CN101467100B - Positive photosensitive resin composition containing polymer having ring structure - Google Patents
Positive photosensitive resin composition containing polymer having ring structure Download PDFInfo
- Publication number
- CN101467100B CN101467100B CN200780021536XA CN200780021536A CN101467100B CN 101467100 B CN101467100 B CN 101467100B CN 200780021536X A CN200780021536X A CN 200780021536XA CN 200780021536 A CN200780021536 A CN 200780021536A CN 101467100 B CN101467100 B CN 101467100B
- Authority
- CN
- China
- Prior art keywords
- composition
- compound
- mass parts
- positive type
- organic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Abstract
To provide a positive photosensitive resin composition which has high sensitivity and is reduced in film thickness reduction in unexposed areas and which, after film formation, retains a high transmission and a film thickness even through high-temperature burning or treatment with a liquid resist stripper and does not crack during ITO sputtering; and a cured film suitable for use as a film material for various displays. [MEANS FOR SOLVING PROBLEMS] The positive photosensitive resin composition comprises: ingredient (A) which is an alkali-soluble acrylic polymer having at least one of carboxy and phenolic hydroxy and at least one of hydroxy other than phenolic hydroxy and amino having active hydrogen and having a number-average molecular weight of 2,000-30,000; ingredient (B) which is an alkali-soluble resin having a ring structure in the backbone; ingredient (C) which is a compound having a vinyl ether group; ingredient (D) which is a compound having a blocked isocyanate group; ingredient (E) which is a photo-acid generator; and a solvent (F).
Description
Technical field
The present invention relates to positive type photosensitive organic compound and reach cured film by its acquisition.In further detail, the present invention relates to be fit to the positive type photosensitive organic compound and the cured film thereof of display material purposes and the various materials that used this cured film.
Background technology
Usually, in the display device of thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL (electroluminescence) element etc., be provided with the electrode protective membrane that formed pattern, planarization film, dielectric film etc.As the material that forms these films; In photosensitive polymer combination; Use following photosensitive polymer combination all the time widely, promptly have and make the photosensitive polymer combination of the few and characteristic that flatness is fully such of process number for the pattern form that obtains needing.
Therefore, these above-mentioned films require to have each following characteristic; Promptly; Thermotolerance, solvent resistance, to toast the processing patience of patience, metal sputtering patience etc. for a long time excellent, good with the cohesiveness of substrate, has the wide fininsh allowance that can form pattern under the various processing conditionss of application target meeting; High sensitivity and high transparent, and inhomogeneous few etc. the characteristic of the film after developing.Therefore, from such angle that requires characteristic, up to now,, generally use the resin that contains naphthoquinone diazo compound (naphthaquinone diazide compound) as above-mentioned photosensitive polymer combination.
Therefore, requiring in the characteristic of such photoresist material,, can enumerate out sensitivity as an important characteristic.Commercial production for display device etc.; The raising of sensitivity can be shortened its production time significantly; Therefore, under the remarkable present situation that increases of requirement of LCD, sensitivity becomes one of desired most important characteristic of this photoresist material.
But the above-mentioned existing photoresist material that contains naphthoquinone diazo compound is not very satisfactory aspect sensitivity.Through improving the dissolubility of polymkeric substance in alkaline-based developer in the material, also can improve sensitivity, but this method there is certain limit; In addition, also has the shortcoming of following that kind, promptly; Unexposed dissolving has also taken place; Thereby the reduction of film residual rate, for the substrate that giant display is used, this becomes the uneven reason of generation film.
Therefore, up to now, the patented claim that several high sensitivity with the photoresist material turn to purpose has been proposed.For example, proposed to contain any at least one radiation sensitive resin composition (for example, the referenced patent document 1) of alkali soluble resins and specific polyol and derivant thereof.But, because the symmetry of the emulsion of this motion material is high, so have problems at aspects such as storage stabilities.
In addition; Proposed to contain the positive radiation line sensitive resin composition (for example, referenced patent document 2) of alkali solubility phenol resin and radiation-sensitive compound, and; The positive type photosensitive organic compound (for example, the referenced patent document 3) that contains specific alkali soluble resins and quinone diazo-compounds.Therefore but these compositions are in binder polymer, to have used novolac resin, existing problems aspect stable in the transparency and when toasting for a long time.
Such as previously discussed, the exploitation of satisfying other characteristic and having a highly sensitive photosensitive polymer combination of level of hope is unusual difficulty, through the simple combination of prior art, is difficult to obtain gratifying photosensitive polymer combination.
In addition, usually, contain the existing photoresist material of naphthoquinone diazo compound; For paintedization of the cured film that prevents to cause by naphthoquinone diazo compound behind the exposure imaging and the reduction of the transparency, and carry out photobleaching, still; Even through this photobleaching operation, light transmission reduction, painted also appears, in addition when toasting under the high temperature of the film that obtains about 250 ℃; Even under than the low temperature of this temperature, for example under 230 ℃, toast for a long time, light transmission also can occur and reduce (painted); And then, be the chemical treatments of solution etc. even utilize amine as anticorrosive additive stripping liquid controlling, take place also that light transmission reduces, the such problem of transparency deterioration; Therefore the existing photoresist material that contains naphthoquinone diazo compound; Aspect such thermotolerance and chemical resistance, existing problems (for example, the referenced patent document 4).
On the other hand, as high sensitivity, high-resolution photosensitive material, developed chemically amplified corrosion-resisitng agent at present.As the existing chemically amplified corrosion-resisitng agent of semiconductor with resist exploitation, can adapt to than i line short wavelength's light source (KrF, ArF) more, can form finer pattern; But under the high temperature of that kind that is used for film curing; In the presence of anticorrosive additive stripping liquid controlling, decompose easily at the heat cross-linking position of the binding site of blocking group, ehter bond in addition, and thermotolerance and chemical resistance significantly reduce; Thereby basically can not be as permanent film (for example, the referenced patent document 5).In addition; Even in chemically amplified corrosion-resisitng agent, introduce the cross-linking system of epoxies, amino plastics class in order to carry out heat curing; So also, make that exposure portion is crosslinked, thereby the new problem with unexposed dissolving difference disappearance etc. occurs owing to receive the influence that causes the acid that the light acid propellant (PAG) in the resist generated by exposure; Therefore, the such introducing of cross-linking system in chemically amplified corrosion-resisitng agent is difficult.
In addition, these materials after the pattern heat curing that makes formation, through sputtering ITO on film, Al, the such metal of Cr, and are processed film.Can know, in general, under the situation of using acryl resin, at high temperature carry out in film, occurring crackle easily among the ITO of sputter.Therefore, require at high temperature have sputter patience, and have the material of high sensitivity, the high heat-resisting transparency.
[patent documentation 1] spy opens flat 4-211255 communique
[patent documentation 2] spy opens flat 9-006000 communique
[patent documentation 3] spy opens flat 8-044053 communique
[patent documentation 4] spy opens flat 4-352101 communique
No. 5075199 instructions of [patent documentation 5] United States Patent (USP)
Summary of the invention
The present invention is the invention of making in view of the above fact; First problem provides a kind of positive type photosensitive organic compound; Said composition has fully high sensitivity, and can be formed on when developing unexposed thickness the degree that reduces to be observed,, in fact thickness does not have the pattern tunicle of minimizing.
And, even second problem provides baking at high temperature, handles with anticorrosive additive stripping liquid controlling, also can keep high-transmission rate, and the cured film that when sputtering ITO, does not crack, the positive type photosensitive organic compound that can obtain such cured film also is provided.
That is, as the 1st scheme, be a kind of positive type photosensitive organic compound, contain following (A) composition, (B) composition, (C) composition, (D) composition and (E) solvent,
(A) composition: the alkali solubility acrylate copolymer, it has and is selected from least a in carboxyl and the phenolic hydroxyl and is selected from the hydroxyl beyond the phenolic hydroxyl and has at least a in the amino of reactive hydrogen, and its number-average molecular weight is 2000～30000;
(B) composition: the alkali soluble resins that in main chain, has aromatic ring or alicyclic structure;
(C) composition: the compound that has plural vinyl ether group in 1 molecule;
(D) composition: the compound that has plural blocked isocyanate base in 1 molecule;
(E) light acid propellant;
(F) solvent.
As the 2nd scheme, be according to the described positive type photosensitive organic compound of the 1st scheme, (B) composition is the alkali soluble resins that is selected from polyimide and the polyimide precursor.
As the 3rd scheme, be that (B) number-average molecular weight of composition alkali soluble resins is 2000～30000 according to the 1st scheme or the described positive type photosensitive organic compound of the 2nd scheme.
As the 4th scheme, be each described positive type photosensitive organic compound according to the 1st scheme～the 3rd scheme, (B) composition is the alkali soluble resins that has by the substituted alkyl of fluorine atom.
As the 5th scheme, be each described positive type photosensitive organic compound according to the 1st scheme～the 4th scheme, (B) composition is the alkali soluble resins that comprises polyimide, this polyimide contains 0.5～20 mass parts with respect to (A) composition 100 mass parts.
As the 6th scheme; It is each described positive type photosensitive organic compound according to the 1st scheme～the 4th scheme; (B) composition is the alkali soluble resins that comprises polyimide precursor, and this polyimide precursor contains 5～100 mass parts with respect to (A) composition 100 mass parts.
As the 7th scheme, be each described positive type photosensitive organic compound according to the 1st scheme～the 6th scheme, (E) composition is the compound that produces sulfonic acid through rayed.
As the 8th scheme, be each described positive type photosensitive organic compound according to the 1st scheme～the 7th scheme, further contain amines as (G) composition.
As the 9th scheme, be each described positive type photosensitive organic compound according to the 1st scheme～the 8th scheme, further contain fluorine class surfactant as (H) composition.
As the 10th scheme, be a kind of cured film, be to use the described positive type photosensitive organic compound of each of the 1st scheme～the 9th scheme to obtain.
As the 11st scheme, be a kind of interlayer dielectric, contain the described cured film of the 10th scheme.
As the 12nd scheme, be a kind of lenticule, contain the described cured film of the 10th scheme.
Positive type photosensitive organic compound of the present invention has fully high sensitivity, and, can be formed on when developing degree that the minimizing of unexposed thickness can not be observed,, in fact unexposed thickness does not have the pattern tunicle of minimizing.In addition, toast, handle, also can keep high-transmission rate with anticorrosive additive stripping liquid controlling even can provide at high temperature, and the cured film that when sputtering ITO, does not crack.
Embodiment
Photosensitive polymer combination of the present invention contains following (A) composition, (B) composition, (C) composition, (D) composition and (E) composition and (F) solvent, and; As required, can contain (G) composition and/or (H) composition, wherein; (A) composition is the alkali solubility acrylate copolymer, and (B) composition is an alkali soluble resins, and (C) composition is the compound with vinyl ether group; (D) composition is the compound with blocked isocyanate base; (E) composition is a light acid propellant, and (G) composition is an amines, and (H) composition is a surfactant.
Below, each composition is elaborated.
(A) composition
(A) composition is the alkali solubility acrylate copolymer; In the structure of polymkeric substance; Have and be selected from least a in carboxyl and the phenolic hydroxyl and be selected from the hydroxyl beyond the phenolic hydroxyl and have at least a in the amino of reactive hydrogen; And its number-average molecular weight with polystyrene calibration (below be called number-average molecular weight) is 2000～30000.
Above-mentionedly be selected from least a in carboxyl and the phenolic hydroxyl; Being can be under the condition of the temperature that improves, with after vinyl ether radical reaction in the compound of (C) composition of stating, thereby thereby and (C) form the group that heat cross-linking forms etchant resist between the component cpd.
In addition; At least a in above-mentioned hydroxyl and the amino that is selected from beyond the phenolic hydroxyl with reactive hydrogen; Be that heat cross-linking body at above-mentioned (A) composition and (C) composition is (in exposure portion; Be the heat cross-linking body further dissociate take off crosslinked body) in, under the condition of the temperature that further improves, the NCO that partly dissociated by end-blocking of being situated between, with after cross-linking reaction takes place between the compound of (D) composition of stating, thereby make film that the group of curing take place.
Here, the amino with active hydrogen means, reactive high, the primary amino radical or the secondary amino group that can discharge proton.Therefore, because amide group does not have active hydrogen, so do not belong to amino with active hydrogen.
(A) the composition polymkeric substance for the skeleton of the high polymer main chain that constitutes polymkeric substance and the kind of side chain etc., does not have special qualification so long as have the alkali solubility acrylate copolymer of such structure and get final product.
Yet, (A) number-average molecular weight of composition polymkeric substance in 2000～30000 scope, more preferably 2000～15000 scope.If number-average molecular weight is excessive, surpassed 30000, then be easy to generate the development residue, sensitivity reduces greatly; On the other hand, if number-average molecular weight is too small, less than 2000; Then when developing, unexposed the quite a large amount of thickness of generation reduces, and the situation that becomes not enough of solidifying is arranged.
Alkali solubility acrylate copolymer as (A) composition; For example can enumerate out, the such monomer with unsaturated double-bond of acrylic ester, methacrylate, styrene carries out homopolymerization or copolymerization and further can be dissolved in the polymkeric substance of aqueous alkali in the polymkeric substance that obtains.
In addition, in the present invention, as (A) composition, also can use the alkali solubility acrylate copolymer that is made up of following multipolymer, said multipolymer is that multiple monomer is carried out polymerization and the multipolymer that obtains (below, be called specific copolymer).In this case, (A) composition alkali solubility acrylate copolymer also can be the blend of multiple specific copolymer.
Promptly; Above-mentioned specific copolymer is the multipolymer that forms as essential formation unit with following monomer; Said monomer is the monomer with the functional group that is used to carry out the heat cross-linking reaction; At least a monomer of promptly suitably selecting in the group of the monomer of at least a functional group from have carboxyl and phenolic hydroxyl; And have the monomer that is used to carry out the functional group that film solidifies, i.e. the suitable at least a monomer of selection in the group of the monomer of at least a functional group from have hydroxyl and the amino that contains active hydrogen except that phenolic hydroxyl, the number-average molecular weight of this specific copolymer is 2000～30000.
In above-mentioned " monomer " with at least a functional group in carboxyl and the phenolic hydroxyl, comprise the monomer with carboxyl, monomer with phenolic hydroxyl, and the monomer with carboxyl and these two kinds of groups of phenolic hydroxyl.These monomers are not limited to have 1 carboxyl or phenolic hydroxyl, also can have a plurality of carboxyls or phenolic hydroxyl.
In addition; In above-mentioned " monomer ", comprise monomer, have the monomer of the amino that contains active hydrogen and have the hydroxyl except that phenolic hydroxyl and contain the monomer of these two kinds of groups of amino of active hydrogen with the hydroxyl except that phenolic hydroxyl with at least a functional group in hydroxyl and the amino that contains active hydrogen except that phenolic hydroxyl.These monomers be not limited to have 1 except that phenolic hydroxyl hydroxyl or contain the amino of active hydrogen, also can have a plurality of except that phenolic hydroxyl hydroxyl or contain the amino of active hydrogen.
Below, enumerate out the object lesson of above-mentioned monomer, but be not limited only to this.
As monomer with carboxyl; For example can enumerate out acrylic acid, methacrylic acid, crotonic acid, list (2-(acryloxy) ethyl) phthalic ester, list (2-(methacryloxy) ethyl) phthalic ester, N-(carboxyl phenyl) maleimide, N-(carboxyl phenyl) Methacrylamide, N-(carboxyl phenyl) acrylic amide etc.
As monomer, for example can enumerate out hydroxy styrenes, N-(hydroxy phenyl) acrylic amide, N-(hydroxy phenyl) Methacrylamide, N-(hydroxy phenyl) maleimide etc. with phenolic hydroxyl.
As monomer with the hydroxyl except that phenolic hydroxyl; For example can enumerate out 2-Hydroxy ethyl acrylate, acrylic acid-2-hydroxy propyl ester, 5-acryloxy-6-hydroxyl ENB-2-carboxylic acid-6-lactone, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, 5-methacryloxy-6-hydroxyl ENB-2-carboxylic acid-6-lactone etc.
And then,, can enumerate out acrylic acid-2-amino ethyl ester, methacrylic acid-2-amino methyl etc. as monomer with the amino that contains active hydrogen.
In addition, specific copolymer can be with monomer with the functional group that is used to carry out the heat cross-linking reaction with have the multipolymer that monomer beyond the monomer that is used to carry out the functional group that film solidifies (below, be called other monomer) forms as constituting the unit.
As other monomer; Specifically; So long as can with the monomer with at least a functional group in carboxyl and the phenolic hydroxyl; And have hydroxyl except that phenolic hydroxyl and carry out copolymerization with the monomer that contains at least a functional group in the amino of active hydrogen and get final product, only otherwise damage the characteristic of (A) composition, just there is not special qualification.
As the concrete example of other monomers, can enumerate out acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and ethylene compounds etc.
As acrylate compounds; For example can enumerate out; Methyl acrylate, acrylic acid ethyl ester, acrylic acid isopropyl esters, acrylic acid benzyl ester, acrylic acid naphthyl ester, acrylic acid anthryl ester, acrylic acid anthryl methyl ester, phenyl acrylate, acrylic acid-2; 2,2-trifluoroethyl ester, acrylic acid tertiary butyl ester, acrylic acid cyclohexyl ester, isobornyl acrylate, acrylic acid-2-methoxy ethyl ester, methoxyl triethylene glycol acrylic ester, acrylic acid-2-ethoxyethyl group ester, acrylic acid tetrahydro furfuryl ester, acrylic acid-3-methoxyl butyl ester, 2-methyl-2-adamantyl acrylic ester, 2-propyl group-2-adamantyl acrylic ester, 8-methyl-8-three ring decyl acrylic ester and 8-ethyl-8-three ring decyl acrylic ester etc.
As methacrylate compound; For example can enumerate out; Methyl methacrylate, methacrylic acid ethyl ester, methacrylic acid isopropyl esters, methacrylic acid benzyl ester, naphthyl, methacrylic acid anthryl ester, methacrylic acid anthryl methyl ester, methacrylic acid phenylester, methacrylic acid-2; 2,2-trifluoroethyl ester, methacrylic acid tertiary butyl ester, methacrylic acid cyclohexyl ester, IBOMA, methacrylic acid-2-methoxy ethyl ester, methoxyl triethylene glycol methacrylate, methacrylic acid-2-ethoxyethyl group ester, methacrylic acid tetrahydro furfuryl ester, methacrylic acid-3-methoxyl butyl ester, 2-methyl-2-adamantyl methacrylate, 2-propyl group-2-adamantyl methacrylate, 8-methyl-8-three ring decyl methacrylates and 8-ethyl-8-three ring decyl methacrylates etc.
As ethylene compounds, for example can enumerate out methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, Vinyl phenyl ether and propyl vinyl ether etc.
As distyryl compound, for example can enumerate out styrene, methyl styrene, chlorostyrene, bromstyrol etc.
As maleimide compound, for example can enumerate out maleimide, N-methyl maleimide, N-phenylmaleimide and N-cyclohexyl maleimide etc.
Method to the specific copolymer that obtains using among the present invention limits especially; For example; Can be through in solvent; Under 50～110 ℃ temperature; Make following substances carry out polyreaction and obtain, said material is: at least a monomer of suitably selecting in the group of the monomer of at least a functional group from have carboxyl and phenolic hydroxyl, from having the hydroxyl except that phenolic hydroxyl and containing in the group of monomer of at least a functional group the amino of active hydrogen the suitably at least a monomer of selection, the monomer except that above-mentioned monomer that adds as required, the polymerization initiator that adds as required etc.As long as at this moment employed solvent can dissolve monomer and the solvent of specific copolymer, the qualification especially that constitutes specific copolymer.As concrete example, can enumerate out the solvent of putting down in writing in following (F) solvent.
The specific copolymer that obtains like this, usually, this specific copolymer is in the state that is dissolved in the solution in the solvent.
In addition, under stirring condition, the solution of the specific copolymer that above-mentioned that kind is obtained is put in ether or the water etc.; It is precipitated again, after the sediment that generates is filtered, cleans, under normal pressure or decompression; Through normal temperature or heat drying, can form the powder of specific copolymer.Through such operation, can remove polymerization initiator, unreacted monomer with specific copolymer coexistence, its result can access the powder of refining specific copolymer.Under situation about can not fully make with extra care through single job, can the powder that obtain be dissolved in the solvent again, carry out above-mentioned operation repeatedly.
In the present invention, can directly use the powder of specific copolymer, perhaps also can this powder be dissolved in for example following (F) solvent again, use with solution state.
(B) composition
(B) composition is the alkali soluble resins that in main chain, has aromatic ring or alicyclic structure.Here said aromatic ring is the cyclic hydrocarbon of benzene, naphthalene, anthracene etc., and said alicyclic ring is meant the cyclic hydrocarbon of cyclo-butane, cyclopentane, cyclohexane, tristane etc.
As alkali soluble resins, can enumerate out polyimide precursor, alkali solubility polyimide, phenol novolac resin, cresols novolac resin, naphthol novolac varnish gum etc. with such ring structure.In these resins, from keeping the viewpoint of high transparent, preferred polyimide precursor, alkali solubility polyimide.
In addition, above-mentioned (B) composition alkali soluble resins, number-average molecular weight is preferably 2000～30000 scope, more preferably 2000～15000 scope.If number-average molecular weight is excessive, surpassed 30000, then be easy to generate the development residue, sensitivity reduces greatly; On the other hand, if number-average molecular weight is too small, less than 2000; Then when developing, unexposed the quite a large amount of thickness of generation reduces, and the situation that becomes not enough of solidifying is arranged.
And then above-mentioned (B) composition alkali soluble resins is preferably the alkali soluble resins with the alkyl that has replaced with fluorine atom, is preferably the polyimide precursor with the alkyl that has replaced with fluorine atom.At this moment; In having the polyimide precursor of aromatic rings; If have the substituted alkyl of fluorine; Therefore then compare with the compound that does not have the substituted alkyl of fluorine, the transparency is higher, and above-mentioned polyimide precursor preferably has with the substituted particularly carbon number of fluorine atom 1～10, preferably carbon number 1～7, the alkyl of carbon number 1～5 most preferably.
Above-mentioned (B) composition alkali soluble resins that uses like this, can with respect to (A) composition alkali solubility acrylate copolymer 100 mass parts, be that the ratio of 0.5～100 mass parts is used, according to the difference of the resin that uses, can select usage ratio arbitrarily.
< polyimide precursor >
In normal Photosensitive resin of the present invention; The above-mentioned polyimide precursor that contains as the alkali soluble resins of (B) composition; The polyamic acid of expression polyamic acid, poly amic acid ester, part imidizate, in general, can be by (a) tetracarboxylic dianhydride compound and (b) diamine compound manufacturing.
(a) tetracarboxylic dianhydride compound that uses in the manufacturing to the above-mentioned polyimide precursor that uses among the present invention does not have restriction especially, and they can use a kind of, perhaps also can use simultaneously more than 2 kinds.As object lesson, can enumerate out PMDA, 3,3 '; 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4; 4 '-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, and 3; 3 ', 4, aromatic tetracarboxylic acid's dianhydrides such as 4 '-diphenyl sulfone tetracarboxylic acid dianhydride; 1,2,3,4-cyclo-butane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2; 3,4-cyclo-butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2; 3,4-cyclo-butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2; 3,4-cyclohexane tetracarboxylic acid dianhydride, and 3,4-dicarboxyl-1,2,3, the alicyclic ring shape tetracarboxylic dianhydride that 4-tetrahydrochysene-1-naphthalene succinic dianhydride is such; 1,2,3, the aliphatics tetracarboxylic dianhydride that 4-ethylene-dimalonic acid dianhydride is such.
(b) diamine compound that uses in the manufacturing to the above-mentioned polyimide precursor that uses among the present invention, not special restriction, they can use a kind of, perhaps also can use simultaneously more than 2 kinds.As object lesson, can enumerate out, 2,4-diaminobenzoic acid, 2; 5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diaminostilbene, 3-phthalic acid, 2; The 5-diaminostilbene, 4-phthalic acid, two (4-amino-3-carboxyl phenyl) ether, two (4-amino-3,5-dicarboxyl phenyl) ether, two (4-amino-3-carboxyl phenyl) sulfone, two (4-amino-3,5-dicarboxyl phenyl) sulfone, 4; 4 '-diamido-3,3 '-dicarboxylate biphenyl, 4,4 '-diamido-3; 3 '-dicarboxyl-5,5 '-dimethyl diphenyl, 4,4 '-diamido-3; 3 '-dicarboxyl-5,5 '-dimethoxy-biphenyl, 1, two (4-amino-3-carboxyl phenoxy group) benzene, 1 of 4-; Two (4-amino-3-carboxyl phenoxy group) benzene of 3-, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] sulfone, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] propane, and 2, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] HFC-236fas, 2 of 2-, 4-diaminophenol, 3; 5-diaminophenol, 2,5-diaminophenol, 4,6-diamino resorcin, 2; 5-diamido quinhydrones, two (3-amino-4-hydroxy phenyl) ether, two (4-amino-3-hydroxy base) ether, two (4-amino-3,5-dihydroxy phenyl) ether, two (3-amino-4-hydroxy phenyl) methane, two (4-amino-3-hydroxy base) methane, two (4-amino-3,5-dihydroxy phenyl) methane, two (3-amino-4-hydroxy phenyl) sulfone, two (4-amino-3-hydroxy base) sulfone, two (4-amino-3; The 5-dihydroxy phenyl) sulfone, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas, 2 of 2-, two (the 4-amino-3-hydroxy base) HFC-236fas, 2 of 2-; 2-two (4-amino-3,5-dihydroxy phenyl) HFC-236fa, 4,4 '-diamido-3; 3 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxy-5; 5 '-dimethyl diphenyl, 4,4 '-diamido-3,3 '-dihydroxy-5; 5 '-dimethoxy-biphenyl, 1, two (the 3-amino-4-hydroxy phenoxy group) benzene, 1 of 4-, two (the 3-amino-4-hydroxy phenoxy group) benzene, 1 of 3-; Two (the 4-amino-3-hydroxy oxygen base) benzene, 1 of 4-, two (the 4-amino-3-hydroxy oxygen base) benzene of 3-, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] sulfone, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] propane, and 2, two [4-(the 3-amino-4-hydroxy phenoxy group) phenyl] HFC-236fas etc. of 2-have the diamine compound of phenol property hydroxyl; 1,3-diamido-4-sulfydryl benzene, 1,3-diamido-5-sulfydryl benzene, 1; 4-diamido-2-sulfydryl benzene, two (4-amino-3-sulfydryl phenyl) ether, and 2, the diamine compound with benzenethiol base, 1 of two (3-amino-4-sulfydryl phenyl) HFC-236fas of 2-etc., 3-diaminobenzene-4-sulfonic acid, 1; 3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, two (4-aminobenzene-3-sulfonic acid) ether, 4,4 '-benzidine-3; 3 '-disulfonic acid, and 4; 4 '-diamido-3,3 '-dimethyl diphenyl-6,6 '-disulfonic acid etc. have sulfonic diamine compound.In addition, can enumerate out p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-methylene-two (2; The 6-MEA), 4,4 '-methylene-two (2-isopropyl-6-methylaniline), 4,4 '-methylene-two (2, the 6-diisopropyl aniline), 2; 4,6-trimethyl-1,3-phenylenediamine, 2,3; 5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, a tolidine, 3,3 '; 5,5 '-tetramethyl benzidine, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(3-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fas, 4 of 2-; 4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride, 4,4 '-diamino-diphenyl ether, 3,4-diamino-diphenyl ether, 4; 4 '-diaminodiphenyl-methane, 2, two (4-anilino-) HFC-236fas, 2 of 2-, two (3-anilino-) HFC-236fas, 2 of 2-, two (3-amino-4-toluyl) HFC-236fas, 1 of 2-; Two (4-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene of 3-, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, and 2, diamine compounds such as two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas of 2-.
In addition, can make the polyimide precursor that has with the substituted alkyl of fluorine atom through following compound and above-mentioned (a) tetracarboxylic dianhydride compound in the compound cited as the example of above-mentioned (b) diamine compound; Wherein, said compound is 2, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] HFC-236fas, 2 of 2-; Two (the 3-amino-4-hydroxy phenyl) HFC-236fas, 2 of 2-; Two (the 4-amino-3-hydroxy base) HFC-236fas, 2 of 2-, 2-two (4-amino-3,5-dihydroxy phenyl) HFC-236fa, 2; Two [4-(the 3-amino-4-hydroxy phenoxy group) phenyl] HFC-236fas, 2 of 2-; Two (3-amino-4-sulfydryl phenyl) HFC-236fas, 2 of 2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fas, 4 of 2-, 4 '-diaminodiphenyl-methane, 2; Two (4-anilino-) HFC-236fas, 2 of 2-; Two (3-anilino-) HFC-236fas, 2 of 2-, two (3-amino-4-toluyl) HFC-236fas, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas of 2-etc. have a diamine compound with the substituted alkyl of fluorine atom.
Under the situation of the above-mentioned polyimide precursor that uses in the present invention by above-mentioned (a) tetracarboxylic dianhydride's compound and the manufacturing of above-mentioned (b) diamine compound; The match ratio of two compounds; That is, (total mole number of (b) diamine compound)/(total mole number of (a) tetracarboxylic dianhydride compound) is preferably 0.7～1.2.Identical with common polycondensation reaction, this mol ratio approaches 1 more, and the degree of polymerization of the polyimide precursor of generation is big more, and molecular weight increases.
In addition, when excessive use above-mentioned (b) diamine compound carries out polymerization, can also make the terminal amino group and the carboxylic acid anhydrides reaction of the polyimide precursor of generation, the protection terminal amino group.
As the example of such carboxylic acid anhydrides, can enumerate out phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenation phthalic anhydride, methyl-5-ENB-2,3-dicarboxylic acid anhydride, itaconic anhydride, tetrabydrophthalic anhydride etc.
In the manufacturing of above-mentioned polyimide precursor, the temperature of reaction of the reaction of above-mentioned (a) tetracarboxylic dianhydride's compound and above-mentioned (b) diamine compound can be selected from-20 ℃～150 ℃, preferred-5 ℃～100 ℃ arbitrary temp.Temperature of reaction is 5 ℃～40 ℃, and the reaction time is the polyimide precursor that can obtain HMW under 1～48 hour the condition.In order to obtain the good polyimide precursor of low-molecular-weight and storage stability, more preferably under 40 ℃～90 ℃ of temperature of reaction, the reaction time is to react more than 10 hours.
Temperature of reaction with under the situation of acid anhydrides protection terminal amino group can be selected from-20 ℃～150 ℃, preferred-5 ℃～100 ℃ arbitrary temp.
The reaction of above-mentioned (a) tetracarboxylic dianhydride's compound and above-mentioned (b) diamine compound can be carried out in solvent.As the solvent that can use at this moment; Can enumerate out N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, N-vinyl pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, metacresol, gamma-butyrolacton, ethyl acetate, butyl acetate, ethyl lactate, 3-methoxypropionic acid methyl esters, 2-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 2-ethoxyl ethyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diglycol monotertiary methyl ether, carbiphene, propylene glycol monomethyl ether, propylene glycol list ethylether, dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, propylene glycol monomethyl ether, carbitol acetic acid esters, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone etc.They can use separately, also can mix use.And then, even can not dissolve the solvent of polyimide precursor, also can in the scope that the polyimide precursor that is generated by polyreaction is not separated out, use with above-mentioned solvent.
The solution that contains the polyimide precursor that obtains like this can directly be used for the preparation of normal Photosensitive resin.In addition, polyimide precursor also can be dropped in the poor solvents such as water, methyl alcohol, ethanol, and precipitate and separate reclaims the back and uses.
In addition, above-mentioned polyimide precursor, can with respect to (A) composition alkali solubility acrylate copolymer 100 mass parts, be that the ratio of 5～100 mass parts, preferred 10～60 mass parts is used.If the use amount of above-mentioned polyimide precursor is very few, be lower than the lower limit of above-mentioned scope, crackle then appears when the ITO sputter sometimes.On the other hand, if the use amount of above-mentioned polyimide precursor is too much, surpass the upper limit of above-mentioned scope, the transparency after then solidifying descends.
< polyimide >
In addition, the alkali soluble resins as (B) composition that uses in the normal Photosensitive resin of the present invention can use polyimide arbitrarily.The polyimide that uses among the present invention, thus be to make above-mentioned polyimide precursor pass through chemical or hot and compound that formed by imidizate more than 50%.In these polyimide, also comprise the multipolymer of polyamidoimide, polyetherimide etc.Preferably have polyimide,, preferably have with the substituted carbon number of fluorine atom 1～10, preferably carbon number 1～7, the alkyl of carbon number 1～5 most preferably particularly from improving the viewpoint of solubleness with the substituted alkyl of fluorine atom.
The polyimide that uses in the positive type photosensitive organic compound of the present invention in order to give alkali solubility, preferably has carboxyl or phenol property hydroxyl or generates the group of carboxylic acid or phenol property hydroxyl through heat or sour effect.The introduction method of carboxyl, phenol property hydroxyl; Can enumerate and send as an envoy to having the monomer methods of carboxyl, phenol property hydroxyl; Seal the only terminal method of amine with the acid anhydrides with carboxyl, phenol property hydroxyl, perhaps when polyimide precursor is carried out imidizate, making the imidizate rate is the method etc. below 99%.Generate the introduction method of the group of carboxylic acid or phenol property hydroxyl through heat or sour effect; Comprise: use the monomer methods that generates carboxyl, phenol property hydroxyl through heat or sour effect, make carboxyl residue behind carboxyl, phenol property hydroxyl or the imidizate that imports in advance through heat or sour effect method with the radical reaction that dissociates.Such polyimide can be through carrying out chemical imidizate or hot-imide obtains behind synthetic above-mentioned polyimide precursor.
In addition, alkali-soluble above-mentioned polyimide, can with respect to alkali solubility acrylate copolymer 100 mass parts of (A) composition, be that the ratio of 0.5～20 mass parts, preferred 1～15 mass parts is used.If the use amount of alkali-soluble above-mentioned polyimide is very few, be lower than the lower limit of above-mentioned scope, crackle then appears when the ITO sputter sometimes.On the other hand, if the use amount of alkali-soluble above-mentioned polyimide is too much, surpass the upper limit of above-mentioned scope, the transparency after then solidifying descends.
< C composition >
(C) composition is the compound that has the vinyl ether group more than 2 in 1 molecule.This composition is so long as have under prebake conditions temperature commonly used, can get final product with the compound that (A) composition alkali solubility acrylate copolymer carries out the vinyl ether group of heat cross-linking more than 2, for its kind and qualification especially of structure in 1 molecule.
Be somebody's turn to do (C) component cpd; With (A) composition alkali solubility acrylate copolymer heat cross-linking after; Be utilized in the existence acid of exposure generation down of light acid propellant; From (A) composition alkali solubility acrylate copolymer, separate (taking off crosslinked), through having used the development of alkaline-based developer, be removed afterwards with (A) composition alkali solubility acrylate copolymer.Therefore, as this compound, generally can be applied in vinyl ether based compound that uses in the composition of vinyl ether type chemically amplified corrosion-resisitng agent etc.Under the situation of using such compound, regulate heat cross-linking density through the use level that changes this compound, the advantage that can control the shape that forms film is arranged.
In addition, as (C) component cpd, in above-mentioned vinyl ether based compound, particularly the compound shown in formula (1) and the formula (2) from the viewpoint that does not have residual film or residue ground to develop at the exposure position, is preferred.
(in the formula, n is 2～10 integer, and k is 1～10 integer, R
1The organic group of expression n valency.)
formula (2)
(in the formula, m representes 2～10 integer.)
The n of formula (1) representes the number of the vinyl ether group in 1 molecule, as n, and more preferably 2～4 integer.In addition, the m of formula (2) also representes the number of the vinyl ether group in 1 molecule, as m, and more preferably 2～4 integer.
Object lesson as compound shown in above-mentioned formula (1) and the above-mentioned formula (2); Can enumerate out two (4-(ethyleneoxy methyl) cyclohexyl methyl) glutarate, three (monoethylene glycol) divinyl ether, hexane diacid divinyl ester, diethylene glycol divinyl ether, three (4-ethyleneoxy) butyl trimellitate, two (4-(ethyleneoxy) butyl) terephthalate, two (4-(ethyleneoxy) butyl) isophthalic acid ester and cyclohexanedimethanol divinyl ether etc.
In addition, (C) component cpd with respect to (A) composition that adds up to 100 mass parts and (B) composition, with 1～80 mass parts, preferably uses with the ratio of 5～40 mass parts.If (C) use amount of component cpd is the very few amount less than the lower limit of above-mentioned scope, then the thickness minimizing at unexposed position becomes significantly, thereby the relief of pattern-like (relief) shape becomes bad.On the other hand, if (C) use amount of component cpd is the too much amount that surpasses the upper limit of above-mentioned scope, then the sensitivity of film reduces greatly, thereby at the residue that produces after the development between pattern.
< D composition >
(D) composition is the compound that has the blocked isocyanate base more than 2 in 1 molecule.This composition so long as can to contain and (C) carried out between the compound of composition heat cross-linking or and then again and carried out taking off the film of crosslinked (A) composition alkali solubility acrylate copolymer between it; The compound that in 1 molecule, has the blocked isocyanate base more than 2 that under the temperature of back baking for example commonly used, carries out heat curing gets final product, for the kind and the qualification especially of structure of (D) composition.
Compound that should (D) composition in 1 molecule, have more than 2, NCO is (NCO) by the blocked isocyanate base of proper protection base end-blocking; If make that like this (D) compound of composition is exposed under the high temperature when heat curing; Then protect base (end-blocking part) thermal dissociation; And come off; Thereby be intermediary, carry out cross-linking reaction each other with the functional group that is used to carry out heat curing (for example the hydroxyl except that phenolic hydroxyl and have the amino of active hydrogen) in (A) the composition alkali solubility acrylate copolymer with the NCO that produces, the compound of this (D) composition for example can be enumerated out, has in 1 molecule that (this group can be identical more than 2; Also can be different separately) formula (3) shown in the compound of group
(in the formula, R
2The organic group at expression end-blocking position).
The compound that has (D) composition of the blocked isocyanate base more than 2 in 1 molecule can obtain through for example making the compound effects that has the NCO more than 2 in suitable end-capping reagent and 1 molecule.
As the compound that has the NCO more than 2 in 1 molecule; For example can enumerate out; IPDI, hexamethylene diisocyanate, di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate etc., in addition; Their dimer, tripolymer, the perhaps reactant of these compounds and di-alcohols, ternary alcohols, two amines, three amines.
As end-capping reagent; For example can enumerate out methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, 2-ethoxy hexanol, 2-N, the alcohols of N-dimethylaminoethanol, cellosolvo, cyclohexanol etc.; Phenol, o-nitrophenol, parachlorophenol, neighbour, or the phenols of paracresol etc.; The lactams of epsilon-caprolactams etc., the oximes of acetoxime, methyl ethyl ketone oxime, methyl isobutyl ketoxime, cyclohexanone oxime, acetophenone oxime, diphenyl-ketoxime etc., pyrazoles, 3; The pyrazoles of 5-dimethyl pyrazole, 3-methylpyrazole etc., the thio-alcohol of lauryl mercaptan, benzenethiol etc.
(D) compound of composition; Be under the such higher temperature of back baking temperature, thereby end-blocking partly produces thermal dissociation carries out cross-linking reaction as intermediary with NCO material; For the compound that makes (D) composition under the such lower temperature of prebake conditions temperature; Do not carry out by NCO cause crosslinked, and make the thermal dissociation temperature of its end-blocking part compare with the prebake conditions temperature, be quite high temperature; As the compound of (D) composition, for example the thermal dissociation temperature of end-blocking part is that 120 ℃～230 ℃ compound is preferred especially.
As the compound of such (D) composition, for example can enumerate out following object lesson.
In the formula, as the compound of (D) composition, when isocyanate compound is during from compound that IPDI derives out; Viewpoint from thermotolerance, filming property; Be preferred,, can enumerate out following compound as such compound.
R in the following formula representes organic group.
In the present invention, (D) compound of composition can use separately a kind of, also can make up in addition use two or more.
In addition, (D) compound of composition, with respect to (A) composition and (B) total 100 mass parts of composition, with 1～80 mass parts, the ratio of preferred 5～40 mass parts is used.If (D) use amount of the compound of composition is the very few amount less than the lower limit of above-mentioned scope; Then heat curing becomes insufficient; Thereby can not obtain satisfied cured film, on the other hand, if (D) use amount of the compound of composition is the too much amount that surpasses the upper limit of above-mentioned scope; Then developing becomes insufficient, thereby produces the development residue.
< E composition >
(E) composition is light acid propellant (PAG).This composition is the irradiation through the light that in exposure, uses; Generate the material of acid (sulfonic acid class, carboxylic acids etc.) directly or indirectly; So long as have the compound of such character; Its kind and structure etc. are limited especially, still especially preferably produce the compound of sulfonic acid through rayed.
Light acid propellant as (E) composition; For example can enumerate out diazomethane compound, salt compound, sulfimine compound, two sulfone based compounds, sulfonic acid derivative compound, nitrobenzyl compound, benzoin tosylate compound, iron arene complex compound, the triaizine compounds that contains halogen, acetophenone derivative compound and contain oxime sulfonates compound of cyanic acid etc.Arbitrary material of light acid propellant at present known or that always use all can, limit especially, can use in the present invention.In addition, in the present invention, (E) light acid propellant of composition can use separately a kind of, also can make up in addition use two or more.
As the object lesson of light acid propellant, can enumerate out following compound.
formula (8)
Chlorinated diphenyl iodine; Diphenyl iodine trifluoro-methanyl sulfonate; The diphenyl iodomethanesulfonate; Diphenyl iodotoluene sulphonate; Brominated diphenyl base salt compounded of iodine; Diphenyl iodine tetrafluoroborate; Diphenyl iodine hexafluoro antimonate; Diphenyl iodine hexafluoro arsenate; Two (right-tert-butyl-phenyl) iodine hexafluorophosphate; Two (right-tert-butyl-phenyl) iodomethanesulfonate; Two (right-tert-butyl-phenyl) iodotoluene sulphonate; Two (right-tert-butyl-phenyl) iodine trifluoro-methanyl sulfonate; Two (right-tert-butyl-phenyl) iodine tetrafluoroborate; Two (right-tert-butyl-phenyl) salt compounded of iodine of chlorination; Two (rubigan) salt compounded of iodine of chlorination; Two (rubigan) iodine tetrafluoroborate; The chlorinated triphenyl sulfonium; The bromination triphenyl sulfonium; The triphenyl sulfonium trifluoro-methanyl sulfonate; Three (p-methoxyphenyl) sulfonium tetrafluoroborate; Three (p-methoxyphenyl) sulfonium hexafluorophosphate; Three (to ethoxyl phenenyl) sulfonium tetrafluoroborate; Lvization San Ben Phosphonium; Bromination San Ben Phosphonium; Three (p-methoxyphenyl) Phosphonium tetrafluoroborates; Three (p-methoxyphenyl) Phosphonium hexafluorophosphates; Three (to ethoxyl phenenyl) Phosphonium tetrafluoroborate.
formula (16)
formula (17)
formula (18)
formula (49)
In addition, (E) light acid propellant of composition, with respect to (A) composition and (B) total 100 mass parts of composition, with 0.5～80 mass parts, the ratio of preferred 1～30 mass parts is used.If (E) use amount of composition light acid propellant is the too few amount less than the lower limit of above-mentioned scope; Then when exposure; Heat cross-linking (C) component cpd from the dissociating and can not carry out fully of (A) composition alkali solubility acrylate copolymer, the relief of the pattern-like that is difficult to obtain hoping, on the other hand; If (E) use amount of the light acid propellant of composition is the too many amounts that surpass the upper limit of above-mentioned scope, then the storage stability variation of positive type photosensitive organic compound.
(F) solvent
(F) solvent that uses in the present invention; Can dissolve the composition of (A) composition～(E); And can dissolve as required following (G) composition that adds and/or (H) become to grade,, its kind and structure etc. not had special qualification so long as have the solvent of such dissolving power.
As such (F) solvent; For example can enumerate out; Glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl propionic acid ethyl ester, ethoxyacetic acid ethyl ester, glycolic acid ethyl ester, 2-hydroxy-3-methyl butyric acid methyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxy-propionic acid ethyl ester, 3-ethoxy-propionic acid methyl ester, pyruvic acid methyl ester, pyruvic acid ethyl ester, acetic acid ethyl ester, acetic acid butyl ester, lactic acid ethyl ester, lactic acid butyl ester, N; Dinethylformamide, DMAC N,N and N-Methyl pyrrolidone etc.
These solvents can use a kind of separately, and perhaps combination is used two or more.
In these (F) solvents, from good, the safe viewpoint of filming property, preferred propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, lactic acid ethyl ester, lactic acid butyl ester etc.These solvents generally use as the solvent that photo anti-corrosion agent material is used.
< G composition >
(G) composition is an amines.For positive type photosensitive organic compound of the present invention,, only otherwise damage effect of the present invention, can and then contain amines from the purpose that improves its storage stability.
Amines as (G) composition; Do not limit especially; For example can enumerate out the tertiary amine of triethanolamine, three butanolamines, triisopropanolamine, Trimethylamine, triethylamine, three n-pro-pyl amine, triisopropylamine, tri-n-butyl amine, tri-tert amine, trioctylphosphine amine, triphenylamine and diazabicyclo octane etc., the aromatic amine of pyridine and 4-dimethylaminopyridine etc.; And the primary amine of benzylamine and n-butylamine etc., the perhaps secondary amine of diethylamide and di-n-butyl amine etc.
(G) amines of composition can use a kind ofly separately, and perhaps combination is used two or more.
When using amines, its amount with respect to (A) composition and (B) total 100 mass parts of composition, for example is 0.001～5 mass parts, in addition according to condition of different, is 0.005～1 mass parts, is preferably 0.01～0.5 mass parts in addition.If (G) use amount of the amines of composition is the too few amount less than the lower limit of above-mentioned scope; Then can not fully improve the storage stability of positive type photosensitive organic compound; On the other hand; If (G) use amount of the amines of composition is the too many amounts that surpass the upper limit of above-mentioned scope, the situation of the sensitivity reduction of positive type photosensitive organic compound is arranged then.
< H composition >
(H) composition is a surfactant.For positive type photosensitive organic compound of the present invention,, only otherwise damage effect of the present invention, can and then contain surfactant from the purpose that improves its coating.
As the surfactant of (H) composition, do not limit especially, for example can enumerate out, fluorine is surfactant, silicone type surface active agent, non-ionics etc.As this surfactant, for example can use the commercially available article of Sumitomo ス リ-エ system (strain) system, big Japanese イ Application キ chemical industry (strain) system or Asahi Glass (strain) system etc.These commercially available article can easily obtain, and are suitable therefore.As its concrete example, the fluorine that can enumerate out エ Off ト Star プ EF301, EF303, EF352 ((strain) ジ エ system コ system), メ ガ Off ア Star Network F171, F173 (big Japanese イ Application キ chemical industry (strain) system), Off ロ ラ-De FC430, FC431 (Sumitomo ス リ-エ system (strain) system), ア サ ヒ ガ-De AG710, サ-Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (strain) system) etc. is a surfactant.
(H) surfactant of composition can use a kind ofly separately, and perhaps combination is used two or more.
When using surfactant, its amount in the positive type photosensitive organic compound of 100 quality %, is generally below the 0.2 quality %, is preferably below the 0.1 quality %.If (H) use amount of the surfactant of composition is set at the amount that surpasses 0.2 quality %, then the improved effect of above-mentioned coating becomes not obvious, becomes uneconomical.
< other adjuvant >
And then; For positive type photosensitive organic compound of the present invention; Only otherwise damage effect of the present invention; The dissolution accelerator etc. that can contain as required, bonding assistant, pigment, dyestuff, preserving stabilizer, foam-breaking agent or polyhydric phenol, the polybasic carboxylic acid etc. of rheology control agent, silane coupling agent etc.< positive type photosensitive organic compound >
Positive type photosensitive organic compound of the present invention; It is the composition that can contain following substances; Said material is that alkali solubility acrylate copolymer, (B) composition are alkali soluble resins, (C) composition compound of promptly having vinyl ether group, (D) composition promptly has the blocked isocyanate base compound, (E) composition are light acid propellant and (F) solvent for (A) composition; And respectively as required, so contain (G) composition be amines, (H) composition be surfactant, and other adjuvants in more than one.
Wherein, the preferred example of positive type photosensitive organic compound of the present invention is described below.
: a kind of positive type photosensitive organic compound; (A) composition based on 100 mass parts; (B) composition that contains 0.5～100 mass parts; Based on (A) composition that adds up to 100 mass parts and (B) composition, contain (C) composition and (D) composition of 1～80 mass parts and (E) composition of 0.5～80 mass parts of 1～80 mass parts, and these compositions are dissolved in (F) solvent.
: like above-mentioned [1] described positive type photosensitive organic compound,, and then contain (G) compositions of 0.001 mass parts～5 mass parts based on (A) composition that adds up to 100 mass parts and (B) composition.
: like above-mentioned [1] perhaps [2] described positive type photosensitive organic compound, and then contain (H) composition below the 0.2 quality %.
To the ratio of the solid constituent in the positive type photosensitive organic compound of the present invention, as long as each composition can be dissolved in the solvent equably, then qualification especially for example is 1～80 quality %, for example is 5～60 quality % in addition, perhaps 10～50 quality %.Here, so-called solid constituent is meant the composition of from whole compositions of positive type photosensitive organic compound, having removed behind (F) solvent.
Modulator approach to positive type photosensitive organic compound of the present invention; Do not limit especially; But as its modulation method; For example can enumerate out; (A) composition (alkali solubility acrylate copolymer) is dissolved in (F) solvent, in this solution with mixed (B) composition (alkali soluble resins), (C) composition (compound), (D) composition (compound), (E) composition (light acid propellant) of regulation and (H) composition (surfactant) with blocked isocyanate base with vinyl ether group, thereby the method for the solution of formation homogeneous; Perhaps, in the suitable stage of this modulation method, as required, and then the method for adding and mixing (G) composition (amines) and/or other adjuvant.
Modulation for positive type photosensitive organic compound of the present invention; Can directly use the solution of the specific copolymer that obtains through the polyreaction in (F) solvent; In this case; When in the solution of this (A) composition, with above-mentioned same adding (B) composition, (C) composition, when (D) becomes to grade to process the solution of homogeneous, with concentration adjustment as purpose, also can so that additional input (F) solvent.At this moment, (F) solvent that in the forming process of specific copolymer, uses and can be identical when the modulation of positive type photosensitive organic compound, in order regulate concentration to use (F) solvent, also can be different.
And, the solution of the positive type photosensitive organic compound of modulation, preferably using the aperture is that filtrator etc. about 0.2 μ m filters, and uses then.
In addition, the polyimide as acrylate copolymer of above-mentioned (A) of the present invention composition and (B) composition are enumerated in the photoresist material, is widely used as various base polymers at present.If but the both is a polymer morphology, then there is the problem of compatibility difference.Therefore; For example be necessary as acrylic monomers and polyimide (for example with reference to the spy open flat 10-55065 communique, the spy opens flat 11-052572 communique, No. 3211108 communique of Jap.P.) such, or as acrylic monomers and dant monomer, be the monomer form use with at least one side.
In positive type photosensitive organic compound of the present invention; Through except aforesaid propylene acid polymer ((A) composition) and polyimide ((B) composition); Also cooperate the solvent of (C) composition～(F); Can solve the problem of the above-mentioned compatibility that does not solve so far, make it become stabilising system, be used for the modulation of cured film thereafter.
< filming and cured film >
The rotary coating of carrying out through rotary coating, flow coat, roller coat, slot coated, slot coated continued, ink-jet application etc.; Positive type photosensitive organic compound of the present invention (for example is coated on the semiconductor substrate; Silicon/silicon dioxide is substrate coated, the silicon nitride substrate, the for example substrate of metals such as aluminium, molybdenum, chromium, glass substrate, quartz base plate, ito substrate etc. have been covered); Afterwards, predrying through carrying out with electric hot plate or baking oven etc., can form and film.Afterwards, carry out heat treated, can form the normal Photosensitive resin film through this is filmed.
As the condition of this heat treated, for example, adopt from 70 ℃～160 ℃ of temperature heating-up temperature and the heat time heating time suitably selected in the scope of 0.3～60 minute time.Are preferably heating-up temperature and heat time heating time 80 ℃～140 ℃, 0.5～10 minute.
In addition, the thickness of the normal Photosensitive resin film that is formed by positive type photosensitive organic compound is for example 0.1～30 μ m, for example is 0.2～10 μ m in addition, and then for example is 0.2～5 μ m.
In addition, formed normal Photosensitive resin film, the heat treated during through formation makes the compound with vinyl ether group of (C) composition and (A) composition alkali solubility acrylate copolymer is crosslinked, forms the film that is insoluble in alkaline-based developer thus.In this case, the temperature of heat treated than the lower situation of the lower limit of above-mentioned temperature range under, heat cross-linking becomes insufficient, produces thickness at unexposed position and reduce sometimes.In addition, when the temperature of heat treated surpasses the upper limit of above-mentioned temperature range, under the situation for excessive temperature, the temporary transient heat cross-linking portion that forms of marquis is cut off once more sometimes, causes that at unexposed position thickness reduces.
The normal Photosensitive resin film that is formed by positive type photosensitive organic compound of the present invention if having the mask of predetermined pattern through use, utilizes ultraviolet ray, ArF, KrF, F
2The light of laser etc. makes public, and then utilizes the effect of the acid of (E) composition light acid propellant (PAG) generation that contains in the normal Photosensitive resin film, and the exposure portion in this film becomes in alkaline-based developer and can dissolve.
Then, to the back heating (PEB) that makes public of eurymeric photosensitive resin film.As the condition of the heating of this situation, adopt from 80 ℃～150 ℃ of temperature heating-up temperature and the heat time heating time suitably selected in the scope of 0.3～60 minute time.
Afterwards, use alkaline-based developer to develop.Thus, in the normal Photosensitive resin film, remove the part of having made public, thereby form the relief of pattern-like.
As operable alkaline-based developer; For example can enumerate out; The WS of alkali metal hydroxide such as potassium hydroxide, NaOH; Aqueous quaternary ammonium hydroxide solution, monoethanolamine, the propylamine, 1 of TMAH, tetraethyl ammonium hydroxide, choline etc., the alkaline aqueous solution of the amine aqueous solution of 2-ethylenediamine etc. etc.And then, in these developer solutions, also can add surfactant etc.
In above-mentioned alkaline-based developer; 0.1 the WS of the tetraethyl ammonium hydroxide of～2.38 quality %; Generally the developer solution as photoresist uses, and under the situation of photosensitive polymer combination of the present invention, also can use this alkaline-based developer; Do not cause the problem of swelling etc., can develop well.
In addition, as developing method, can use the liquid method (puddle) of covering, infusion process, shake any of infusion process.At this moment development time is generally 15～180 seconds.
After development, the eurymeric photosensitive resin film is carried out for example 20～90 seconds the washing that utilizes flowing water, then through using pressurized air or compressed nitrogen, perhaps carry out air-dryly through rotation, remove the moisture on the substrate, the result has obtained forming the film of pattern.
Then; For such formation the film of pattern, carry out back baking for heat curing, specifically; Use electric hot plate, baking oven etc. to heat the film that obtain excellences such as thermotolerance, the transparency, smooth voltinism, low water absorbable, chemical resistance thus, has good embossed pattern.
As the back baking, generally adopt following method, that is, under the heating-up temperature of from the scope of 140 ℃～250 ℃ of temperature, selecting, under the situation on the electric hot plate, carry out 5～30 minutes processing, under the situation in baking oven, carry out 30～90 minutes processing.
And, through so back baking, can obtain as purpose, have a cured film of good pattern form.
That kind as previously discussed; Utilize positive type photosensitive organic compound of the present invention, can form that the thickness at the in fact unexposed position of the degree that has fully high sensitivity and can not observe when developing does not reduce, have filming of fine pattern.
In addition; As stated, positive type photosensitive organic compound of the present invention, solvent of above-mentioned through cooperating (A) composition～(F) and (G) composition that adds as required and/or (H) composition; Obtain cured film by this resin combination, do not have the cured film of destruction of the film of crackle etc. when being formed on the ITO sputter.
Therefore; Can obtain following effect: promptly; It not only is fit to liquid crystal or the purposes of the various membrane materials in the OLED display of the array planarization film etc. of the inapplicable TFT type liquid crystal cell of chemically amplified corrosion-resisitng agent institute so far, also the purposes of suitable lenticule etc.
Embodiment
Below, through enumerating embodiment, further explain the present invention, but the present invention is not limited to these embodiment.
[abbreviation of using among the embodiment]
The implication of the abbreviation of in following embodiment, using is described below.
MAA: methacrylic acid
MMA: methyl methacrylate
HEMA: methacrylic acid-2-hydroxyethyl ester
CHMI:N-cyclohexyl maleimide
AIBN: azoisobutyronitrile
CBDA: cyclo-butane tetracarboxylic acid dianhydride
ABL:2,2 '-trifluoromethyl-4,4 '-benzidine
The NMP:N-methyl pyrrolidone
TA: trimellitic anhydride
6FDA:4,4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides
DDS:4,4 '-diamino diphenyl sulfone
DBA:3, the 5-diaminobenzoic acid
PGMEA: propylene glycol methyl ether acetate
PGME: propylene glycol monomethyl ether
PAG1: チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) system CGI1397 (trade name) (2-methyl-α-[5-[[(sulfonyl propyl base) oxygen base] imino group]-2 (5H)-thenylidenes] benzene acetonitrile
PVE1:1,4-cyclohexanedimethanol divinyl ether
NCO1: デ グ サ AG makes VESTAGON (registered trademark) B1065 (trade name)
(R representes organic group.)
NCO2: デ グ サ AG makes VESTAGON (registered trademark) BF1540 (trade name)
(R representes organic group.)
R30: big Japanese イ Application キ chemical industry (strain) system メ ガ Off ア Star Network R30 (trade name)
GT4: ダ イ セ Le chemical industry (strain) system エ Port リ-De GT-401 (trade name) (epoxidation ethylene-dimalonic acid four-(3-cyclohexenyl group methyl) modified 6-caprolactone)
MPTS: gamma-methyl allyl acyloxypropyl trimethoxysilane
P200: Japan's compound probability (strain) is made 4 of 1 mole of P-200 (trade name); The 2-diazo-1 of 4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol and 2 moles; The emulsion that 2-naphthoquinones-5-sulfonic acid chloride (1,2-Naphthoquinone-2-diazido-5-sulfonyl Chloride) synthesizes through condensation reaction
P5: the flourish chemical industry of crowd (strain) system レ ヂ ト Star プ PSM-4327 (trade name) phenol novolac resin
P6: ball is apt to the multipolymer of petro chemical industry (strain) system マ Le カ リ Application カ-CHM (trade name) polycarboxylated styrene and methacrylic acid-2-hydroxy methacrylate
[mensuration of number-average molecular weight and weight-average molecular weight]
The number-average molecular weight and the weight-average molecular weight of the specific copolymer that obtains according to following synthetic example; Under following condition, measure; Promptly; Use Japanese beam split (strain) system GPC device (Shodex (registered trademark) chromatographic column KF803L and KF804L), make the stripping solvents tetrahydrofurane mobile in chromatographic column (column temperature: 40 ℃), carry out wash-out with 1ml/ minute flow.In addition, following number-average molecular weight (below, be called Mn) and weight-average molecular weight (below, be called Mw), represent with the polystyrene corrected value.
[manufacturing of specific copolymer, polyimide and polyimide precursor]
< synthetic example 1 >
As the monomer component that constitutes specific copolymer; Use the MAA of 15.5g, the CHMI of 35.3g, the HEMA of 25.5g, the MMA of 23.7g; As radical polymerization initiator, use the AIBN of 5g, in the solvent PGMEA of 200g; Make these compounds under 60 ℃～100 ℃ temperature, carry out polyreaction, solution (the specific copolymer concentration: 27.5 quality %) that obtain Mn thus and be 4100, Mw is (A) composition (specific copolymer) of 7600.(P1)
< synthetic example 2 >
CBDA25.0g, ABL48.0g were reacted 24 hours at 23 ℃ in NMP242.1g, obtain polyimide precursor solution thus.Through in this polyimide precursor solution, adding TA8.6g and NMP34.6g; 23 ℃ of reactions 24 hours, solution (the polyimide precursor concentration: 20.0 quality %) that obtain Mn thus and be 4000, Mw is (B) composition (polyimide precursor that the terminal envelope of amine is ended) of 7400.(P2)
< synthetic example 3 >
After polyimide precursor solution (P2) 250.0g that obtains in the synthetic example 2 is diluted with N-Methyl pyrrolidone 250.0g, add acetic anhydride 35.8g and pyridine 27.6g, in 23 ℃ of reactions 2 hours, the ring-opening reaction of dewatering.This solution is put in 50% methanol aqueous solution, and filtration, drying obtain (B) composition (polyimide) powder then.The Mn of the polyimide that is obtained is 4000, Mw is 7400, and the imidizate rate is 78%.(P3)
< synthetic example 4 >
Make 6FDA17.8g, DDS4.92g and DBA3.12g in PGMEA145.6g, the solution that 75 ℃ of reactions 20 hours, obtain Mn thus and be 4200, Mw is (B) composition (polyimide precursor) of 8400.(P4)
[manufacturing of positive type photosensitive organic compound]
< embodiment 1～3, comparative example 1～4 >
According to the composition shown in the following table 1; In the solution of (A) composition, with mixed (B) composition of regulation or (B) solution of composition (in comparative example, not comprising (B) composition), (C) composition, (D) composition, (E) composition and (F) solvent; And (H) composition; At room temperature stirred 3 hours, and formed the solution of homogeneous, thereby modulate the positive type photosensitive organic compound of each embodiment and each comparative example.
[table 1]
| (A) solution of composition (g) | (B) subtract branch ※(g) | (C) composition (g) | (D) composition (g) | (E) composition (g) | (F) solvent (g) | (H) composition (g) | |
| Embodiment 1 | P1 9.0 | P2 8.25 | PVE1 0.62 | NCO1 ?0.41 | PAG1 0.21 | PGMEA ?3.75? | R30 ?0.0028 |
| Embodiment 2 | P1 14.3 | P3 0.21 | PVE1 0.62 | NCO1 ?0.41 | PAG1 0.21 | PGMEA ?5.75? | R30 ?0.0028 |
| Embodiment 3 | P1 10.5 | P4 8.25 | PVE1 0.62 | NCO1 ?0.41 | PAG1 0.21 | PGMEA ?2.75? | R30 ?0.0028 |
| Comparative example 1 | P1 15 | ?- | PVE1 0.62 | NCO1 ?0.41 | PAG1 0.21 | PGMEA ?5.75? | R30 ?0.0028 |
| Comparative example 2 | P1 15 | ?- | PVE1 0.62 | NCO2 ?0.41 | PAG1 0.21 | PGMEA ?5.75? | R30 ?0.0028 |
| Comparative example 3 | P5 15 | ?- | PVE1 0.62 | NCO1 ?0.41 | PAG1 0.21 | PGMEA ?5.75? | R30 ?0.0028 |
| Comparative example 4 | P6 15 | ?- | PVE1 0.62 | NCO1 ?0.41 | PAG1 0.21 | PGME 5.75 | R30 ?0.0028 |
※ P2 and P4 are the solution of (B) composition
< comparative example 5 >
In the specific copolymer solution (P1) that 5.5g obtains in as the example 1 alkali solubility acrylate copolymer, synthetic; Mix the conduct 1 of 1.1g; The P200 of 2-quinone diazo-compounds, 1.1g's is the MPTS, the PGMEA as solvent of 25.6g of conduct bonding assistant of the R30 as surfactant, the 0.25g of GT4, the 0.0039g of cross-linked compound as epoxy; At room temperature stirred 8 hours, and formed the solution of homogeneous, modulate positive type photosensitive organic compound thus.
Each composition for embodiment that obtains 1～3 and comparative example 1～5; Respectively sensitivity, thickness are reduced light transmission (transparency), ITO sputter patience, MEA patience and stable on heating projects behind (unexposed position), the high-temperature baking, estimate according to following order.
In addition, when obtaining cured film, for comparative example 5 by positive type photosensitive organic compound; Stage after development, before the back baking is carried out photobleaching, on the other hand, and for embodiment 1～10 and comparative example 1～4; Do not carry out this photobleaching; The back heating (PEB) but the stage after exposure, before developing makes public, so in this, both evaluation orders have the difference of following that kind.
[evaluation of sensitivity]
< embodiment 1～3, comparative example 1～4 >
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the silicon wafer, under 110 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.Thickness uses FILMETRICS system F20 to measure.Utilize キ ヤ ノ Application system ultraviolet lamp PLA-600FA, use certain hour to be 5.5mW/cm to this light intensity of filming irradiation 365nm
2Ultraviolet ray, then under 110 ℃ temperature, heating (PEB) after carrying out 120 seconds exposure on the electric hot plate.Dipping 60 seconds in the TMAH of 0.4 quality % (below, the be called TMAH) WS afterwards after developing, carries out 20 seconds flowing water washing with ultrapure water.Will be at the lowest exposure amount (mJ/cm of the residual disappearance of dissolving at exposure position
2) as sensitivity.
< comparative example 5 >
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the silicon wafer, under 110 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.Thickness uses FILMETRICS system F20 to measure.Utilize キ ヤ ノ Application system ultraviolet lamp PLA-600FA, use certain hour to be 5.5mW/cm to this light intensity of filming irradiation 365nm
2Ultraviolet ray, dipping 60 seconds in the TMAH of 0.4 quality % (below, the be called TMAH) WS afterwards after developing, carries out 20 seconds flowing water washing with ultrapure water.Will be at the lowest exposure amount (mJ/cm of the residual disappearance of dissolving at exposure position
2) as sensitivity.
[evaluation that thickness reduces]
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the silicon wafer, under 110 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.This film flooded 60 seconds in the TMAH WS of 0.4 quality % after, carry out 20 seconds flowing water washing with ultrapure water.Then, measure the thickness of this film, the thickness of estimating the unexposed position that is caused by development reduces degree.In this was estimated, thickness used FILMETRICS system F20 to measure.
[evaluation of ITO sputter patience]
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the silicon wafer, under 110 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.This is filmed 230 ℃ of heating 30 minutes, carry out the back baking thus, forming thickness is filming of 1.9 μ m.At ITO thickness 5000 Ethylmercurichlorendimides, sputtering pressure 0.35Pa, Ar flow 74cm
3/ minute, under 200 ℃ of substrate heating-up temperatures, 37.6 minutes the condition of sputtering time,, this carries out the ITO sputter on filming.Film with the observation by light microscope sputter is surperficial, does not have the situation note of crackle to do zero on the surface, have the situation of crackle to remember on the surface to do *.
[evaluation of the transparency]
< embodiment 1～3, comparative example 1～4 >
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the quartz base plate, under 120 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.This is filmed in the TMAH WS of 0.4 quality % dipping after 60 seconds, carry out 20 seconds flowing water washing with ultrapure water.Then carried out the back baking in 30 minutes through heating down at 230 ℃, forming thickness is the cured film of 1.9 μ m.For this cured film, use ultraviolet-visible pectrophotometer (the system SHIMADZU UV-2550 of (strain) Shimadzu Seisakusho Ltd. model), under 200～800nm wavelength, measure.And then, this was filmed in heating under 250 ℃ after 30 minutes the mensuration transmissivity.In this was estimated, thickness used the F20 of FILMETRICS society system to measure.
< comparative example 5 >
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the quartz base plate, under 120 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.4 μ m.This is filmed in the TMAH WS of 0.4 quality % dipping after 60 seconds, carry out 20 seconds flowing water washing with ultrapure water.Utilize キ ヤ ノ Application system ultraviolet lamp PLA-600FA, film with 800mJ/cm to this
2, the irradiation 365nm light intensity be 5.5mW/cm
2Ultraviolet ray, then through 230 ℃ down heating carried out back baking in 30 minutes, the formation thickness is the cured film of 1.9 μ m.For this cured film, use ultraviolet-visible pectrophotometer (the system SHIMADZU UV-2550 of (strain) Shimadzu Seisakusho Ltd. model), under the wavelength of 200～800nm, measure.And then, this was filmed in heating under 250 ℃ after 30 minutes the mensuration transmissivity.In this was estimated, thickness used the F20 of FILMETRICS society system to measure.
[evaluation of MEA patience]
< embodiment 1～3, comparative example 1～4 >
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the quartz base plate, under 120 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.This is filmed in the TMAH WS of 0.4 quality % dipping after 60 seconds, carry out 20 seconds flowing water washing with ultrapure water.Then carried out the back baking in 30 minutes through heating down for 230 ℃ in temperature, forming thickness is the cured film of 1.9 μ m.This was filmed in the monoethanolamine that is heated to 60 ℃ of temperature dipping after 20 minutes, with pure water washing 20 seconds.Then after on the electric hot plate of 180 ℃ of temperature dry 10 minutes, carry out the mensuration of thickness and transmissivity.The situation note that thickness after the back baking is handled with MEA, dried thickness and transmissivity not have to change is made MEA patience zero, with situation about reducing remember work *.
< comparative example 5 >
After using the rotary coating machine to be coated on positive type photosensitive organic compound on the quartz base plate, under 120 ℃ temperature, on electric hot plate, carry out 120 seconds prebake conditions, forming thickness is filming of 2.5 μ m.This is filmed in the TMAH WS of 0.4 quality % dipping after 60 seconds, carry out 20 seconds flowing water washing with ultrapure water.Utilize キ ヤ ノ Application system ultraviolet lamp PLA-600FA, film with 800mJ/cm to this
2The light intensity of irradiation 365nm is 5.5mW/cm
2Ultraviolet ray, then through 230 ℃ down heating carried out back baking in 30 minutes, the formation thickness is the cured film of 1.9 μ m.This was filmed in the monoethanolamine that is heated to 60 ℃ of temperature dipping after 20 minutes, with pure water washing 20 seconds.Then under 180 ℃ temperature, after on the electric hot plate dry 10 minutes, carry out the mensuration of thickness and transmissivity.The situation note that thickness after the back baking is handled with MEA, dried thickness and transmissivity not have to change is made MEA patience zero, with situation about reducing remember work *.
[stable on heating evaluation]
In above-mentioned [evaluation of MEA patience], substrate is become silicon wafer by quartz base plate, in addition, use the same method, form the cured film of thickness 1.9 μ m.Cut this cured film, make an experiment, carry out DTA-TG and measure.Temperature when sample quality is reduced by 5 quality % reduces by 5% temperature as quality, estimates.
[evaluation result]
The result who carries out above-mentioned evaluation is as shown in table 2 below.
[table 2]
| Sensitivity (mJ/cm 2) | Thickness reduces ※(μm) | ITO sputter patience | Transmissivity (%) | MEA patience | The temperature of quality minimizing 5% (℃) | |
| Embodiment 1 | 25 | Do not have | ○ | 81 | ○ | 305 |
| Embodiment 2 | 23 | Do not have | ○ | 90 | ○ | 305 |
| Embodiment 3 | 27 | Do not have | ○ | 78 | ○ | 305 |
| Comparative example 1 | 23 | Do not have | × | 92 | ○ | 305 |
| Comparative example 2 | 35 | Do not have | × | 92 | ○ | 305 |
| Comparative example 3 | 40 | Do not have | ○ | 20 | × | 250 |
| Comparative example 4 | 35 | Do not have | × | 65 | × | 240 |
| Comparative example 5 | 120 | 0.2 | × | 92 | × | 305 |
※ " thickness does not reduce " is meant according to measuring the result and can knows, does not find the minimizing of film thickness
In embodiment 1～3, all have high sensitivity, in measuring the result, the thickness that does not in fact observe unexposed reduces, and ITO sputter patience is high, and then has high-transmission rate, and is also high to the patience of MEA.
Comparative example 1 and 2 has high sensitivity, does not in fact also observe the minimizing of unexposed thickness, has shown high-transmission rate, MEA patience and thermotolerance, but when the ITO sputter, observes crackle.
Comparative example 3 has ITO sputter patience, but transmissivity, poor heat resistance is perhaps observed thickness and reduced after MEA handles.
Comparative example 4 is observed the crackle that causes owing to the ITO sputter, and transmissivity, poor heat resistance are perhaps observed thickness and reduced after MEA handles.
Comparative example 5 has muting sensitivity, thickness occurs at unexposed and reduces, and when the ITO sputter, finds crackle, observes because MEA handles the reduction of the transmissivity that causes.
The industry utilizability
Positive type photosensitive organic compound of the present invention; Be preferably used as the material of the cured film of diaphragm in the various displays such as forming thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL, planarization film, dielectric film etc.; Especially; The material of the embossed film of the reflectance coating downside of also preferred diaphragm, array planarization film, reflective display, the dielectric film of organic EL etc. as the interlayer dielectric that forms TFT type liquid crystal cell, color filter; And then, also preferably as the various electronic materials of microlens material etc.
Claims (10)
1. a positive type photosensitive organic compound contains following A composition, B composition, C composition, D composition, E composition and F solvent,
The A composition is the alkali solubility acrylate copolymer, and it has and is selected from least a in carboxyl and the phenolic hydroxyl and is selected from the hydroxyl beyond the phenolic hydroxyl and has at least a in the amino of reactive hydrogen, and its number-average molecular weight is 2000～30000;
The B composition is the alkali soluble resins that in main chain, has aromatic ring or alicyclic structure, and this alkali soluble resins is that number-average molecular weight is 2000～30000 polyimide precursor or polyimide;
The C composition is the compound that has plural vinyl ether group in 1 molecule, and with respect to the A composition and the B composition that add up to 100 mass parts, the C composition is 1～80 mass parts;
The D composition is that the thermal dissociation temperature that has plural blocked isocyanate base, end-blocking part in 1 molecule is 120 ℃～230 ℃ a compound, and with respect to total 100 mass parts of A composition and B composition, the D composition is 1～80 mass parts;
The E composition is a light acid propellant, and with respect to total 100 mass parts of A composition and B composition, the E composition is 0.5～80 mass parts.
2. positive type photosensitive organic compound according to claim 1, B composition are to have by the polyimide precursor of the substituted alkyl of fluorine atom or polyimide.
3. positive type photosensitive organic compound according to claim 1, the B composition is a polyimide, this polyimide contains 0.5～20 mass parts with respect to A composition 100 mass parts.
4. positive type photosensitive organic compound according to claim 1, the B composition is a polyimide precursor, this polyimide precursor contains 5～100 mass parts with respect to A composition 100 mass parts.
5. positive type photosensitive organic compound according to claim 1, E composition are the compounds that produces sulfonic acid through rayed.
6. positive type photosensitive organic compound according to claim 1 as the G composition, further contains amines.
7. positive type photosensitive organic compound according to claim 1 as the H composition, further contains fluorine class surfactant.
8. cured film is to use each described positive type photosensitive organic compound of claim 1～7 to obtain.
9. an interlayer dielectric contains the described cured film of claim 8.
10. a lenticule contains the described cured film of claim 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP166267/2006 | 2006-06-15 | ||
| JP2006166267 | 2006-06-15 | ||
| PCT/JP2007/061903 WO2007145249A1 (en) | 2006-06-15 | 2007-06-13 | Positive photosensitive resin composition containing polymer having ring structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101467100A CN101467100A (en) | 2009-06-24 |
| CN101467100B true CN101467100B (en) | 2012-06-06 |
Family
ID=38831763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780021536XA Active CN101467100B (en) | 2006-06-15 | 2007-06-13 | Positive photosensitive resin composition containing polymer having ring structure |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5163899B2 (en) |
| KR (1) | KR101388998B1 (en) |
| CN (1) | CN101467100B (en) |
| TW (1) | TWI411885B (en) |
| WO (1) | WO2007145249A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8828651B2 (en) | 2005-07-25 | 2014-09-09 | Nissan Chemical Industries, Ltd. | Positive-type photosensitive resin composition and cured film manufactured therefrom |
| US8168371B2 (en) | 2007-01-22 | 2012-05-01 | Nissan Chemical Industries, Ltd. | Positive photosensitive resin composition |
| KR101113063B1 (en) * | 2008-05-22 | 2012-02-15 | 주식회사 엘지화학 | Photosensitive composition comprising polyimide and novolak resin |
| JP5571914B2 (en) * | 2009-07-17 | 2014-08-13 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device |
| KR101844738B1 (en) * | 2010-08-05 | 2018-04-03 | 닛산 가가쿠 고교 가부시키 가이샤 | Resin composition, liquid crystal orientation agent, and phase difference agent |
| KR101915138B1 (en) * | 2010-10-21 | 2018-11-06 | 닛산 가가쿠 가부시키가이샤 | Composition for forming overlaying film for resist for euv lithography |
| WO2014034301A1 (en) * | 2012-09-03 | 2014-03-06 | 富士フイルム株式会社 | Photosensitive resin composition, method for forming curable film, curable film, organic el display device, and lcd device |
| WO2014034302A1 (en) * | 2012-09-03 | 2014-03-06 | 富士フイルム株式会社 | Photosensitive resin composition, method for forming curable film, curable film, organic el display device, and lcd device |
| CN103941544A (en) * | 2014-01-26 | 2014-07-23 | 京东方科技集团股份有限公司 | Photoresist, and preparation method and application method thereof |
| WO2017057281A1 (en) * | 2015-09-30 | 2017-04-06 | 東レ株式会社 | Negative photosensitive resin composition, cured film, element and display device each provided with cured film, and method for manufacturing display device |
| JP6988485B2 (en) * | 2016-11-02 | 2022-01-05 | 東レ株式会社 | A method for manufacturing a resin composition, a resin sheet, a cured film, an organic EL display device, a semiconductor electronic component, a semiconductor device, and an organic EL display device. |
| US20210149304A1 (en) * | 2017-09-26 | 2021-05-20 | Toray Industries, Inc. | Photosensitive resin composition, cured film, element comprising cured film, organic el display device comprising cured film, method for producing cured film, and method for producing organic el display device |
| KR102288387B1 (en) * | 2018-09-03 | 2021-08-10 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer and electronic device using the same |
| WO2020065860A1 (en) * | 2018-09-27 | 2020-04-02 | 日立化成株式会社 | Photosensitive resin composition, pattern cured film and manufacturing method therefor, semiconductor element, and electronic device |
| JP7267812B2 (en) * | 2019-03-29 | 2023-05-02 | 太陽ホールディングス株式会社 | Photosensitive resin compositions, dry films, cured products, and electronic components |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570765A (en) * | 2003-07-21 | 2005-01-26 | 财团法人工业技术研究院 | Positive photoresistive agent composition and method for forming photoresistive pattern |
| CN1603957A (en) * | 2003-10-03 | 2005-04-06 | 住友化学工业株式会社 | Chemical amplification type positive resist composition and a resin therefor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4424630B2 (en) | 1999-07-13 | 2010-03-03 | 三菱レイヨン株式会社 | Chemically amplified resist composition and resist pattern forming method |
| AU2002228655A1 (en) * | 2000-11-29 | 2002-06-11 | E.I. Du Pont De Nemours And Company | Photoresist compositions comprising bases and surfactants for microlithography |
| CN1324402C (en) * | 2001-10-30 | 2007-07-04 | 钟渊化学工业株式会社 | Photosensitive resin composition and photosensitive films and laminates made by using the same |
| JP2004212678A (en) * | 2002-12-27 | 2004-07-29 | Kyocera Chemical Corp | Photosensitive resin composition and method for forming positive pattern |
| JP2005115249A (en) * | 2003-10-10 | 2005-04-28 | Fuji Photo Film Co Ltd | Photosensitive polymide composite and pattern forming method using same |
| JP4511234B2 (en) * | 2004-04-21 | 2010-07-28 | 株式会社カネカ | Photosensitive resin composition |
| JP4753036B2 (en) * | 2005-07-25 | 2011-08-17 | 日産化学工業株式会社 | Positive photosensitive resin composition and cured film obtained therefrom |
-
2007
- 2007-06-13 KR KR1020087028699A patent/KR101388998B1/en active IP Right Grant
- 2007-06-13 WO PCT/JP2007/061903 patent/WO2007145249A1/en active Application Filing
- 2007-06-13 CN CN200780021536XA patent/CN101467100B/en active Active
- 2007-06-13 JP JP2008521237A patent/JP5163899B2/en active Active
- 2007-06-15 TW TW096121849A patent/TWI411885B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570765A (en) * | 2003-07-21 | 2005-01-26 | 财团法人工业技术研究院 | Positive photoresistive agent composition and method for forming photoresistive pattern |
| CN1603957A (en) * | 2003-10-03 | 2005-04-06 | 住友化学工业株式会社 | Chemical amplification type positive resist composition and a resin therefor |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2001-27804A 2001.01.30 |
| JP特开2004-212678A 2004.07.29 |
| JP特开2005-115249A 2005.04.28 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101467100A (en) | 2009-06-24 |
| KR101388998B1 (en) | 2014-04-24 |
| WO2007145249A1 (en) | 2007-12-21 |
| TW200817840A (en) | 2008-04-16 |
| TWI411885B (en) | 2013-10-11 |
| KR20090016670A (en) | 2009-02-17 |
| JP5163899B2 (en) | 2013-03-13 |
| JPWO2007145249A1 (en) | 2009-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101467100B (en) | Positive photosensitive resin composition containing polymer having ring structure | |
| CN1904736B (en) | Positive-type photosensitive resin composition and cured film manufactured therefrom | |
| KR101369486B1 (en) | Positive Photosensitive Resin Composition and Cured Film Obtained Therefrom | |
| JP2008076740A (en) | Negative photosensitive resin composition containing compound having polymerizable group | |
| CN103229101A (en) | Photosensitive resin composition for microlenses | |
| CN1954264B (en) | Positive photosensitive resin composition, and interlayer dielectrics and micro lenses made therefrom | |
| JP5077526B2 (en) | Positive photosensitive resin composition containing a compound having an unsaturated group at the terminal | |
| CN101010634A (en) | Composition including polyamide acid for forming lower layer reflection preventing film | |
| CN101517492B (en) | Method for manufacturing transparent cured film using positive-working photosensitive resin layer for half exposure | |
| KR101285640B1 (en) | Positive Type Photosensitive Resin Composition And Cured Film Manufactured Therefrom | |
| JP4753036B2 (en) | Positive photosensitive resin composition and cured film obtained therefrom | |
| JP2008256974A (en) | Positive photosensitive resin composition | |
| KR101927829B1 (en) | Negative photosensitive resin composition | |
| TW201107367A (en) | Photosensitive polyester composition for forming thermoset film | |
| JP5585796B2 (en) | Positive photosensitive resin composition containing a compound having an unsaturated group at the terminal | |
| JP7383921B2 (en) | Polymer-containing compositions, polymers and methods for producing polymers | |
| KR20160092774A (en) | Photosensitive resin composition and organic insulating film using same | |
| TW201413387A (en) | Positive photosensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |