crystal indicator of the present invention is characterised in that to possess cured film of the present invention.
As liquid crystal indicator of the present invention, except having the formed planarization film of described photosensitive polymer combination of the present invention of use or interlayer dielectric, there is no particular restriction, can enumerate the known liquid crystal indicator that adopts various structures.
For example, the concrete example of the TFT possessed as liquid crystal indicator of the present invention (Thin-Film Transistor), can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to the electrical characteristics excellence, is preferably used after therefore can combining with these TFT.
In addition, as the adoptable liquid crystal drive mode of liquid crystal indicator of the present invention, can enumerate: twisted-nematic (Twisted Nematic, TN) mode, vertical orientation (Vertical Alignment, VA) mode, coplanar switching (In-Plane Switching, IPS) mode, fringing field switching (Fringe Field Switching, FFS) mode, optical compensation curved (Optically Compensated Bend, OCB) mode etc.
In panel forms, even if at colorful optical filter array (Color Filter on Array, COA) in the liquid crystal indicator of mode, also cured film of the present invention be can use, the organic insulating film (115) of Japanese Patent Laid-Open 2005-284291 communique or the organic insulating film (212) of Japanese Patent Laid-Open 2005-346054 communique for example can be used as.
In addition, as the concrete orientation mode of the adoptable liquid crystal orienting film of liquid crystal indicator of the present invention, can enumerate friction matching method, light orientation method etc.In addition, also can obtain polymkeric substance orientation support by polymer-stabilized alignment (Polymer Sustained Alignment, the PSA) technology of putting down in writing in Japanese Patent Laid-Open 2003-149647 or Japanese Patent Laid-Open 2011-257734.
In addition, photosensitive polymer combination of the present invention and cured film of the present invention are not limited to described purposes, can be used for various uses.For example; except planarization film or interlayer dielectric, also can be aptly for the diaphragm of colored filter or in order to the thickness of the liquid crystal layer by liquid crystal indicator, remain in fixing pad or solid photographic element lenticule be arranged on colored filter etc.
Fig. 2 means the concept sectional view of an example of the liquid crystal indicator 10 of active matrix mode.This color liquid crystal display arrangement 10 has the liquid crystal panel of back light unit 12 for the back side, and liquid crystal panel disposes the element of the TFT16 corresponding with being configured in all pixels between the 2 sheet glass substrates 14,15 that are pasted with light polarizing film.In each element on being formed at glass substrate, by being formed on the connect up ito transparent electrode 19 of tangible one-tenth pixel electrode of contact hole 18 in cured film 17.Be provided with the layer of liquid crystal 20 and dispose the RGB colored filter 22 of black matrix" on ito transparent electrode 19.
Light source as backlight, be not particularly limited, and can use known light source.Such as enumerating: White LED, blue red green etc. multi-colored led, fluorescent light (cold-cathode tube), organic EL etc.
In addition, liquid crystal indicator also can be made the device of 3D (stereopsis) type or the device of touching control panel.And then, also can be made as flexible type, can be used as the 2nd phase insulation film (48) of Japanese Patent Laid-Open 2011-145686 communique or the phase insulation film (520) of Japanese Patent Laid-Open 2009-258758 communique.
[organic EL display]
Organic EL display of the present invention is characterised in that to possess cured film of the present invention.
As organic EL display of the present invention, except thering is the formed planarization film of described photosensitive polymer combination of the present invention of use or interlayer dielectric, there is no particular restriction, can enumerate the known various organic EL displays or the liquid crystal indicator that adopt various structures.
For example, the concrete example of the TFT possessed as organic EL display of the present invention (Thin-Film Transistor), can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to the electrical characteristics excellence, is preferably used after therefore can combining with these TFT.
Fig. 1 means the formation concept map of an example of organic EL display.The constructed profile of the substrate in the organic EL display of expression bottom-emission type, and there is planarization film 4.
Form the TFT1 of bottom gate type on glass substrate 6, and form the dielectric film 3 that comprises Si3N4 under the state that covers this TFT1.After illustrated contact hole has been omitted in formation herein on dielectric film 3, form the distribution 2 (being highly 1.0 μ m) that is connected in TFT1 via this contact hole on dielectric film 3.Distribution 2 is in order to by between TFT1 or the line that the organic EL formed in step thereafter is connected with TFT1.
And then, in order to make the concavo-convex planarization produced by forming of distribution 2, imbedding under the concavo-convex state produced by distribution 2, form planarization film 4 on dielectric film 3.
Form the organic EL of bottom-emission type on planarization film 4.That is the first electrode 5 that, makes to comprise ITO is connected in distribution 2 via contact hole 7 and is formed on planarization film 4.In addition, the first electrode 5 is equivalent to the anode of organic EL.
Form the dielectric film 8 of the shape of the periphery that covers the first electrode 5, by this dielectric film 8 is set, can prevent the short circuit between formed the second electrode in the first electrode 5 and step thereafter.
And then, although not shown in Fig. 1, but carry out successively evaporation via desired pattern shade hole transmission layer, organic luminous layer, electron transfer layer are set, then, form the second electrode that comprises Al on whole above substrate, then by being fitted to seal with glass for sealing plate and UV cured type epoxy resin, and obtain the organic EL display that connects the active array type formed in order to the TFT1 that it is driven on each organic EL.
Photosensitive polymer combination of the present invention is due to hardening and cured film excellent, therefore will use the formed resist pattern of photosensitive polymer combination of the present invention to make dividing wall is used as MEMS (micro electro mechanical system) (Micro-Electro-Mechanical Systems, MEMS) with the structure member of element or is assembled rear use as the part of Mechanical Driven part.As this kind of MEMS element, such as enumerating: surface acoustic wave filter (Surface Acoustic Wave Filter), bulk accoustic wave filter (BulkAcoustic Wave Filter), gyro sensor, the parts such as micro-shutter, image sensor, Electronic Paper, ink gun, biochip, sealant for display.Example has illustration in the special table of Jap.P. 2007-522531 communique, Japanese Patent Laid-Open 2008-250200 communique, Japanese Patent Laid-Open 2009-263544 communique etc. more specifically.
Photosensitive polymer combination of the present invention is due to flatness or transparency excellence, therefore also can be used to form accumulation horizon (16) and the planarization film (57) put down in writing in Fig. 2 of Japanese Patent Laid-Open 2011-107476 communique for example, the dividing wall (12) of putting down in writing in Fig. 4 of Japanese Patent Laid-Open 2010-9793 communique (a) and planarization film (102), the accumulation horizon of putting down in writing in Figure 10 of Japanese Patent Laid-Open 2010-27591 communique (221) and the 3rd interlayer dielectric (216b), the 2nd interlayer dielectric (125) of putting down in writing in Fig. 4 of Japanese Patent Laid-Open 2009-128577 communique (a) and the 3rd interlayer dielectric (126), the planarization film of putting down in writing in Fig. 3 of Japanese Patent Laid-Open 2010-182638 communique (12) and pixel separation dielectric film (14) etc.In addition, also can be aptly for the thickness of the liquid crystal layer in order to by liquid crystal indicator, remain fixing pad, or the crystalline substance of facsimile recorder, electronic copier, solid photographic element etc. carries the imaging optical system of colored filter or the lenticule of the joints of optical fibre.
Embodiment
Below, enumerate embodiment and be described more specifically the present invention.Only otherwise break away from purport of the present invention, the material shown in following embodiment, use amount, ratio, contents processing, handling procedure etc. can suitablely change.Therefore, scope of the present invention is not limited to concrete example shown below.Moreover as long as, in advance without special instruction, " part ", " % " are quality criteria.
In following synthesis example, following symbol means respectively following compound.
V-65:2,2 '-azo two (2,4-methyl pentane nitrile) (manufacturing with the pure pharmaceutical worker's industry of light)
V-601: dimethyl-2,2 '-azo two (propionic acid 2-methyl esters) (manufacturing with the pure pharmaceutical worker's industry of light)
MAEVE: methacrylic acid 1-ethoxy ethyl ester
MATHF: methacrylic acid tetrahydrochysene-2H-furans-2-base ester
MATHP: methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester
CHOEMA: methacrylic acid 1-(cyclohexyloxy) ethyl ester
StOEVE:4-(1-ethoxy ethoxy) styrene
T-BuMA: Tert-butyl Methacrylate
The 1-ethoxyethylether of P-Ph-1:4-hydroxybenzoic acid (3-methacryloxypropyl) ester
StCOOEVE: the 1-ethoxyethylether of styrene carboxylic acid
NBMA: n-butoxy Methacrylamide (NBMA, Tokyo changes into manufacture)
IBMAA: isobutoxy Methacrylamide (Tokyo changes into manufacture)
MMAA: methoxy acrylamide (manufacture of MRC UNITEC company)
GMA: glycidyl methacrylate
M100: methacrylic acid 3,4-epoxycyclohexyl methyl esters (Daicel chemical industry (share) manufacture)
OXE-30: methacrylic acid (3-Ethyloxetane-3-yl) methyl esters (Osaka organic chemistry industry (share) is manufactured)
AllyMA: allyl methacrylate
MAA-GMA: following structure
Figure BDA00002864124900601
HEMA: 2-hydroxyethyl methacrylate
THFFMA: tetrahydrofurfuryl methacrylate
St: styrene
MMA: methyl methacrylate
MAA: methacrylic acid
AA: acrylic acid
HO-MS: following structure (HO-MS, common prosperity society manufactures)
Figure BDA00002864124900611
HO (A)-HH: following structure (HO (A)-HH, common prosperity society manufactures)
PHS: 4-Vinyl phenol
Ph-1:4-hydroxybenzoic acid (3-methacryloxypropyl) ester
HEMA: 2-hydroxyethyl methacrylate (manufacturing with the pure pharmaceutical worker's industry of light)
AcAc: glycol monomethyl acetoacetate monomethacrylates (following structure)
Figure BDA00002864124900613
DCPM: methacrylic acid two ring pentyl esters
EDM: diethylene glycol ethyl-methyl ether (eastern nation chemical industry is manufactured, Hisolve EDM)
Synthesizing of<polymer A-1 >
Synthesize the polymer A-1 as multipolymer (A) as following.
Add 0.5 part of phenothiazine in 144.2 parts of ethyl vinyl ethers (2 molar equivalent), after one side is cooled to below 10 ℃ and simultaneously drips 86.1 parts of methacrylic acids (1 molar equivalent) in reactive system, stir 4 hours under room temperature (25 ℃).After 5.0 parts of interpolation p-toluenesulfonic acid pyridines, at room temperature stir 2 hours, then at room temperature place a night.To adding 5 parts, 5 parts of sodium bicarbonates and sodium sulphate in reactant liquor, at room temperature stir 1 hour, after being filtered, insolubles carrying out reduced pressure concentration below 40 ℃, yellow oil to residue is carried out decompression distillation, and obtains as 134.0 parts of the methacrylic acid 1-ethoxy ethyl esters (MAEVE) of 43 ℃～45 ℃/7mmHg of boiling point (bp.) cut of colorless oil.
Diethylene glycol ethyl-methyl ether (eastern nation chemical industry is manufactured, Hisolve EDM, 45g) is added in there-necked flask as solvent, is warming up to 90 ℃ under nitrogen environment.Last 2 hours and drip the methyl methacrylate (MMA as monomer component in this solution, with the pure pharmaceutical worker's industry of light, manufacture, 3.27g), methacrylic acid 1-ethoxy ethyl ester (MAEVE, 22.45g), methacrylic acid hydroxyl ethyl ester (HEMA, with the pure medicine manufacture of light, 6.57g), methacrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters (OXE-30, Osaka organic chemistry industry is manufactured, 20.26g), and n-butoxy Methacrylamide (NBMA, Tokyo changes into manufacture, 9.43g), and as the dimethyl 2 of polymerization initiator, 2 '-two (propionic acid 2-the methyl esters) (V-601 of azo, with the pure pharmaceutical worker's industry of light, manufacture, 7.36g, with respect to monomer, be 8mol%), and they are dissolved.Drip and finish rear the stirring 2 hours.Further add V-601 (1.84g is 2mol% with respect to monomer) in this solution, and then stir 2 hours, then finish reaction.Obtain thus polymer A-1.Weight average molecular weight is 12000.
Change monomeric species etc. as shown in following table, and similarly synthetic polymer A-2～polymer A-8, polymkeric substance C-1～polymkeric substance C-3, polymkeric substance C-5.
<polymkeric substance C-4's is synthetic >
Under stream of nitrogen gas, methacrylic acid 1-ethoxy ethyl ester (79.06 mass parts (0.5 molar equivalent)), methacrylic acid (43.05 mass parts (0.5 molar equivalent)) and the mixed solution of diethylene glycol ethyl-methyl ether (99.9 mass parts) are heated to 70 ℃.One is stirred in the face of this mixed solution, and one side is lasted 2.5 hours and drip the mixed solution of free radical polymerization initiator V-65 (manufacturing 4.5 mass parts with the pure pharmaceutical worker's industry of light (share)) and diethylene glycol ethyl-methyl ether (90.0 mass parts).After dripping end, under 70 ℃, reaction is 5 hours, obtains thus the diethylene glycol ethyl-methyl ethereal solution (solid component concentration: 40 quality %) of polymkeric substance C-1.
Further add glycidyl methacrylate (56.86 mass parts (0.4 molar equivalent)), benzyl triethyl ammonium ammonium (2.41 mass parts), diethylene glycol ethyl-methyl ether (85.3 mass parts) in described polymkeric substance C-1 solution, and reacted under 75 ℃, obtain thus the diethylene glycol ethyl-methyl ethereal solution (solid component concentration: 40 quality %) of polymkeric substance C-4.The polymkeric substance C-4 obtained to pass through the weight average molecular weight that gel permeation chromatography (Gel Permeation Chromatography, GPC) measures be 20,000.
<CHOEMA's is synthetic >
The method identical with the synthetic method of the MAEVE with in described polymer A-1 synthetic carried out the synthetic of CHOEMA.
<MATHF's is synthetic >
First methacrylic acid (86g, 1mol) is cooled to 15 ℃, then adds camphorsulfonic acid (4.6g, 0.02mol).Drip 2-dihydrofuran (71g, 1mol, 1.0 equivalents) in this solution.Stir after 1 hour, add saturated sodium bicarbonate (500mL), and utilize ethyl acetate (500mL) to be extracted, after utilizing magnesium sulphate to carry out drying, insolubles is filtered, then carrying out reduced pressure concentration below 40 ℃, the yellow oil of residue is carried out to decompression distillation, and obtain methacrylic acid tetrahydrochysene as 54 ℃～56 ℃/3.5mmHg of boiling point (bp.) cut of colorless oil-2H-furans-2-base ester (MATHF) 125g (productive rate is 80%).
<Ph-1's is synthetic >
Under agitation, in the acetonitrile 100ml solution of 4-HBA (3-hydroxypropyl) ester 23g, add 1-METHYLPYRROLIDONE 20ml, and then add methacrylic chloride 16g.After one side stirs and is simultaneously reacted in 8 hours under 35 ℃, reaction mixture is poured out to frozen water, separated out crystallization is carried out to leaching, from ethyl acetate/normal hexane, carry out recrystallization, and obtain 4-HBA (3-methacryloxypropyl) ester.
<P-Ph-1's is synthetic >
P-Ph-1 is by utilizing 1-ethoxyethylether protection Ph-1 to obtain.
Synthesizing of<polymer A-9 >
In polymer A-2 synthetic, with respect to the monomer total amount, further add thiomalic acid 1.5mol%, in addition, similarly synthetic with polymer A-2.
Figure BDA00002864124900641
Figure BDA00002864124900651
The preparation of<photosensitive polymer combination >
To become the mode of the solid constituent ratio that following souvenir carries, make polymkeric substance (A composition), acid producing agent (B composition), polymkeric substance (C composition), sensitizer (E composition), crosslinking chemical (F composition), connect airtight modifying agent (G composition), quencher (H composition), interfacial agent (I composition) dissolve and be mixed in solvent, utilize the teflon filter made device that bore is 0.2 μ m to be filtered, and obtain the photosensitive polymer combination of various embodiment and comparative example.
Moreover solvent is used the mixed solvent of propylene glycol monomethyl ether acetate/diethylene glycol ethyl-methyl ether/1,3-BDO diacetate=60/37/3 (mass ratio), and adjusted in the mode that viscosity becomes 5mPas.
The details of the contracted notation of each compound used in expression embodiment, comparative example is as described below.
<B composition >
B-1:PAG-103 (BASF AG manufactures for trade name, the structure shown in following)
B-2:PAI-101 (BASF AG manufactures for trade name, the structure shown in following)
B-3: α-(oxyimino)-2-phenylacetonitrile (synthesis example is described thereafter)
B-4: the structure shown in following (synthesis example is described thereafter)
B-5: the structure shown in following (synthesis example is described thereafter)
B-6: the structure shown in following (synthesis example is described thereafter)
B-7: the structure shown in following (synthesis example is described thereafter)
B-8: the structure shown in following (synthesis example is described thereafter)
B-9:TPS-1000 (greening is learned (Midori Kagaku) company and manufactured for trade name, the structure shown in following)
NQD:4,4 '-[1-[4-[1-[4-hydroxyphenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.0 moles)
Figure BDA00002864124900671
<B-3's is synthetic >
Phenylacetonitrile (5.85g, Tokyo changes into company and manufactures) is blended in tetrahydrofuran (50ml, and the manufacture of the pure medicine of light company), then is placed in ice bath reactant liquor is cooled to below 5 ℃.Then, drip SM-28 (sodium methoxide 28% methanol solution, 11.6g, and the manufacture of the pure medicine of light company), under ice bath, stir and reacted in 30 minutes.Then, one side remains one side below 20 ℃ by interior temperature and drips isoamyl nitrite (7.03g, Tokyo changes into company and manufactures), and dropping at room temperature reacts reactant liquor 1 hour after finishing.Obtained reactant liquor be fed in the water (150mL) that is dissolved with NaOH (1g) and it is dissolved fully, then adding ethyl acetate (100ml) and carry out separatory, obtaining the water layer with object of about 180ml.And then, again add ethyl acetate (100ml), utilizing concentrated hydrochloric acid to make water layer become pH is the acidity below 3, then product is extracted, concentrates.If utilize hexane to be cleaned obtained coarse crystallization, with 63% productive rate, obtain α-(oxyimino)-2-phenylacetonitrile (4.6g).
Make α-(oxyimino)-2-phenylacetonitrile 11.5g be dissolved in tetrahydrofuran: in 100ml (manufacturing with the pure medicine of light company), then to be placed in ice bath reactant liquor is cooled to below 5 ℃.Then, drip methane sulfonyl chloride 9.9g (manufacturing with the pure medicine of light company), one side remains one side below 20 ℃ by interior temperature and drips triethylamine 9.55g (manufacturing with the pure medicine of light company) then, then under ice bath, stirs and is reacted in 1 hour.
Obtained reactant liquor is dropped in water 500mL, and at room temperature stir one hour.If to obtained pulverous precipitate filtered, drying, with 90% productive rate, obtain that α-(sulfonyloxy methyl oxygen base imino group)-2-phenylacetonitrile (compd B-3) is (16g).The H-NMR spectrum of this compound shows the potpourri that product is oxime structural isomerism thing (suitable/anti-(syn/anti)), and it exists than being syn:anti=25/75.
<B-4's is synthetic >
The method of putting down in writing in paragraph [0108] according to the special table of Jap.P. 2002-528451 communique, synthetic α-(tolysulfonyl oxygen base imino group) phenylacetonitrile (compd B-4).
<B-5's is synthetic >
1-1. synthetic mesophase thing B-5A's is synthetic
Under room temperature (25 ℃), 2-aminobenzene mercaptan (31.3g, Tokyo changes into industry (share) manufacture) is dissolved in toluene (100mL, and the pure pharmaceutical worker's industry of light (share) manufacture).Then, in obtained solution, drip phenylacetyl chlorine (40.6g, Tokyo changes into industry (share) manufacture), at room temperature stir 1 hour, then under 100 ℃, stir and reacted in 2 hours.To adding water 500mL in obtained reactant liquor, make separated out salt dissolve, Toluene oil is divided extracted, and utilize rotary evaporator to be concentrated extract, and obtain synthetic mesophase thing B-5A.
1-2.B-5 synthetic
The synthetic mesophase thing B-5A (2.25g) that makes to obtain in this way is placed in ice bath reactant liquor is cooled to below 5 ℃ after being blended in tetrahydrofuran (10mL, and the pure pharmaceutical worker's industry of light (share) is manufactured).Then, in reactant liquor, drip tetramethyl ammonium hydroxide (Alfa Acer company manufactures for 4.37g, 25 quality % methanol solutions), under ice bath, stir and reacted in 0.5 hour.And then one side remains one side below 20 ℃ by interior temperature and drips isoamyl nitrite (7.03g), then dropping stirs one hour till after finishing, reactant liquor being warming up to room temperature.
Then, after being cooled to below 5 ℃ by reactant liquor, drop into paratoluensulfonyl chloride (1.9g) (Tokyo changes into industry (share) manufacture), one side keeps one side below 10 ℃ to stir 1 hour.Drop into water (80mL), and stir 1 hour under 0 ℃ thereafter.After obtained precipitate is filtered, drop into isopropyl alcohol (Isopropyl alcohol, IPA) 60mL, stir 1 hour after being heated to 50 ℃, and filtered while hot, drying, obtain thus the compound (described structure) of B-5 (1.8g).
The B-5's obtained 1H-NMR spectrum (300MHz, deuterated dimethyl sulfoxide (Deuterated Dimethyl Sulfoxide) ((D 3C) 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 described 1The H-NMR measurement result, the rotamerism thing that the B-5 that deduction obtains is independent a kind.
<B-6's is synthetic >
Add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g) in the suspension solution of beta naphthal (10g), chlorobenzene (30mL), mixed liquor is heated to 40 ℃ after the reaction 2 hours.Under ice bath is cooling, to dripping the HCl aqueous solution (60mL) of 4N in reactant liquor, then adds ethyl acetate (50mL) and carry out separatory.Add sal tartari (19.2g) in organic layer, under 40 ℃, reaction is after 1 hour, add the HCl aqueous solution (60mL) of 2N and carry out separatory, after organic layer is concentrated, utilize diisopropyl ether (10mL) to pull an oar again (reslurry) to crystallization, then filtered, dry and obtain ketonic compound (6.5g).
Add acetic acid (7.3g), 50 quality % aqueous hydroxylamine solutions (8.0g) in the suspension solution of obtained ketonic compound (3.0g), methyl alcohol (30mL), and heat backflow.Place cooling after, add water (50mL), separated out crystallization is filtered, after utilizing cold methanol to be cleaned, in addition dry and obtain oxime compound (2.4g).
Obtained oxime compound (1.8g) is dissolved in acetone (20mL), at the cooling lower interpolation triethylamine of ice bath (1.5g), paratoluensulfonyl chloride (2.4g), is warming up to after room temperature reaction 1 hour.Add water (50mL) in reactant liquor, after separated out crystallization is filtered, utilize methyl alcohol (20mL) to pull an oar again, then filtered, the dry and compound (described structure) that obtains B-6 (2.3g).
Moreover, B-6's 1H-NMR spectrum (300MHz, CDCl 3) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), (7.6 dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
<B-7's is synthetic >
Beta naphthal (20g) is dissolved in DMA (150mL), reacts 2 hours under 100 ℃ after interpolation sal tartari (28.7g), 2-bromine ethyl caprilate (52.2g).To adding water (300mL) in reactant liquor, ethyl acetate (200mL) carries out separatory, after organic layer is concentrated, add 48 quality % sodium hydrate aqueous solutions (23g), ethanol (50mL), water (50mL), and carry out reaction in 2 hours.Reactant liquor is poured out to the HCl aqueous solution (500mL) of 1N, separated out crystallization is filtered, washed and, after obtaining the carboxylic acid crude product, adds polyphosphoric acid 30g and react 30 minutes under 170 ℃.Reactant liquor is poured out to water (300mL), add ethyl acetate (300mL) and carry out separatory, after organic layer is concentrated, utilize silica gel column chromatography (silica gel column chromatography) to be made with extra care, and obtain ketonic compound (10g).
Add sodium acetate (30.6g), oxammonium hydrochloride (25.9g), magnesium sulphate (4.5g) in the suspension solution of obtained ketonic compound (10.0g), methyl alcohol (100mL), and carry out adding in 24 hours hot reflux.Place cooling after, add water (150mL), ethyl acetate (150mL) carries out separatory, utilizes water 80mL to carry out separatory 4 times to organic layer, and after being concentrated, utilize silica gel column chromatography to make with extra care and obtain oxime compound (5.8g).
For obtained oxime (3.1g), similarly carry out the sulfonic acid esterification with the compound of B-6, and the compound (described structure) of acquisition B-7 (3.2g).
Moreover, B-7's 1H-NMR spectrum (300MHz, CDCl 3) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), (7.5 dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (dd, 1H), 2.4 (s, 3H), (2.2 ddt, 1H), 1.9 (ddt, 1H), 1.4～1.2 (m, 8H), 0.8 (t, 3H).
<B-8's is synthetic >
Replace the paratoluensulfonyl chloride in B-6 with benzene sulfonyl chloride, in addition, with the compound (described structure) of the synthetic B-8 of the mode identical with B-6.
Moreover, B-8's 1H-NMR spectrum (300MHz, CDCl 3) be δ=8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q, 1H), 1.7 (d, 3H).
<E composition >
E-1:DBA (Kawasaki changes into industry manufacture for trade name, 9,10-dibutoxy anthracene)
E-2:NBCA (following structure, dark fund changes into (share) and manufactures)
Figure BDA00002864124900711
<F composition >
F-1:JER157S65 (Mitsubishi Chemical parent corporation manufactures for trade name, phenol novolak type epoxy resin)
F-2:Nikalac MW-100LM (three and chemistry (Sanwa Chemical) company manufacture)
F-3:EX-111 (length rapids changing into (Nagase chemteX) company manufactures)
F-4:EX-212L (the long rapids company that changes into manufactures)
F-5:Kayarad DPHA (Japanese chemical drug company manufacture)
F-6:Celloxide2021P (manufacture of Daicel company)
F-7:Duranate 17B-60P (chemistry (Asahi Kasei Chemicals) company of Asahi Chemical Industry manufactures)
F-8:Denacol EX-321L (the long rapids company that changes into manufactures)
<G composition >
G-1:KBM-403 (trade name, the 3-glycidoxypropyltrimewasxysilane, the structure shown in following, SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured)
G-2:KBE-403 (SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured for trade name, 3-glycidoxypropyl triethoxysilane)
G-3:KBE-1003 (SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured for trade name, vinyltriethoxysilane)
G-4:KBM-502 (SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured for trade name, 3-methacryloxypropyl dimethoxy silane)
G-5:KBM-5103 (SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured for trade name, 3-acryloxy propyl trimethoxy silicane)
G-6:KBM-803 (SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured for trade name, 3-sulfydryl propyl trimethoxy silicane)
G-7:KBM-903 (SHIN-ETSU HANTOTAI's chemical industry (share) is manufactured for trade name, 3-TSL 8330)
Figure BDA00002864124900721
<H composition >
H-1:1,5-diazabicyclo [4.3.0]-5-nonene
H-2: triphenyl imidazoles
H-3: following structure
Figure BDA00002864124900722
<I composition >
I-1: the represented non-ionic surfactant that contains perfluoroalkyl by following structural formula
I-2: silicone-based interfacial agent SH-8400 (eastern beautiful DOW CORNING silicone)
Figure BDA00002864124900731
<other adjuvants >
AO-60: hindered phenol Adekastab AO-60 (Ai Dike manufacture)
SE-1: salicylic acid
SE-2: following compound
Figure BDA00002864124900732
SE-3: citric acid
SA-1: following compound
Figure BDA00002864124900741
The evaluation of<light sensitivity >
By each photosensitive polymer combination slot coated at glass substrate (Corning1737, thick 0.7mm (Corning Incorporated's manufacture)) upper after, carry out prebake conditions with 95 ℃/140 seconds and make solvent evaporates on heating plate, thereby form the photosensitive polymer combination layer that thickness is 4.0 μ m.
Then, the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that utilizes Canon (Canon) (share) to manufacture, exposed to obtained photosensitive polymer combination layer via the shade of stipulating.Then, utilize alkaline-based developer (the tetramethyl ammonium hydroxide aqueous solution of 0.4 quality %), after with 23 ℃/60 seconds, the photosensitive composite layer after exposure being developed, utilize ultrapure water drip washing 20 seconds.
To line and space (Line and Space) the Optimum i x ray exposure x amount (Eopt) while being resolved with 1: 1 couple of 9 μ m be made as light sensitivity by these operations.Moreover metewand is as described below.The level that A, B, C are practical upper no problem.
A: less than 40mJ/cm 2
B:40mJ/cm 2Above, less than 60mJ/cm 2
C:60mJ/cm 2Above, less than 80mJ/cm 2
D:80mJ/cm 2Above, less than 150mJ/cm 2
E:150mJ/cm 2Above
Below only embodiment 8 is carried out to the light sensitivity evaluation.Its reason is: t-BuMA is the low compound of script light sensitivity.
By the photosensitive polymer combination slot coated, at glass substrate, (Corning 1737, thick 0.7mm (Corning Incorporated's manufacture)) upper after, carry out prebake conditions with 95 ℃/140 seconds and make solvent evaporates on heating plate, thereby form the photosensitive polymer combination layer that thickness is 4.0 μ m.
Then, the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that utilizes Canon's (share) to manufacture, exposed to obtained photosensitive polymer combination layer via the shade of stipulating.Then, after utilizing 60 ℃ of heating plates to carry out heating in 1 minute to the substrate after exposing, utilize alkaline-based developer (the tetramethyl ammonium hydroxide aqueous solution of 2.38 quality %) to be developed with 23 ℃/60 seconds, then utilize ultrapure water drip washing 20 seconds.
Optimum i x ray exposure x amount (Eopt) while will be by these operations being resolved with the line of 1: 1 couple of 9 μ m and space is made as light sensitivity.Moreover metewand is identical.
The mensuration of<specific insulation >
[making sample]
After being coated on aluminium base by material, carry out 2 minutes dryings under 90 ℃, then utilize extra-high-pressure mercury vapour lamp to carry out the 300mJ exposure, and then, under 230 ℃, utilize baking oven to carry out heating in 30 minutes, and form the cured film that thickness is 3 μ m.To carry out the aluminium-vapour deposition person of forming as the specific insulation test sample on this cured film.
[mensuration]
After under 23 ℃, relative humidity 60%, the condition of 24 hours, described specific insulation test sample being carried out to damping, utilize ultra-high resistance meter (ULTRA HIGH RESISTANCE METER) (Advantest (ADVANTEST) manufacture) to carry out specific insulation mensuration.
Assay method is according to JIS K6911, applying voltage 10V, the condition of 1 minute is measured volume resistance measured value (Ω).
Area and sample thickness according to this measured value with the aluminium electrode, calculate specific insulation (Ω cm) (more high better).The level that A, B, C are practical upper no problem.
A:5.0 * 10 16More than Ω cm
B:3.0 * 10 16More than Ω cm, less than 5.0 * 10 16Ω cm
C:1.0 * 10 16More than Ω cm, less than 3.0 * 10 16Ω cm
D:5.0 * 10 15More than Ω cm, less than 1.0 * 10 16Ω cm
E: less than 5.0 * 10 15Ω cm
The evaluation of<solvent resistance >
By each photosensitive polymer combination slot coated, at glass substrate, (Corning 1737, thick 0.7mm (Corning Incorporated's manufacture)) upper after, carry out prebake conditions with 95 ℃/140 seconds and make solvent evaporates on heating plate, thereby form the photosensitive polymer combination layer that thickness is 3.0 μ m.Utilize extra-high-pressure mercury vapour lamp to carry out the 300mJ exposure, and then, under 230 ℃, utilize baking oven to carry out heating in 60 minutes, and form cured film.
Thickness (T to obtained cured film 1) measured.And, make the substrate that is formed with this cured film temperature is being controlled to the dimethyl sulfoxide (DMSO) of 60 ℃: monoethanolamine=in solution flood 10 minute after, to the thickness (t of cured film dipping after at 5: 5 1) measured, and calculate by the dipping produce the Thickness Variation rate | t 1-T 1|/T 1} * 100[%].Show the result in following table.The level that A, B, C are practical upper no problem.
A: less than 2%
More than B:2%, less than 3%
More than C:3%, less than 4%
More than D:4%, less than 6%
More than E:6%
<embodiment 22 >
Embodiment 22 is in embodiment 21, and substrate is changed to 6 inches silicon wafers from glass substrate (Corning 1737,0.7mm thick (Corning Incorporated's manufacture)), in addition, similarly carries out.
<embodiment 26 >
Embodiment 26 is in embodiment 23, solvent is replaced to propylene glycol monomethyl ether acetate/diethylene glycol ethyl-methyl ether/1, the mixed solvent of 3-butylene glycol diacetate=60/37/3 (mass ratio), and adjusted in the mode that the viscosity of composition becomes 35mPas, and all coatings are made as to spin coating, in addition, similarly carry out.
Figure BDA00002864124900771
Figure BDA00002864124900781
Figure BDA00002864124900791
Figure BDA00002864124900801
As described in table and, as clear and definite, known photosensitive polymer combination of the present invention has high light sensitivity, specific insulation and solvent resistance.Especially, the contain-NH-CH in known total polymer composition 2The many persons of ratio of the Component units of-O-R and the Component units that contains crosslinking group obtain more excellent effect.
<embodiment 30 >
Embodiment 30 is in embodiment 23, and the PLA-501F exposure machine that exposure machine is manufactured from Canon's (share) is altered to the FX-803M (gh-Line stepper) that Nikon (Nikon) (share) is manufactured, and in addition, similarly carries out.Being evaluated as of light sensitivity " A ".
<embodiment 31 >
Embodiment 31 is in embodiment 23, and the PLA-501F exposure machine that exposure machine is manufactured from Canon's (share) is altered to 355nm laser explosure machine and carries out the 355nm laser explosure, in addition, similarly carries out.Herein, as 355nm laser explosure machine, " AEGIS " (wavelength is 355nm, and pulse width is 6nsec) of using V science and technology (V-Technology) incorporated company to manufacture, exposure is that " PE10B-V2 " that use OPHIR company to manufacture measures.
Being evaluated as of light sensitivity " A ".
<embodiment 32 >
Embodiment 32 is in embodiment 23, and the PLA-501F exposure machine that exposure machine is manufactured from Canon's (share) is altered to ultraviolet ray (Ultraviolet, UV)-LED light source exposure machine, in addition, similarly carries out.Being evaluated as of light sensitivity " A ".
As mentioned above, no matter known substrate, exposure machine are how, the photosensitive polymer combination of embodiment all shows excellent light sensitivity, and the shape of formed pattern is also excellent.
<embodiment 33 >
Make the organic EL display (with reference to Fig. 1) that uses thin film transistor (TFT) (TFT) by following method.
Form the TFT1 of bottom gate type on glass substrate 6, and form and comprise Si under the state that covers this TFT1 3N 4Dielectric film 3.Then, after illustrated contact hole has been omitted in formation herein on this dielectric film 3, form the distribution 2 (being highly 1.0 μ m) that is connected in TFT1 via this contact hole on dielectric film 3.This distribution 2 is in order to by between TFT1 or the line that the organic EL formed in step thereafter is connected with TFT1.
And then, in order to make the concavo-convex planarization produced by forming of distribution 2, imbedding under the concavo-convex state produced by distribution 2, form planarization film 4 on dielectric film 3.Forming planarization film 4 on dielectric film 3 is that the photosensitive polymer combination of embodiment 16 is spin-coated on substrate, carry out prebake conditions (90 ℃ * 2 minutes) on heating plate after, uses high-pressure mercury-vapor lamp to irradiate 45mJ/cm from shade 2(illumination is 20mW/cm 2) i ray (365nm), then utilize alkaline aqueous solution developed and form pattern, and carry out the heat treated of 60 minutes under 230 ℃.
Coating during the photosensitive resin coating composition is good, in the cured film obtained after exposure, development, calcining, does not see the generation of fold or slight crack.And then the average jump of distribution 2 is 500nm, the thickness of the planarization film 4 of made is 2,000nm.
Then, form the organic EL of bottom-emission type on obtained planarization film 4.At first, the first electrode 5 that makes to comprise ITO is connected in distribution 2 via contact hole 7 and is formed on planarization film 4.Thereafter, painting erosion resistant agent, and carry out prebake conditions, exposed via the shade of desired pattern, then developed.Using this resist pattern as shade, by the wet etching with the ITO etchant, carry out pattern processing.50 ℃ under, use anticorrosive additive stripping liquid controlling (Remover 100, peace intelligence electronic material (AZ Electronic Materials) company manufacture) described resist pattern peeled off thereafter.The first electrode 5 obtained in this way is equivalent to the anode of organic EL.
Then, form the dielectric film 8 of the shape of the periphery that covers the first electrode 5.The photosensitive polymer combination of embodiment 22 is used for to dielectric film 8, with described identical method, to form dielectric film 8.By this dielectric film 8 is set, can prevent the short circuit between formed the second electrode in the first electrode 5 and step thereafter.
And then, in vacuum deposition apparatus, carry out successively evaporation via desired pattern shade hole transmission layer, organic luminous layer, electron transfer layer are set.Then, form the second electrode that comprises Al on whole above substrate.Take out obtained described substrate from evaporator, by being fitted to seal with glass for sealing plate and UV cured type epoxy resin.
As above, obtain the organic EL display that connects the active array type formed in order to the TFT1 that it is driven on each organic EL.Execute alive result via driving circuit, known its is to manifest good display characteristic and the high organic EL display of reliability.
<embodiment 34 >
In the active array type LCD of putting down in writing, form as follows cured film 17 as interlayer dielectric in Fig. 1 of No. 3321003 communique of Jap.P., and obtain the liquid crystal indicator of embodiment 34.
That is, use the photosensitive polymer combination of embodiment 25, the identical method of formation method with the planarization film 4 of the organic EL display with in described embodiment 33, form cured film 17 as interlayer dielectric.
Obtained liquid crystal indicator is applied to the result of driving voltage, known its is to manifest good display characteristic and the high liquid crystal indicator of reliability.

Claims (19)

1. a positive type photosensitive organic compound comprises: (A) meet at least one component of polymer of following (1) and following (2),
(1) (A1) have contain acidic group by the Component units (a1) of the base of sour decomposability base protection, contain by-NH-CH 2The Component units of the part-structure that-O-R is represented (a2), wherein R is the carbon number alkyl that is 1～20, and the multipolymer of described (a2) Component units that contains crosslinking group (a3) in addition,
(2) (A2) have and contain acidic group by the Component units (a1) of the base of sour decomposability base protection and contain by-NH-CH 2The multipolymer of the Component units (a2) of the part-structure that-O-R (R is the alkyl that carbon number is 1～20) is represented, and the polymkeric substance that (C) there is described (a2) Component units that contains crosslinking group (c2) in addition;
(B) light acid producing agent; And
(D) solvent.
2. positive type photosensitive organic compound according to claim 1, wherein: described Component units (a2) is by the represented Component units of following general formula (1),
General formula (1)
Figure FDA00002864124800011
In described formula, R 1Mean hydrogen atom or methyl, R 2Mean the alkyl that carbon number is 1～20.
3. positive type photosensitive organic compound according to claim 1 and 2, wherein: described Component units (a1) is by the represented Component units of formula (A2 '),
Formula (A2 ')
Figure FDA00002864124800021
In formula, R 1And R 2Mean respectively hydrogen atom, alkyl or aryl, at least R 1And R 2Any be alkyl or aryl, R 3Mean alkyl or aryl, R 1Or R 2With R 3Can link and form cyclic ether, R 4Mean hydrogen atom or methyl, X means singly-bound or arlydene.
4. positive type photosensitive organic compound according to claim 1 and 2, wherein: in described (A) component of polymer, any contained polymkeric substance comprises that the Component units that contains carboxylic acid is as other constituents (a4).
5. positive type photosensitive organic compound according to claim 1 and 2, wherein: described Component units (a2) or Component units (c2) Component units for containing epoxy radicals and/or oxa-cyclobutyl.
6. positive type photosensitive organic compound according to claim 1 and 2, wherein: comprise that oxime sulfonates compound or salt compound are as (B) light acid producing agent.
7. positive type photosensitive organic compound according to claim 1 and 2, wherein: in positive light sensitivity composition, that contained total polymer composition is described Component units (a2) more than 10 % by mole, the total polymer composition more than 20 % by mole, be described Component units (a3) and/or described Component units (c2).
8. positive type photosensitive organic compound according to claim 1 and 2, wherein: in positive type photosensitive organic compound 30 quality % of contained polymkeric substance above be described (1) multipolymer.
9. positive type photosensitive organic compound according to claim 1 and 2, wherein: in described (A) component of polymer, any contained polymkeric substance comprises that the Component units that contains carboxylic acid is as other constituents (a4), described Component units (a2) or Component units (c2) Component units for containing epoxy radicals and/or oxa-cyclobutyl.
10. positive type photosensitive organic compound according to claim 1 and 2, wherein: in described (A) component of polymer, any contained polymkeric substance comprises that the Component units that contains carboxylic acid is as other constituents (a4), in positive type photosensitive organic compound, more than 30 quality % of contained polymkeric substance, is described (1) multipolymer.
11. positive type photosensitive organic compound according to claim 1 and 2, wherein: described Component units (a2) or Component units (c2) Component units for containing epoxy radicals and/or oxa-cyclobutyl, in positive light sensitivity composition, that contained total polymer composition is described Component units (a2) more than 10 % by mole, the total polymer composition more than 20 % by mole, be described Component units (a3) and/or described Component units (c2).
12. positive type photosensitive organic compound according to claim 1 and 2, wherein: in described (A) component of polymer, any contained polymkeric substance comprises that the Component units that contains carboxylic acid is as other constituents (a4), described Component units (a2) or Component units (c2) Component units for containing epoxy radicals and/or oxa-cyclobutyl, in positive light sensitivity composition, that contained total polymer composition is described Component units (a2) more than 10 % by mole, the total polymer composition more than 20 % by mole, be described Component units (a3) and/or described Component units (c2).
13. positive type photosensitive organic compound according to claim 1 and 2, wherein: in described (A) component of polymer, any contained polymkeric substance comprises that the Component units that contains carboxylic acid is as other constituents (a4), described Component units (a2) or Component units (c2) Component units for containing epoxy radicals and/or oxa-cyclobutyl, in positive light sensitivity composition, that contained total polymer composition is described Component units (a2) more than 10 % by mole, the total polymer composition more than 20 % by mole, be described Component units (a3) and/or described Component units (c2), in positive type photosensitive organic compound, more than 30 quality % of contained polymkeric substance, be described (1) multipolymer.
14. the manufacture method of a cured film is characterized in that comprising:
(1) positive type photosensitive organic compound according to claim 1 and 2 is applied to the step on substrate;
(2) remove the step of solvent from applied photosensitive polymer combination;
(3) step of utilizing active radioactive ray to be exposed;
(4) step of utilizing aqueous developer solution to be developed; And
(5) carry out the rear baking procedure of thermmohardening.
15. the manufacture method of cured film according to claim 14, wherein: after described development step, before rear baking procedure, comprise the step of carrying out blanket exposure.
16. a cured film, it is positive type photosensitive organic compound according to claim 1 and 2 is hardened and form.
17. cured film according to claim 16, wherein: it is interlayer dielectric.
18. a liquid crystal indicator, comprise cured film according to claim 16.
19. an organic electroluminescence display device and method of manufacturing same, comprise cured film according to claim 16.
CN2013100614028A 2012-02-28 2013-02-27 Photo-curable resin composition, method for manufacturing cured film, cured film, organic el device and liquid crystal display Pending CN103293858A (en)

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CN107207868A (en) * 2015-02-19 2017-09-26 日本瑞翁株式会社 Resin combination, resin film and electronic unit

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014054455A1 (en) * 2012-10-02 2014-04-10 日産化学工業株式会社 Negative photosensitive resin composition
JP6136727B2 (en) * 2013-08-02 2017-05-31 Jsr株式会社 Radiation sensitive resin composition, cured film, method for forming the same, and display element
WO2015072415A1 (en) * 2013-11-13 2015-05-21 積水化学工業株式会社 Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6279444A (en) * 1985-10-03 1987-04-11 Kuraray Co Ltd Crosslinkable resist
CN1737683A (en) * 2004-08-16 2006-02-22 富士胶片株式会社 Planographic printing plate precursor
TW201015222A (en) * 2008-09-12 2010-04-16 Sumitomo Chemical Co A method for treating a resist layer and a use of positive resist composition
CN101876789A (en) * 2009-05-01 2010-11-03 富士胶片株式会社 Positive type photosensitive organic compound and the cured film formation method of having used said composition
TW201140232A (en) * 2010-01-15 2011-11-16 Fujifilm Corp Photosensitive resin composition, cured film and method of producing the same, organic EL display device, and liquid crystal display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6279444A (en) * 1985-10-03 1987-04-11 Kuraray Co Ltd Crosslinkable resist
CN1737683A (en) * 2004-08-16 2006-02-22 富士胶片株式会社 Planographic printing plate precursor
TW201015222A (en) * 2008-09-12 2010-04-16 Sumitomo Chemical Co A method for treating a resist layer and a use of positive resist composition
CN101876789A (en) * 2009-05-01 2010-11-03 富士胶片株式会社 Positive type photosensitive organic compound and the cured film formation method of having used said composition
TW201140232A (en) * 2010-01-15 2011-11-16 Fujifilm Corp Photosensitive resin composition, cured film and method of producing the same, organic EL display device, and liquid crystal display device

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104658906A (en) * 2013-11-22 2015-05-27 上海和辉光电有限公司 Manufacturing method of semiconductor planarization layer
CN104658906B (en) * 2013-11-22 2017-09-01 上海和辉光电有限公司 A kind of preparation method of semiconductor planarization layer
CN106687865A (en) * 2014-09-30 2017-05-17 富士胶片株式会社 Method for manufacturing TFT substrate, organic EL display device, method for manufacturing organic EL display device, liquid crystal display device, and method for manufacturing liquid crystal display device
CN106687865B (en) * 2014-09-30 2020-01-03 富士胶片株式会社 TFT substrate, organic EL display device, and method for manufacturing liquid crystal display device
CN105895661A (en) * 2015-02-17 2016-08-24 富士胶片株式会社 Method For Manufacturing Thin Film Transistor Substrate And Application Thereof
CN105895661B (en) * 2015-02-17 2019-03-01 富士胶片株式会社 The manufacturing method and its application of thin film transistor base plate
TWI710839B (en) * 2015-02-17 2020-11-21 日商富士軟片股份有限公司 Method for manufacturing thin film transistor substrate, organic electroluminescence display device and manufacturing method thereof, liquid crystal display device and manufacturing method thereof
CN107207868A (en) * 2015-02-19 2017-09-26 日本瑞翁株式会社 Resin combination, resin film and electronic unit
CN107207868B (en) * 2015-02-19 2020-11-06 日本瑞翁株式会社 Resin composition, resin film, and electronic component
CN105938299A (en) * 2015-03-06 2016-09-14 东友精细化工有限公司 Chemically amplified photosensitive resin composition and insulation layer prepared from the same
CN105938299B (en) * 2015-03-06 2020-10-09 东友精细化工有限公司 Chemically amplified photosensitive resin composition and insulating film produced therefrom

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