CN101517492B - Method for manufacturing transparent cured film using positive-working photosensitive resin layer for half exposure - Google Patents
Method for manufacturing transparent cured film using positive-working photosensitive resin layer for half exposure Download PDFInfo
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- CN101517492B CN101517492B CN2007800346563A CN200780034656A CN101517492B CN 101517492 B CN101517492 B CN 101517492B CN 2007800346563 A CN2007800346563 A CN 2007800346563A CN 200780034656 A CN200780034656 A CN 200780034656A CN 101517492 B CN101517492 B CN 101517492B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
Abstract
The present invention provides a method for manufacturing a transparent cured film having a wide exposure margin while maintaining a high level of sensitivity, especially a method for manufacturing a transparent cured film, which can be applied to the manufacture of a TFT flattening film in a semitransmission liquid crystal display element, and is used particularly for simultaneously forming contact holes and reflection concavoconvexes by half exposure. A method for manufacturing a transparent cured film, characterized by comprising stacking two positive-working photosensitive resin layers different from each other in exposure sensitivity on a base material so that the lower-sensitivity positive-working photosensitive resin layer is located between the base material and the higher-sensitivity positive-working photosensitive resin layer, exposing the positive-working resin layers to light, heating the exposed positive-working resin layers, developing the assembly, and post-baking the assembly. A display element comprising a transparent cured film produced by the above method.
Description
Technical field
The manufacturing approach of the transparent cured film that the present invention relates to use positive-working photosensitive resin layer and get.
At length say, relate to the two-layer positive-working photosensitive resin layer that the exposure sensitivity that on base material, forms is different and make public, last operation, thereby the method for manufacturing transparent cured film through drying by the fire later.
Wherein, Can be used for carrying out half exposure through the photo-sensitive resin that will have said structure; Thereby reflection horizon and the smooth transmission layer and the method for contact hole so that high precision is made arbitrary shape relate to the application when making liquid crystal display element of semi-transmission type especially.
Background technology
In general, thin film transistor (TFT) (TFT) type liquid crystal display cells has the structure of reflection-type, Semitransmissive, transmission-type etc., can suitably select according to the device that uses respectively.Wherein especially more use day and night can the high Semitransmissive that shows subtly in indoor and outdoor.In such liquid crystal display element of semi-transmission type, in order TFT to be carried out planarization and to widen aperture opening ratio and use planarization film.On such planarization film, improve reflection efficiency for the light scattering property that keeps the reflecting part, so make irregular concavo-convex on the surface.Metal on this is concavo-convex that aluminium, molybdenum is such is as reflecting plate and pixel electrode system film.On the other hand, use the such transparency electrode of ITO as pixel electrode at transmissive portions.On planarization film, form contact hole in order to make these pixel electrodes and common electrode conducting.
As the method for making so concavo-convex and contact hole; The following method of many uses promptly through using photosensitive material on substrate, to make the thick film projection, further is coated with photosensitive material above that projection is carried out planarization to a certain degree; Thereby make reflection with concavo-convex, form contact hole then.
But,,, therefore, require to improve this output so can not improve the output (production efficiency) that element is made because such method needs 2 use photosensitive materials to form pattern.
Therefore in recent years, people propose also to have gradually adopted after the coating photosensitive material, through be situated between by half-tone mask make public (half exposure) come to make simultaneously contact hole and reflection with concavo-convex method.
Here employed photosensitive material requires following all characteristics: anti-excellent in workability such as thermotolerance, solvent resistance; Good adhesion with substrate; Has the broad finish allowance (margin) that under various processing conditionss, can form pattern with high precision according to application target; And be high sensitivity and high transparent, and film is inhomogeneous less after developing, or the like.
Therefore, require the aspect of characteristic from these, all the time, as above-mentioned photosensitive material, the general photosensitive polymer combination that contains naphthoquinone two azide.
Yet,, can enumerate sensitivity and finish allowance as important characteristic in the desired characteristic of this photoresist material.Because the raising of sensitivity; Can make in the commercial production of display device etc. and significantly shorten its production time; So under the present situation that the requirement of LCD enlarges markedly, sensitivity has become one of desired most important characteristic of this photoresist material.In addition, in order to form high-precision reflection horizon according to design, finish allowance is important, and in recent years along with substrate maximizes, from improving the aspect of qualification rate, exposure allowance, development allowance must broads.
But, contain the existing photoresist material of above-mentioned naphthoquinone two azide, can not be fully satisfied aspect sensitivity.Though can improve sensitivity through the dissolubility of polymkeric substance in alkaline-based developer that improves in the material; But there is boundary in this method, also has drawback, and promptly unexposed dissolving also takes place and residual film ratio decline; This uses substrate for giant display, is to cause the uneven reason of film.
Therefore, up to the present, for the photoresist material is carried out high sensitivityization and has proposed several schemes.
For example, the someone has proposed radiation sensitive resin composition, wherein contain alkali soluble resins and specific polyol and derivant thereof at least a (for example; Referenced patent document 1); But the existing photoresist material that contains naphthoquinone two azide when Jie is made public by half-tone mask, carry out high sensitivityization more; The exposure allowance of half exposure area has the tendency of reduction more, can not realize the raising of high sensitivity and exposure allowance simultaneously.
On the other hand; As high sensitivity, high-resolution photosensitive material, people have developed chemically amplified corrosion-resisitng agent now, and have proposed; The existing chemically amplified corrosion-resisitng agent of developing with resist as semiconductor; The light source (KrF, ArF) shorter can also be used for, finer pattern (for example, the referenced patent document 2) can be formed than i line wavelength.
But; Even above-mentioned chemically amplified corrosion-resisitng agent; Solidify at film under the high temperature of employed that kind, and in the presence of anticorrosive additive stripping liquid controlling, also decompose easily at the binding site of protection base, the heat cross-linking position of ehter bond; So thermotolerance and chemical resistance are significantly low, possibly use as permanent film hardly.
In addition; Even for can heat curing and will the cross-linking system of epoxies, amino plastics class be imported in the chemically amplified corrosion-resisitng agent; Also since through the exposure and by the photoacid generator in the resist (below; Be also referred to as PAG) influence of the acid that produces, and produce exposure portion carry out crosslinked, with unexposed new problems such as dissolving contrast disappearances, therefore be difficult to this cross-linking system importing chemically amplified corrosion-resisitng agent.
In such situation, making liquid crystal display element of semi-transmission type, when particularly making planarization film, the peristome bore through adjusting half exposure mask pattern, make public at interval, thereby form contact hole, relief pattern is used in reflection.But the adjustment amount of mask is limited, for precision forms relief pattern well, must reduce the exposure sensitivity of planarization film.Therefore in order to form contact hole, must increase exposure, consequently, be difficult to improve the output of making element.
Patent documentation 1: the spy opens flat 4-211255 communique
Patent documentation 2: No. 5075199 instructions of United States Patent (USP)
Summary of the invention
The objective of the invention is, in order to overcome aforesaid problem, and be provided at the manufacturing approach of keeping the transparent cured film that has broad exposure allowance (margin) under the highly sensitive state.The object of the invention especially provides a kind of manufacturing approach of transparent cured film; Said transparent cured film can be used when the TFT planarization film in making liquid crystal display element of semi-transmission type, especially for forming contact hole simultaneously and reflect with concavo-convex through half exposure.
Promptly; As first scheme be; A kind of manufacturing approach of transparent cured film, this manufacturing approach comprises following operation: at the different two-layer positive-working photosensitive resin layer of base material superimposed layer exposure sensitivity, make the operation of positive-working photosensitive resin layer between said base material and highly sensitive positive-working photosensitive resin layer of muting sensitivity, the operation that the two-layer positive-working photosensitive resin layer behind this lamination is made public; With the make public operation of back heating of this two-layer positive-working photosensitive resin layer; With the operation that this two-layer positive-working photosensitive resin layer develops, the operation of this two-layer positive-working photosensitive resin layer being carried out the back baking
The manufacturing approach of this transparent cured film is characterised in that, the positive-working photosensitive resin layer of this muting sensitivity is to contain following (A) composition, (B) composition, (C) composition and (D) positive-working photosensitive resin layer of composition,
(A) composition is an alkali soluble resins,
(B) composition is the compound that has two above vinyl ether groups in 1 molecule,
(C) composition is the compound that toasts through the back and (A) composition carries out cross-linking reaction,
(D) composition is a photoacid generator.
Be that according to the manufacturing approach of the described transparent cured film of first scheme, said exposure is half exposure as alternative plan.
As third party's case be, according to the manufacturing approach of first scheme or the described transparent cured film of alternative plan, heating is carried out under 80 ℃～140 ℃ of temperature after the said exposure, and the baking of said back is carried out under 150 ℃～270 ℃ of temperature.
As cubic case be; Manufacturing approach according to each described transparent cured film of first scheme～third party's case; Said highly sensitive positive-working photosensitive resin layer is to contain following (A) composition, (B) composition, (C) composition and (D) positive-working photosensitive resin layer of composition
(A) composition is an alkali soluble resins,
(B) composition is the compound that has two above vinyl ether groups in 1 molecule,
(C) composition is the compound that toasts through the back and (A) composition carries out cross-linking reaction,
(D) composition is a photoacid generator.
As the 5th scheme is the manufacturing approach according to each described transparent cured film of first scheme～cubic case; In the positive-working photosensitive resin layer of said muting sensitivity; Based on 100 mass parts (A) composition, contain 1～80 mass parts said (B) composition, said (C) composition of 1～70 mass parts and 0.5～50 mass parts said (D) composition.
As the 6th scheme is the manufacturing approach according to each described transparent cured film of first scheme～the 5th scheme, and base material is the base material that has formed the TFT element.
As the 7th scheme is a kind of tft array planarization film, comprises the transparent cured film that each the described manufacturing approach by first scheme～the 5th scheme obtains.
As the case from all directions, be a kind of display element, have the transparent cured film that each the described manufacturing approach by first scheme～the 5th scheme obtains.
As the 9th scheme, be a kind of liquid crystal display cells, have the transparent cured film that each the described manufacturing approach by first scheme～the 5th scheme obtains.
The transparent cured film of gained of the present invention; Because have effects such as highly sensitive and exposure allowance broad of 1 when exposure, thus be particularly suitable for high sensitivity simultaneously precision form well in the manufacturing of liquid crystal display element of semi-transmission type of concavo-convex and contact hole of TFT planarization film and use.
Embodiment
The present invention is a kind of manufacturing approach of transparent cured film; It is characterized in that; Comprise following operation; Promptly the two-layer positive-working photosensitive resin layer that exposure sensitivity is different carries out lamination on base material, makes the positive-working photosensitive resin layer of muting sensitivity between said base material and highly sensitive positive-working photosensitive resin layer, the back heating (Post Exposure Bake:PEB) that will make public by this two-layer positive-working photosensitive resin layer that forms then, make public, develop, the back baking.
At length say; The present invention is a kind of manufacturing approach of transparent cured film; This manufacturing approach comprises following operation; That is, thereby be stacked in the operation on the base material, the operation that the two-layer positive-working photosensitive resin layer behind this lamination is made public at the positive-working photosensitive resin layer that forms muting sensitivity on the base material and then at the highly sensitive positive-working photosensitive resin layer of this muting sensitivity layer superimposed layer two-layer positive-working photosensitive resin layer that exposure sensitivity is different; With the make public operation of back heating of this two-layer positive-working photosensitive resin layer; With the operation that this two-layer positive-working photosensitive resin layer develops, with the operation that this two-layer positive-working photosensitive resin layer carries out the back baking, the manufacturing approach of this transparent cured film is characterised in that; The positive-working photosensitive resin layer of this muting sensitivity is to contain following (A) composition, (B) composition, (C) composition and (D) positive-working photosensitive resin layer of composition
(A) composition is an alkali soluble resins,
(B) composition is the compound that has two above vinyl ether groups in 1 molecule,
(C) composition is the compound that toasts through the back and (A) composition carries out cross-linking reaction,
(D) composition is a photoacid generator.
Manufacturing method according to the invention; Can carry out lamination through two-layer positive-working photosensitive resin layers on base material that exposure sensitivity is different; Thereby when Jie is made public by half-tone mask; In the positive-working photosensitive resin layer of highly sensitive positive-working photosensitive resin layer (below, be called high sensitivity) and muting sensitivity (below, be called the muting sensitivity layer), form different pattern forms.That is, manufacturing method according to the invention can utilize 1 exposure in high sensitivity and muting sensitivity layer, to form the pictures different shape through being situated between by half-tone mask.
In the present invention; Because according to making muting sensitivity layer that kind between said base material and high sensitivity carry out lamination; So when developing; As unexposed remaining high sensitivity and muting sensitivity layer, be removed and remaining muting sensitivity layer in half exposure portion, high sensitivity, in exposure portion fully, positive-working photosensitive resin layer (high sensitivity and muting sensitivity layer) is removed fully and base material exposes.
Here said half exposure portion can develop with the exposure that is less than the portion of exposure fully, and can form the part of desirable image (image).
In order to obtain desirable image, require to suppress the muting sensitivity layer of lamination and mixing of high sensitivity.Under the inadequate situation of inhibition of said two-layer mixing, the interface of muting sensitivity layer and high sensitivity becomes unintelligible, is difficult to obtain desirable image when partly making public.
In the present invention; When forming the muting sensitivity layer,, carry out predrying (heat treated) then through being coated with the solution of the positive type photosensitive organic compound that forms this layer; Thereby it is crosslinked that the composition that this resin combination is contained carries out each other, on base material, forms the film that is insoluble in organic solvent thus.Therefore, when on the muting sensitivity layer, forming high sensitivity afterwards, even coating forms the positive type photosensitive organic compound solution of this layer, the muting sensitivity layer can not mix with high sensitivity yet.
And; Under the situation of high sensitivity and muting sensitivity layer being shone respectively less than the light of the required exposure that begins to develop; Film reduces and to be suppressed during development, and after irradiation began to develop the light of required exposure, develop rapidly (high precision and highly sensitive) was preferred.
Here, in half exposure portion, the difference of the exposure when exposure the when dissolving of muting sensitivity layer finishes during development and high sensitivity begin to dissolve is half exposure allowance.The poor sensitivity of this and high sensitivity and muting sensitivity layer is closely related, and this two-layer poor sensitivity allowance of more greatly then partly making public is big more.That is, the sensitivity of high sensitivity is high more, and the sensitivity of muting sensitivity layer is low more, and the exposure allowance is just wide more.In order to obtain high-precision image, the allowance of preferably partly making public is more than the 10mJ.
On the other hand, in order to improve the output of making element, the high sensitivity that the muting sensitivity layer has to a certain degree is important.This is because if excessively increase the muting sensitivity layer required exposure that begins to develop in order to improve half exposure allowance, then the result can reduce the sensitivity of muting sensitivity layer, causes output to reduce on the contrary.
So, as the muting sensitivity layer, the chemical amplifying type photographic layer that preference such as sensitivity are higher.
Therefore, requiring high sensitivity is than the more highly sensitive photographic layer of highly sensitive muting sensitivity layer, the preferred higher chemical amplifying type photographic layer of sensitivity.
Positive-working photosensitive resin layer used in the present invention can obtain transparent cured film through after forming desired image, carrying out the back baking as stated.
Below narrate for preferred positive-working photosensitive resin layer.
< muting sensitivity positive-working photosensitive resin layer (muting sensitivity layer) >
Muting sensitivity layer used in the present invention is formed by following positive type photosensitive organic compound, and said positive type photosensitive organic compound contains: have in 1 molecule as the alkali soluble resins of (A) composition, conduct (B) composition two above vinyl ether groups compound, conduct (C) composition pass through that back baking and (A) composition carry out the compound of cross-linking reaction and as the photoacid generator of (D) composition.
Usually, the muting sensitivity layer can be processed solution morphology through above-mentioned positive type photosensitive organic compound is dissolved in (E) solvent, again with this solution coat on base material and carry out drying, thereby form.Below narrate for each composition.
[(A) composition]
(A) composition is an alkali soluble resins; As preferred resin; Can enumerate following alkali soluble resins: have in the resin structure can and as the functional group that carries out the heat cross-linking reaction between the compound with vinyl ether group of (B) composition; And can and as (C) composition pass through carry out the functional group that is used for film curing that heat curing is reacted between the compound that back baking and (A) composition carry out cross-linking reaction, and number-average molecular weight is 2000～50000 alkali soluble resins.
In other words; (A) composition is an alkali soluble resins, as preferred resin, can enumerate following alkali soluble resins; Promptly; Having in the resin structure can be through preliminary drying and as the functional group that carries out the heat cross-linking reaction between the compound with vinyl ether group of (B) composition, thereby and can carry out the functional group that is used for film curing that cross-linking reaction is carried out the heat curing reaction through back baking and (C) composition, and number-average molecular weight is 2000～50000 alkali soluble resins.
The functional group that is used for the heat cross-linking reaction; Be can be under higher temperature vinyl ether group in the compound of (temperature of preliminary drying) and (B) composition react; Thereby and (B) carrying out the group of heat cross-linking between the compound of composition, its representational functional group is selected from least a in carboxyl and the phenol property hydroxyl.
In addition; Be used for the functional group that film solidifies; Be can be (to exposure portion in the heat cross-linking body of above-mentioned (A) composition and (B) composition; Be separating in the crosslinked body after the heat cross-linking body further dissociates), under higher temperature (back baking temperature), and (C) carry out cross-linking reaction between the compound of composition, thus the group that film is solidified.
As hereinafter described; At (C) composition is to have under the situation of compound of 2 above blocked isocyanate bases; Be situated between the NCO that partly dissociates by block between the compound of the functional group that being used for of (A) becoming that branch has, film solidified and (C) composition and carry out cross-linking reaction, thereby make film curing.
As the representative functional group that is used for the functional group that film solidifies, be at least a in hydroxyl and the amino that has reactive hydrogen that is selected from except that phenol property hydroxyl.
Here, what is called has the amino of reactive hydrogen, and meaning the primary amino radical or the secondary amino group that can discharge proton through reaction.Therefore, amide group is not owing to having reactive hydrogen, so do not belong to the amino that has reactive hydrogen.
(A) alkali soluble resins of composition is so long as have the alkali soluble resins of this structure and get final product, and the polymeric main chain backbone that constitutes resin and side chain kind etc. are not limited especially.
But (A) number-average molecular weight of the resin of composition is in 2000～50000 the scope.If number-average molecular weight surpasses 50000 and excessive, then be easy to generate the development residue, sensitivity descends significantly.On the other hand, if number-average molecular weight less than 2000 and too small, the film that exposure portion produces a great deal of when then developing reduces, and solidifies insufficient sometimes.
As the alkali soluble resins of (A) composition, for example can enumerate, acrylic resin, polycarboxylated styrene are resin or polyimide precursor or polyimide etc.
In the present invention, can use by multiple monomer carry out polymerization and the alkali soluble resins that forms of multipolymer (below, be called specific copolymer) as (A) composition.At this moment, (A) alkali soluble resins of composition can be the potpourri of multiple specific copolymer.
Promptly; Above-mentioned specific copolymer is the multipolymer that forms as essential formation unit with alkali-soluble monomer of following performance and following monomer with the functional group that is used for film curing; Its number-average molecular weight (polystyrene calibration) is 2000～50000; The alkali-soluble monomer of said performance is at least a monomer of suitably selecting at least one side's from have carboxyl and phenol property hydroxyl the monomer, and said to have the monomer that is used for the functional group that film solidifies be at least a monomer of from the monomer with hydroxyl and at least one side of the amino that has reactive hydrogen except that phenol property hydroxyl, suitably selecting.
In addition; The number-average molecular weight of above-mentioned specific copolymer and weight-average molecular weight; For example; The GPC device (Shodex (registered trademark) post KF803L and KF804L) that can use Japanese beam split (strain) to make is measured the eluting solvent tetrahydrofuran was flow through the condition that (40 ℃ of column temperature) in the post make it wash-out with flow 1ml/ minute under.
Above-mentioned " monomer with at least one side in carboxyl and the phenol property hydroxyl " comprises monomer with carboxyl, has the monomer of phenol property hydroxyl and have carboxyl and the monomer of phenol property hydroxyl.These monomers are not limited to have a carboxyl or phenol property hydroxyl, also can have a plurality of.
In addition, above-mentioned " having hydroxyl and the monomer that has at least one side in the amino of reactive hydrogen except that phenol property hydroxyl " comprises monomer with the hydroxyl except that phenol property hydroxyl, has the monomer of the amino that has reactive hydrogen and has the hydroxyl except that phenol property hydroxyl and have the monomer of the amino of reactive hydrogen.These monomers be not limited to have one except that phenol property hydroxyl hydroxyl or have the amino of reactive hydrogen, also can have a plurality of.
Below, enumerate the concrete example of above-mentioned monomer, but be not limited to these.
As monomer with carboxyl; For example can enumerate acrylic acid, methacrylic acid, crotonic acid, list (2-(acryloyl-oxy) ethyl) phthalic ester, list (2-(methacryloxypropyl) ethyl) phthalic ester, N-(carboxyl phenyl) maleimide, N-(carboxyl phenyl) Methacrylamide, N-(carboxyl phenyl) acrylic amide etc.
As monomer, for example can enumerate hydroxy styrenes, N-(hydroxy phenyl) acrylic amide, N-(hydroxy phenyl) Methacrylamide, N-(hydroxy phenyl) maleimide etc. with phenol property hydroxyl.
As monomer with the hydroxyl except that phenol property hydroxyl; For example can enumerate acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, 5-acryloyl-oxy-6-hydroxyl ENB-2-carboxylic acid-6-lactone, 2-hydroxyethyl methacry-late, methacrylic acid-2-hydroxypropyl acrylate, 5-methacryloxypropyl-6-hydroxyl ENB-2-carboxylic acid-6-lactone etc.
And then, as monomer, can enumerate acrylic acid-2-amino ethyl ester, methacrylic acid-2-amino methyl etc. with the amino that has reactive hydrogen.
In addition, specific copolymer also can be also with except monomer with the functional group that is used for heat cross-linking reaction with have the multipolymer that monomer the monomer that is used for the functional group that film solidifies (below, be called other monomer) forms as constituting the unit.
Other monomer specifically; So long as can with have in carboxyl and the phenol property hydroxyl at least one monomer and have the hydroxyl except that phenol property hydroxyl and at least one the monomer of monomer copolymerization that has in the amino of reactive hydrogen gets final product; Only otherwise the characteristic of infringement (A) composition, just restriction especially.
As the concrete example of other monomer, can enumerate acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and ethylene compounds etc.
As acrylate compounds; For example can enumerate; Methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthracene methyl esters, phenyl acrylate, acrylic acid-2; 2,2-trifluoro ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, IBOA, acrylic acid-2-methoxyl ethyl ester, methoxyl triethylene glycol acrylic ester, acrylic acid-2-ethoxy ethyl ester, tetrahydrofurfuryl acrylate, 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; Methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthracene methyl esters, phenyl methacrylate, methacrylic acid-2; 2,2-trifluoro ethyl ester, metering system tert-butyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid-2-methoxyl ethyl ester, methoxyl triethylene glycol methacrylate, methacrylic acid-2-ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, 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 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 styrene, methyl styrene, chlorostyrene, bromstyrol etc.
As maleimide compound, for example can enumerate maleimide, N-methyl maleimide, N-phenylmaleimide and N-cyclohexyl maleimide etc.
To the not restriction especially of method that obtains specific copolymer used in the present invention; For example; Can through make at least a monomer suitably selected at least one the monomer from have carboxyl and phenol property hydroxyl, from having the hydroxyl except that phenol property hydroxyl and having at least a monomer suitably selected at least one the monomer the amino of reactive hydrogen, as required the monomer except that above-mentioned monomer and polymerization initiator as required etc.; In solvent, under 50～110 ℃ temperature, carry out polyreaction, thereby obtain.At this moment, the solvent of use does not limit so long as can dissolve the monomer that constitutes specific copolymer and get final product with the solvent of specific copolymer especially.As concrete example, the described solvent of stating after can enumerating of (E) solvent.
The specific copolymer that obtains like this is the solution state that in solvent, dissolves of this specific copolymer normally.
In addition; Can under agitation drop into through solution and make it to precipitate again in ether, the water etc. the specific copolymer that get as stated; The sediment that generates is filtered, washs, under normal pressure or reduced pressure, carry out normal temperature or heat drying then, thereby process the powder of specific copolymer.Through such operation, can remove the polymerization initiator, the unreacted monomer that coexist with specific copolymer, the result is the powder that obtains the specific copolymer of purifying.Under can not situation, can the powder that obtain dissolving once more in solvent be repeated aforesaid operations with the abundant purifying of single job.
In the present invention, can directly use the powder of specific copolymer, dissolving once more in (E) solvent that perhaps can this powder be stated after is for example used thereby process solution state.
In addition; Alkali soluble resins as (A) composition; Can use polyamic acid, poly amic acid ester, part imidizate polyimide precursors such as polyamic acid, contain carboxylic acid group's polyimide such as polyimide, they are not so long as alkali-soluble can the use limited kind especially.
From development property, to the deliquescent viewpoint of the solvent that uses, the number-average molecular weight of above-mentioned polyimide precursor, polyimide (polyethylene oxide and polyglycol calibration value) is in 2000～50000 the scope.
In addition; Number-average molecular weight and weight-average molecular weight to above-mentioned polyimide precursor, polyimide; For example; The GPC device (Shodex (registered trademark) post KD802, KD803 and KD804) that can use Japanese beam split (strain) to make, at the N with eluting solvent 0.1mol% lithium bromide, dinethylformamide solution makes it to measure under the such condition of wash-out to flow through in the post (40 ℃ of column temperature) in flow 1ml/ minute.
Generally can obtain as the above-mentioned polyamic acid of polyimide precursor through (a) tetracarboxylic dianhydride compound and (b) diamine compound are carried out polycondensation.
To the not restriction especially of (a) tetracarboxylic dianhydride compound, if enumerate concrete example, then can enumerate PMDA, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4; 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4, aromatic tetracarboxylic acids such as 4 '-diphenyl sulfone tetracarboxylic dianhydride; 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3; 4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1; 2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, 3,4-dicarboxyl-1; 2,3, the ester ring type tetracarboxylic dianhydride that 4-tetrahydrochysene-1-naphthalene succinic dianhydride is such, 1,2,3, the aliphatics tetracarboxylic dianhydride that 4-butane tetracarboxylic acid dianhydride is such.
Can these compound combinations more than a kind or 2 kinds be used.
In addition, to (b) diamine compound also not restriction especially, for example can enumerate 2; 4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diaminostilbene; 3-phthalic acid, 2, the 5-diaminostilbene, (4-amino-3 for 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; 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, 1,4-two (4-amino-3-carboxyl phenoxy group) benzene, 1,3-two (4-amino-3-carboxyl phenoxy group) benzene, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] sulfone, two [4-(4-amino-3-carboxyl phenoxy group) phenyl] propane, 2,2-two [4-(4-amino-3-carboxyl phenoxy group) phenyl] HFC-236fa; 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4; 6-diamino resorcin, 2, (4-amino-3 for 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; The 5-dihydroxy phenyl) sulfone, 2,2-two (3-amino-4-hydroxy phenyl) HFC-236fa, 2,2-two (4-amino-3-hydroxy base) HFC-236fa, 2, (4-amino-3 for 2-two; The 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, 1,4-two (3-amino-4-hydroxy phenoxy group) benzene, 1; 3-two (3-amino-4-hydroxy phenoxy group) benzene, 1,4-two (4-amino-3-hydroxy oxygen base) benzene, 1,3-two (4-amino-3-hydroxy oxygen base) benzene, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] sulfone, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] propane, 2; 2-two [4-(3-amino-4-hydroxy phenoxy group) phenyl] HFC-236fa etc. has the diamine compound of phenol property hydroxyl, and 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, 2,2-two (3-amino-4-sulfydryl phenyl) HFC-236fa etc. has the diamine compound of benzenethiol base; 1,3-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, 4; 4 '-diamido-3,3 '-dimethyl diphenyl-6,6 '-disulfonic acid etc. have sulfonic diamine compound.Can also enumerate 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; 2-two [4-(3-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride, 4; 4 '-diamino-diphenyl ether, 3,4-diamino-diphenyl ether, 4,4 '-MDA, 2,2-two (4-anilino-) HFC-236fa, 2; 2-two (3-anilino-) HFC-236fa, 2,2-two (3-amino-4-toluyl groups) HFC-236fa, 1,4-two (4-amino-benzene oxygen) benzene, 1; 3-two (4-amino-benzene oxygen) benzene, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2, diamine compounds such as 2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa.
Can these compound combinations more than a kind or 2 kinds be used.
Polyamic acid used in the present invention is under the situation about being made by (a) tetracarboxylic dianhydride compound and (b) diamine compound; The match ratio of preferred two compounds, promptly < (b) total mole number of diamine compound/(a) total mole number of tetracarboxylic dianhydride's compound>is 0.7～1.2.The same with common polycondensation reaction, this mol ratio degree of polymerization near the polyamic acid of 1 generation more is big more, thereby molecular weight increases.
In addition, when excessive use diamine compound carries out polymerization, thereby can make the terminal amino group of carboxylic acid anhydrides and remaining polyamic acid react the protection terminal amino group.
As the example of such carboxylic acid anhydrides, can enumerate phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenation phthalic anhydride, methyl-5-ENB-2,3-dicarboxylic anhydride, itaconic anhydride, tetrabydrophthalic anhydride etc.
When making polyamic acid, the temperature of reaction that diamine compound and tetracarboxylic dianhydride's compound react can be selected-20～150 ℃ arbitrary temp, is preferably-5～100 ℃ arbitrary temp.In order to obtain the polyamic acid of HMW, can in 5 ℃～40 ℃ of temperature of reaction, the scope in 1 hour～48 hours reaction time, suitably select.For obtain low-molecular-weight and storage stability high by the polyamic acid of part imidizate, more preferably be selected from 40 ℃～90 ℃ of temperature of reaction, reaction time more than 10 hours.
In addition, by under the situation of acid anhydrides protection, temperature of reaction can be selected-20～150 ℃ arbitrary temp, is preferably-5～100 ℃ arbitrary temp with terminal amino group.
The reaction of diamine compound and tetracarboxylic dianhydride's compound can be carried out in solvent.As operable solvent at this moment; Can enumerate N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, N-vinyl pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, metacresol, gamma-butyrolacton, ethyl acetate, acetate butyl, 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, glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl methyl ether, Propylene Glycol Dimethyl Ether, dipropylene glycol dimethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, propylene glycol methyl ether acetate, carbitol acetic acid esters, ethyl cellosolve acetate, cyclohexanone, MEK, methyl isobutyl ketone, 2-heptanone etc.They both can use separately, also can mix use.And then, even the insoluble solvent of separating polyamic acid as long as in the scope that the polyamic acid that polyreaction generated is not separated out, just can mix use in above-mentioned solvent.
The solution that contains the polyamic acid that obtains like this can directly be used to modulate the solution of positive type photosensitive organic compound.In addition, also can make polyamic acid in lean solvents such as water, methyl alcohol, ethanol, carry out precipitate and separate and reclaim, use then.
The polyamic acid that obtains so also can carry out esterification with carboxyl, uses as poly amic acid ester.
The polyamic acid that obtains so both can use separately, also can use simultaneously with above-mentioned alkali soluble resins.
In addition, in the present invention, can use polyimide arbitrarily.As polyimide used in the present invention is to make polyimide precursors such as above-mentioned polyamic acid carry out the product of imidizate more than 50% through chemical method or by the use of thermal means.Also contain multipolymers such as polyamidoimide, polyetherimide in these polyimide.
In order to give alkali solubility, the polyimide in the positive type photosensitive organic compound used in the present invention preferably has carboxyl or phenol property hydroxyl, perhaps has the group that can generate carboxylic acid or phenol property hydroxyl through heat or acid effect.
As the method that in polyimide, imports carboxyl, phenol property hydroxyl, can use following method: using monomer methods with carboxyl or phenol property hydroxyl, using the terminal method of acid anhydrides sealing amine with carboxyl or phenol property hydroxyl or when polyimide precursor is carried out imidizate, make the imidizate rate is the method etc. below 99%.
In addition, in polyimide, import to utilize heat or acid effect and generate the method for the group of carboxylic acid or phenol property hydroxyl, following method is arranged: use the monomer methods of utilizing heat or acid effect and generating carboxyl or phenol property hydroxyl; Make the method for reacting through the carboxylic acid residues behind heat or acid the effect group that dissociates and the carboxyl, phenol property hydroxyl or the imidizate that import in advance.
Such polyimide can obtain through carrying out chemical imidizate or hot-imide after synthetic above-mentioned polyimide precursor.
As the method for chemical imidizate, generally use and in polyimide precursor solution, add excessive acetic anhydride via and pyridine, make it ℃ method of reacting in room temperature～100.In addition, as the method for hot-imide, the general method that polyimide precursor solution is dewatered and heated simultaneously 180 ℃～250 ℃ of temperature of using.
The polyimide that obtains so not only can use separately but also can use simultaneously with above-mentioned other alkali soluble resins (for example specific copolymer etc.).
[(B) composition]
(B) composition is the compound that has two above vinyl ether groups in 1 molecule.It does not limit its kind and structure so long as the compound that can be under preliminary drying temperature commonly used carries out having in the 1 such molecule of heat cross-linking two above vinyl ether groups with (A) alkali soluble resins of composition get final product especially.
The compound that is somebody's turn to do (B) composition is after the alkali soluble resins with (A) composition carries out heat cross-linking; Owing to the acid that in the presence of photoacid generator, makes public and generate; Thereby separate (separating crosslinked) from the alkali soluble resins of (A) composition; Develop through the use alkaline-based developer then, thereby be removed with the alkali soluble resins of (A) composition.Therefore as this compound, generally can use in the composition of vinyl ether type chemically amplified corrosion-resisitng agent employed vinyl ether based compound etc.Under the situation of using this compound, have and can adjust heat cross-linking density through the use level that changes this compound, thus the advantage of the image that control forms.
And, as the compound of (B) composition, can there be the aspect that residual film, residue ground develop, the compound shown in preferred formula (1) and the formula (2) especially among the above-mentioned vinyl ether based compound from the exposure position.
(in the formula, n is 2～10 integer, and k is 1～10 integer, R
1The organic group of expression n valency.)
(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 2～4 integer more preferably.And the m of formula (2) also representes the number of the vinyl ether group in a part, as m, and 2～4 integer more preferably.
Concrete example as the compound shown in above-mentioned formula (1) and the above-mentioned formula (2); Can enumerate two (4-(ethene yloxymethyl) cyclohexyl methyl) glutarate, triethylene glycol divinyl ether, hexane diacid divinyl ester, diethylene glycol divinyl ether, three (4-(vinyl oxygen base) butyl) trimellitate, two (4-(vinyl oxygen base) butyl) terephthalate, two (cyclohexanedimethanol divinyl ethers such as 4-(vinyl oxygen base) butyl isophthalic acid ester and 1,4 cyclohexane dimethanol divinyl ether etc.
In addition, with respect to 100 mass parts (A) composition, (B) compound of composition can use with the ratio of 1～80 mass parts, preferably uses with the ratio of 5～40 mass parts.If (B) use amount of the compound of composition is the too small amount of the lower limit of not enough above-mentioned scope, then unexposed film subtracts significantly, so the undulations of the pattern that forms is bad.On the other hand, if (B) use amount of the compound of composition is the mistake volume that surpasses the upper limit of above-mentioned scope, then the sensitivity of film descends significantly, so between pattern, produce residue after developing.
[(C) composition]
(C) composition is through the compound that toast the back and (A) composition carries out cross-linking reaction, is fit to use the compound that has two above blocked isocyanate bases in 1 molecule.It so long as with respect to by and (B) carry out heat cross-linking or further and (B) separate the film that the alkali soluble resins of crosslinked (A) composition forms between the compound of composition between the compound of composition; The compound that can under back baking temperature for example commonly used, carry out having in the 1 such molecule of heat curing two above blocked isocyanate bases get final product, and its kind and structure are not limited especially.
Be somebody's turn to do the compound of (C) composition; Be to have two above NCOs (blocked isocyanate base that NCO) is formed in 1 molecule by proper protection base block; If under the high temperature when being exposed to heat curing; Then thermal dissociation takes place and breaks away from protection base (block part), thereby the functional group (for example going out hydroxyl and the amino with reactive hydrogen outside the phenol property hydroxyl) that is used for heat curing in the alkali soluble resins with (A) composition of being situated between by the NCO that generates carries out the compound of cross-linking reaction each other, for example can enumerate; Have two compounds in 1 molecule with the group shown in the following formula (3) (this group can be identical, can also be different separately).
(in the formula, R
2The organic group of expression block part.)
The compound that has (C) composition of two above blocked isocyanate bases in 1 molecule for example can obtain through making the compound effect that has two above NCOs in suitable block agent and 1 molecule.
As the compound that has two above NCOs in 1 molecule; For example can enumerate; IPDI, 1; 6-hexamethylene diisocyanate, methylene two (4-cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate etc., or their dimer, tripolymer, or the reactant of they and glycols, three alcohols, two amines, three amines.
As the block agent; For example can enumerate; Methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, 2-ethoxy hexanol, 2-N; Alcohols such as N-dimethylaminoethanol, cellosolvo, cyclohexanol, lactams such as phenols such as phenol, o-nitrophenol, parachlorophenol, orthoresol, metacresol or paracresol, epsilon-caprolactams, oximes such as acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, acetophenone oxime, diphenyl-ketoxime; Pyrazoles, 3, thio-alcohols such as pyrazoleses such as 5-dimethyl pyrazole, 3-methylpyrazole, dodecyl mercaptans, benzenethiol.
(C) compound of composition is under the such higher temperatures of back baking temperature, and block partly thermal dissociation takes place and is situated between and carried out the compound of cross-linking reaction by NCO.For under the such lower temperature of preliminary drying temperature; Do not carry out crosslinked through NCO; As the compound of (C) composition, the thermal dissociation temperature of preferred especially block part is higher than the compound of preliminary drying temperature far away, and for example the thermal dissociation temperature of block part is 120 ℃～230 ℃ a compound.
As the compound of this (C) composition, can enumerate for example following concrete example.
In the formula, from the aspect of thermotolerance, filming property, more preferably isocyanate compound is the compound of IPDI derivant (C) composition, as such compound, can enumerate following compound.
R in the following formula representes organic group.
In the present invention, (C) compound of composition can use separately a kind of, can also be more than two kinds combination use.
In addition, (C) compound of composition can use with the ratio of 3～70 mass parts with respect to 100 mass parts (A) composition, preferably uses with the ratio of 5～40 mass parts.If (C) use amount of the compound of composition is the too small amount of the lower limit of not enough above-mentioned scope; Then heat curing is insufficient; So can not get satisfied cured film, on the other hand, if (C) use amount of the compound of composition is the mistake volume that surpasses the upper limit of above-mentioned scope; It is insufficient then to develop, so produce the development residue.
[(D) composition]
(D) composition is photoacid generator (being also referred to as PAG).It is owing to produced acid (sulfonic acid class, carboxylic acids etc.) material directly or indirectly by the employed rayed of exposure, gets final product so long as have the material of such character, to not restriction especially such as its kind and structure.
Photoacid generator as (D) composition; For example can enumerate diazomethane compound, salt compound, sulfimine compound, two sulfone based compounds, sulfonic acid compound, nitrobenzene idol acyl compound, benzoin tosylate compound, iron-aromatic hydrocarbons complex, the triaizine compounds that contains halogen, acetophenone derivs compound and contain the oxime sulfonates compound etc. of cyanic acid.Any all can use photoacid generator that all the time known or employed all the time in the present invention, not restriction especially.In addition, in the present invention, (D) photoacid generator of composition can use separately a kind of, can also be more than two kinds combination use.
As the concrete example of this photoacid generator, can enumerate following compound.But these compounds are the few in the extremely most adaptable photoacid generator, are not limited to these certainly.
The diphenyl lodine chloride; Diphenyl TFMS iodine; Diphenylmethyl sulfonic acid iodine; Diphenylmethyl benzene sulfonic acid iodine; The diphenyl IBr; Diphenyl tetrafluoro boric acid iodine; The diphenyl hexafluoro-iodide antimonate; Diphenyl hexafluoroarsenate iodine; Two (to tert-butyl-phenyl) iodonium hexafluorophosphate; Two (to tert-butyl-phenyl) methane-sulforic acid iodine; Two (to tert-butyl-phenyl) toluenesulfonic acid iodine; Two (to tert-butyl-phenyl) TFMS iodine; Two (to tert-butyl-phenyl) tetrafluoro boric acid iodine; Two (to tert-butyl-phenyl) lodine chloride; Two (rubigan) lodine chloride; Two (rubigan) tetrafluoro boric acid iodine; Triphenyl chlorination sulfonium; Triphenyl bromination sulfonium; Triphenyl TFMS sulfonium; Three (p-methoxyphenyl) tetrafluoro boric acid sulfonium; Three (p-methoxyphenyl) hexafluoro phosphonic acids sulfonium; Three (to ethoxyl phenenyl) tetrafluoro boric acid sulfonium; Triphenyl phosphonium chloride; The triphenyl phosphonium bromide; Three (p-methoxyphenyl) Si Fu Peng Suan Phosphonium; Three (p-methoxyphenyl) six fluorinated phosphonic acid Phosphonium; Three (to ethoxyl phenenyl) Si Fu Peng Suan Phosphonium;
In addition, with respect to the alkali soluble resins of 100 mass parts (A) composition, (D) photoacid generator of composition can use with the ratio of 0.5～50 mass parts, preferably uses with the ratio of 1～30 mass parts.If (D) use amount of the photoacid generator of composition is the too small amount of the lower limit of not enough above-mentioned scope; Can not carry out compound the dissociating of (B) composition of heat cross-linking when then making public from the alkali soluble resins of (A) composition; So being difficult to obtain desirable pattern rises and falls; On the other hand, if (D) use amount of the photoacid generator of composition is the mistake volume that surpasses the upper limit of above-mentioned scope, then the storage stability variation of positive type photosensitive organic compound.
[(E) solvent]
Positive type photosensitive organic compound used in the present invention contains the composition of above-mentioned (A) composition～(D), usually these compositions is dissolved in (E) solvent, the solution that obtains is coated with, thereby forms positive-working photosensitive resin layer.
Should (E) solvent be dissolving (A) composition～(D) composition, and dissolving add as required after state the solvent that (F) becomes to grade, get final product so long as have so solvent solvent, its kind and structure etc. are not limited especially.
As such (E) solvent; For example can enumerate; 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, MEK, cyclopentanone, cyclohexanone, 2-heptanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N; Dinethylformamide, DMAC N,N and N-Methyl pyrrolidone etc.
These solvents can use a kind of separately, or combination is used more than two kinds.
In these (E) solvents, viewpoint such as good and security height, more preferably propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, ethyl lactate, butyl lactate etc. from filming property.These solvents generally can be used as the solvent that is used for photo anti-corrosion agent material and use.
[(F) composition]
(F) composition is a surfactant.When modulating the solution of above-mentioned positive type photosensitive organic compound,, can in the limit of not damaging effect of the present invention, further add surfactant in order to improve its coating etc.
As the surfactant of (F) composition, restriction especially for example can not enumerated, and fluorine is that surfactant, silicone type surface active agent, nonionic are surfactant etc.As this surfactant, for example can use the commercially available article of the manufacturing of Sumitomo ス リ one エ system (strain), big Japanese イ Application キ chemical industry (strain) manufacturing or Asahi Glass (strain) manufacturing etc.Because these commercially available article can easily obtain, so be fit to.As its concrete example, can enumerate エ Off ト Star プ EF301, EF303, EF352 ((strain) ジ エ system コ manufacturing), メ ガ Off ア Star Network F171, F173, R-30 (big Japanese イ Application キ chemical industry (strain) manufacturing), Off ロ ラ one De FC430, FC431 (manufacturing of Sumitomo ス リ one エ system (strain)), ア サ ヒ ガ one De AG710, サ one Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 fluorine such as (Asahi Glass (strain) manufacturings) is surfactant.
These surfactants can use a kind of separately, or combination is used more than two kinds.
Under the situation of using surfactant, its content is generally below the 0.2 quality % in the positive type photosensitive organic compound solution of 100 quality %, is preferably below the 0.1 quality %.Even the dosage of surfactant of (F) composition is set at the amount that surpasses 0.2 quality %, the also passivation of the improved effect of above-mentioned coating is so uneconomical.
[other adjuvant]
And then in the limit of not damaging effect of the present invention, positive type photosensitive organic compound used in the present invention can contain adhesive aids such as rheology control agent, silane coupling agent as required; Pigment, dyestuff, preserving stabilizer; Foam-breaking agent, or cosolvents such as polyhydric phenol, polybasic carboxylic acid etc.
For example, can use silane coupling agent in order to improve with the adhesiveness of substrate.
Below show its concrete example; For example can enumerate; Gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-amino propyl silane, 2-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane, N-amino-ethyl-gamma-amino propyl trimethoxy silicane, 3-uride base propyl-triethoxysilicane, γ-NCO propyl-triethoxysilicane, n-octyl triethoxysilane, vinyl three (2-methoxy ethoxy) silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidyl propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan, 3-decoyl sulfenyl-1-propyl-triethoxysilicane etc.
[positive type photosensitive organic compound and solution thereof]
Pass through back baking and (A) composition that positive type photosensitive organic compound used in the present invention contains the compound that has two above vinyl ether groups in 1 molecule of alkali soluble resins, (B) composition of (A) composition, (C) composition carry out the compound of cross-linking reaction and (D) photoacid generator of composition.Usually, with these (A) compositions～(D) composition dissolves in (E) solvent, with the form supply formation positive-working photosensitive resin layer of solution.And then, can contain surfactant of (F) composition and in other adjuvant more than one respectively as required.
Wherein, the preferred example of this positive type photosensitive organic compound and said composition solution is following.
: positive type photosensitive organic compound, based on 100 mass parts (A) composition, contain (B) composition of 1～80 mass parts, (C) composition of 3～70 mass parts and (D) composition of 0.5～50 mass parts.
: the solution of positive type photosensitive organic compound, be composition with above-mentioned [1] in (E) solvent, dissolve and.
: the solution of positive type photosensitive organic compound, in the solution of the composition of above-mentioned [2], also contain (F) composition below the 0.2 quality %.
To the ratio of the solid constituent in the above-mentioned positive type photosensitive organic compound solution, as long as can make each composition uniform dissolution in solvent, restriction especially for example is not 1～80 quality %, for example is again 5～60 quality % or 8～50 quality %.Here, so-called solid constituent is meant the composition of from total composition of positive type photosensitive organic compound solution, removing behind (E) solvent.
Not restriction especially of modulator approach to positive type photosensitive organic compound solution; As this modulator approach; Can enumerate following method; For example; (A) composition (alkali soluble resins) is dissolved in (E) solvent, then in this solution with regulation mixed (B) composition (compound that has plural vinyl ether group in 1 molecule), (C) composition (carrying out the compound of cross-linking reaction through back baking and (A) composition), (D) composition (photoacid generator) and (F) composition (surfactant), thereby process the method for homogeneous solution; Or, further add other adjuvant as required and carry out method of mixing in the suitable stage of this modulator approach.
When modulating this positive type photosensitive organic compound solution; Can directly use the solution of the specific copolymer that gets through the polyreaction in the solvent; In this case; Add in the solution of this (A) composition likewise that (B) composition, (C) composition, (D) become to grade and when processing homogeneous solution, with above-mentioned in order to adjust further additional input solvent of concentration.At this moment, the solvent that is used to adjust concentration when employed solvent is with modulation positive type photosensitive organic compound solution in the forming process of specific copolymer both can be identical, also can be different.
And the positive type photosensitive organic compound solution of modulation is use after filtrator etc. about 0.2 μ m filters using the aperture preferably.
< high sensitivity positive-working photosensitive resin layer (high sensitivity) >
High sensitivity used in the present invention gets final product so long as sensitivity fully is higher than the positive-working photosensitive resin layer of the sensitivity of above-mentioned muting sensitivity layer, not restriction especially.As such high sensitivity, can use positive type photosensitive organic compound.
High sensitivity used in the present invention can be identical with the employed positive type photosensitive organic compound kind of muting sensitivity layer.From the aspect that high sensitivity and output improve, and control pattern form easily, preferred this situation is set out in the unexposed portion film subtracts when suppressing to develop aspect.
In this case, in order to increase the poor sensitivity of muting sensitivity layer and high sensitivity, (B) composition and (C) component content are less than in the muting sensitivity layer (B) composition and (C) component content (quality) in the positive type photosensitive organic compound of preferred high sensitivity.Specifically; (B) composition and (C) composition in the positive type photosensitive organic compound of preferred high sensitivity are 10～80% and (C) 30～70% the content of component content (quality) of (B) component content (quality) that positive type photosensitive organic compound contained of muting sensitivity layer.More preferably (B) composition and (C) composition in the positive type photosensitive organic compound of high sensitivity are 10～50% and (C) 40～60% the content of component content (quality) of (B) component content (quality) that positive type photosensitive organic compound contained of muting sensitivity layer.
In addition; High sensitivity used in the present invention; Under situation about using with the positive type photosensitive organic compound of muting sensitivity layer identical type; The employed positive type photosensitive organic compound of this high sensitivity can obtain through likewise operating with the modulator approach of [positive type photosensitive organic compound and the solution thereof] of above-mentioned < muting sensitivity positive-working photosensitive resin layer (muting sensitivity layer) >.
At this moment; Preferably be higher than the time that keeps needs under the temperature of room temperature through the mixed solution that will contain the solvent of (A) composition～(E) and (F) composition as required; Come to carry out to a certain extent following heat cross-linking reaction; Thereby obtain except that the solvent of (A) composition～(E) and (F) composition as required, also contain (A) composition and (B) the positive type photosensitive organic compound solution of the crosslinked body of composition.
More preferably through this mixed solution was kept 2 hours～5 days under 30 ℃～70 ℃ temperature; Thereby obtain except that the solvent of (A) composition～(E) and (F) composition as required, also contain (A) composition and (B) the positive type photosensitive organic compound solution of the crosslinked body of composition.
Owing under said temperature and time conditions, modulate; So the resin combination solution homogeneity that obtains improves, therefore, when the film formation process that is supplied in thereafter; Photoacid generator efficient in film is disperseed well, thereby realizes improving the sensitivity of the film that obtains tremendously.
If whipping temp is to be higher than 70 ℃ high temperature; Then carry out cross-linking reaction, curing reaction,, cause the sensitivity of the film that obtains to reduce significantly so composition solution becomes inhomogeneous; In addition; If for to be lower than 30 ℃ low temperature, then can not improve the homogeneity of composition solution, so can not realize improving sensitivity.
< formation of positive-working photosensitive resin layer (photographic layer) and pattern >
Among the present invention; Two-layer positive-working photosensitive resin layers on base material that exposure sensitivity is different carry out lamination; Make the positive-working photosensitive resin layer of muting sensitivity between said base material and highly sensitive positive-working photosensitive resin layer, but to the restriction especially of formation method of these layers.
For example, can be with the solution of the positive type photosensitive organic compound of muting sensitivity layer usefulness, through (for example at the substrate of the employed that kind of semiconductor; Silicon/silicon dioxide is substrate coated, and silicon nitride substrate, metal be the substrate that is covered such as aluminium, molybdenum, chromium for example; Glass substrate, quartz base plate, ito substrate etc.; And the substrate that on them, has formed elements such as transistor) on; Utilize spin coating, flow coat, roller coat, slot coated, the spin coating after slit, spraying etc. to be coated with, carry out with electric hot plate or baking oven etc. then predrying, thereby form the muting sensitivity layer.Then, use the method identical to be coated with the muting sensitivity layer through the positive type photosensitive organic compound solution that high sensitivity is used, carry out with electric hot plate or baking oven etc. then predrying, thereby form high sensitivity.
As this pre-dried condition, for example can adopt, suitably be selected from heating-up temperature and heat time heating time in 70 ℃～160 ℃ of temperature, the scope of 0.3 minute～60 minutes time.Are preferably heating-up temperature and heat time heating time 80 ℃～140 ℃, 0.5 minute～10 minutes.
Desolvate through in this is predrying, removing, or it is crosslinked that the compound with vinyl ether group of (B) composition and (A) resin of composition are carried out, thereby form the film that is insoluble in alkaline-based developer.At this moment; Be lower than in predrying temperature under the situation of lower limit of said temperature scope, solvent remains in the film morely and can not form target pattern sometimes, mixes with the muting sensitivity layer when being coated with high sensitivity sometimes; And then heat cross-linking becomes fully sometimes, subtracts so unexposed portion produces film.In addition, surpass the upper limit of said temperature scope and under the too high situation, unexposed portion carries out crosslinked and poor visualization takes place sometimes in predrying temperature, the also temporary transient sometimes heat cross-linking part fracture once more that forms, thus cause that at unexposed portion film subtracts.
In addition, the thickness of positive-working photosensitive resin layer (having the layer of muting sensitivity layer and high sensitivity concurrently) for example is 0.1～30 μ m, for example is again 0.2～10 μ m, and then for example is 0.2～5 μ m.
At this moment, muting sensitivity layer and high sensitivity thickness separately can be selected arbitrarily in the limit of not damaging effect of the present invention.
If with the positive-working photosensitive resin layer of aforesaid method gained, use half-tone mask, with ultraviolet ray, ArF, KrF, F with predetermined pattern
2Light such as laser make public, then because the effect of the acid that photoacid generator produced of (D) composition of being contained in the positive-working photosensitive resin layer, so exposure portion becomes and dissolves in alkaline developer solution in this film.
Above-mentioned exposure is light or ArF, KrF or the F through having at least a kind of wavelength in i line, g line and the h line preferably
2The light of laser carries out.
Next, to make public back heating of positive-working photosensitive resin layer.As heating condition at this moment, can adopt the heating-up temperature and the heat time heating time that suitably are selected from 80 ℃～140 ℃ of temperature, the scope of 0.3 minute～60 minutes time.
Then, use alkaline-based developer to develop.Thus, in positive-working photosensitive resin layer, in the part of half exposure, have only high sensitivity to be removed, also be removed at part, the muting sensitivity layer of exposure fully, so form the fluctuating of pattern-like with high sensitivity.
As operable alkaline-based developer; For example can enumerate; The WS of alkali metal hydroxide such as potassium hydroxide, NaOH; The WS of quaternary ammonium hydroxides such as TMAH, tetraethyl ammonium hydroxide, choline, alkaline aqueous solutions such as amine aqueous solution such as monoethanolamine, propylamine, ethylenediamine.And then, can add surfactant etc. in these developer solutions.
Among above-mentioned; 0.1 the tetraethyl ammonium hydroxide WS of～2.38 quality % generally is used as the developer solution of photoresist and uses; Also can pass through in the photosensitive polymer combination of the present invention to use this alkaline-based developer, thereby under the state that does not cause problems such as swelling, develop well.
In addition, as developing method, can use multiple liquid method, infusion process, shake in proofing method etc. any.At this moment development time is generally 15 seconds～and 180 seconds.
After the development, washed for example 20～90 seconds through positive-working photosensitive resin layer being utilized flowing water, then through use pressurized air or compressed nitrogen, or it is air-dry to utilize rotation to carry out, thereby removes the moisture on the base material, has obtained forming the film of pattern.
< formation of transparent cured film >
Then; This has been formed the film of pattern, in order to make it heat curing, through carrying out the back baking; Specifically; Wait and heat through use electric hot plate, baking oven, thereby obtain excellences such as thermotolerance, the transparency, flatness, low water absorbable, chemical resistance, and have the film of good fluctuating (relief) pattern.
As back baking, generally adopt following method, promptly with the heating-up temperature in the scope that is selected from 150 ℃～270 ℃ of temperature, under the situation on the electric hot plate, handled 5 minutes～30 minutes, method such as handled 30 minutes～90 minutes under the situation in baking oven.
And, through carrying out this back baking, can obtain transparent cured film target, that have good pattern form.
In the present invention, through give the muting sensitivity layer higher the transparency and give the higher backflow property of high sensitivity (reflow), thereby can make the tft array planarization film of liquid crystal display element of semi-transmission type.
As above, through manufacturing approach of the present invention, can form abundant high sensitivity and when developing the film of unexposed portion subtract very little, partly make public the allowance broad, have filming of fine pattern.
Therefore, can realize high yield in the manufacturing process of the various films in liquid crystal or the OLED display, for example interlayer dielectric, diaphragm, dielectric film, wave filter etc. at the array planarization film of for example TFT type liquid crystal cell.
Embodiment
Below, enumerate embodiment, illustrate in greater detail the present invention, but the present invention is not limited by these embodiment.
[the employed abbreviation of embodiment]
The meaning of the employed abbreviation of following examples is following.
MAA: methacrylic acid
MMA: methyl methacrylate
HEMA: methacrylic acid 2-hydroxyl ethyl ester
CHMI:N-cyclohexyl maleimide
AIBN: azoisobutyronitrile
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) makes CGI1397 (trade name)/compound name: 2-methyl-α-[5-[[(third sulphonyl) oxygen] imino group]-(5H)-thenylidene] benzene acetonitrile (compound of formula (7))
PVE1: three (4-(vinyl oxygen base) butyl) trimellitate
PVE2:1,4-cyclohexanedimethanol divinyl ether
NCO1: デ グ サ AG makes VESTAGON (registered trademark) B 1065 (trade name)/compound names: epsilon-caprolactams block polyisocyanate (compound of formula (S-4))
R30: big Japanese イ Application キ chemical industry (strain) is made メ ガ Off ア Star Network R-30 (trade name) (fluorine is a surfactant)
MPTS: gamma-methyl allyl acyloxypropyl trimethoxysilane
P200: Japan's compound probability (strain) is made P-200 (trade name) and is passed through 1 mole 4; 4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] biphenol and 2 mole 1; 2-naphthoquinones-2-diazido-5-sulfonic acid chloride carries out condensation reaction and synthetic emulsion (1, the 2-quinone di-azido compound)
GT4: epoxidation BTCA four-(3-cyclohexenyl group methyl) modified 6-caprolactone
[mensuration of number-average molecular weight and weight-average molecular weight]
Number-average molecular weight and weight-average molecular weight to the specific copolymer that obtains according to following synthetic example; The GPC device (Shodex (registered trademark) post KF803L and KF804L) that uses Japanese beam split (strain) to make makes it the eluting solvent tetrahydrofuran was flow through (40 ℃ of column temperature) in the post with flow 1ml/ minute to measure under the condition of wash-out.In addition, following number-average molecular weight (below, be called Mn) and weight-average molecular weight (below, be called Mw) represent with the polystyrene calibration value.
< synthetic example 1 >
Use 19.4g MAA, 35.3g CHMI, 25.5g HEMA, 19.8g MMA as the monomer component that constitutes specific copolymer; Use 5g AIBN as radical polymerization initiator; Through making them in 212.5g solvent PGMEA, carry out polyreaction for 60 ℃～100 ℃, thereby obtain that Mn is 4100, Mw is (A) composition (specific copolymer) solution (specific copolymer concentration: 32.0 quality %) of 7600 in temperature.(P1)
< synthetic example 2 >
Use 15.5g MAA, 35.3g CHMI, 25.5g HEMA, 23.7g MMA as the monomer component that constitutes specific copolymer; Use 5g AIBN as radical polymerization initiator; Through making them in 212.5g solvent PGMEA, carry out polyreaction for 60 ℃～100 ℃, thereby obtain that Mn is 4400, Mw is (A) composition (specific copolymer) solution (specific copolymer concentration: 32.0 quality %) of 7000 in temperature.(P2)
< composition example 1～5 >
According to the composition shown in the following table 1; Through in the solution of (A) composition; With regulation mixed (B) composition, (C) composition, (D) composition and (E) solvent, and (F) composition, stirred 30 minutes for 23 ℃ in temperature; Or stirred 3 three days and process homogeneous solution, thereby modulate the positive type photosensitive organic compound solution of each embodiment and each comparative example at 35 ℃.
[table 1]
| (A) solution of composition (g) | (B) composition (g) | (C) composition (g) | (D) composition (g) | (E) solvent (g) | (F) composition (g) | Modulation condition temperature/time | |
| Composition example 1 | ?P1?25 | PVE2 2.4 | NCO1 1.6 | PAG1 0.32 | PGMEA 11.8 | R30 0.0062 | 23 ℃ 30 minutes |
| Composition example 2 | ?P1?25 | PVE1 2.4 | NCO1 1.6 | PAG1 0.32 | PGMEA 11.8 | R30 0.0062 | 23 ℃ 30 minutes |
| Composition example 3 | ?P2?25 | PVE1 0.4 | NCO1 0.8 | PAG1 0.32 | PGMEA 16.8 | R30 0.0047 | 35 ℃ 3 days |
| Composition example 4 | ?P2?25 | PVE1 0.4 | NCO1 0.8 | PAG1 0.24 | PGMEA 16.5 | R30 0.0047 | 35 ℃ 3 days |
| Composition example 5 | ?P1?25 | PVE1 2.4 | NCO1 0.8 | PAG1 0.32 | PGME 7.5 | R30 0.0058 | 23 ℃ 30 minutes |
< composition example 6 >
As alkali soluble resins solution; In the specific copolymer solution (P1) of synthetic routine 1 gained of 17.2g; The P200 that mixes 1.1g is as 1; The GT4 of 2-quinone di-azido compound, 1.1g as epoxy be the R30 of cross-linked compound, 0.0039g as the MPTS of surfactant, 0.25g as the PGMEA that adheres to auxiliary agent, 5.2g as solvent, stirring at room 8 hours, thus modulation positive type photosensitive organic compound solution.
< composition example 7 >
As alkali soluble resins solution; In the specific copolymer solution (P2) of synthetic routine 2 gained of 17.2g; The P200 that mixes 1.7g is as 1; The GT4 of 2-quinone di-azido compound, 1.1g as epoxy be the R30 of cross-linked compound, 0.0039g as the MPTS of surfactant, 0.25g as adhering to auxiliary agent, 6.5g PGMEA as solvent, stirring at room 8 hours, thus modulation positive type photosensitive organic compound solution.
< embodiment 1～4 and comparative example 1～3 >
The two membranes of embodiment 1～embodiment 4 shown in the his-and-hers watches 2, and each monofilm of comparative example 1～comparative example 3 measure respectively that light transmission (transparency) after the high-temperature baking, sensitivity, unexposed film subtract, the allowance of partly making public.
In addition, when obtaining cured film by positive type photosensitive organic compound, for comparative example 2 and 3, the stage after developing, before the baking of back is carried out photobleaching.On the other hand, because for embodiment 1～4 and comparative example 1, do not carry out this photobleaching, the back heating (PEB) but the stage after exposure, before developing makes public so from this respect, both evaluation orders are described below, is different.
[evaluation of the light transmission (transparency) after the high-temperature baking]
< embodiment 1～4 >
Use spinner to be coated on the quartz base plate with positive type photosensitive organic compound solution lower floor, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form filming of thickness 2.0 μ m.Then use spinner on this is filmed, to be coated with the upper strata and use positive type photosensitive organic compound solution, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form filming of thickness 1.0 μ m.With this dipping 60 seconds of filming in 0.4% TMAH (below, the be called TMAH) WS, carry out flowing water washing 20 seconds with ultrapure water then.Next toast through carrying out the back in 30 minutes 230 ℃ of heating, thus the cured film of formation thickness 2.4 μ m.This cured film is measured the initial stage transmissivity with ultraviolet visible spectrophotometer ((strain) Tianjin, island is made and made manufacturing SHIMADZUUV-2550 model) with the 400nm wavelength.And then this is filmed 250 ℃ of heating 30 minutes, likewise measure heating back transmissivity then with the 400nm wavelength.The F20 that thickness uses FILMETRICS to make in this evaluation measures.
< comparative example 1 >
Use spinner to be coated on the quartz base plate positive type photosensitive organic compound solution, then under 120 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form filming of thickness 3.0 μ m.With this dipping 60 seconds of filming in 0.4% the TMAH WS, carry out flowing water washing 20 seconds with ultrapure water then.Next toast through carrying out the back in 30 minutes 230 ℃ of heating, thus the cured film of formation thickness 2.4 μ m.This cured film is measured the initial stage transmissivity with ultraviolet visible spectrophotometer ((strain) Tianjin, island is made and made manufacturing SHIMADZU UV-2550 model) with the 400nm wavelength.And then this is filmed 250 ℃ of heating 30 minutes, likewise measure heating back transmissivity then with the 400nm wavelength.The F20 that thickness uses FILMETRICS to make in this evaluation measures.
< comparative example 2 and 3 >
Use spinner to be coated on the quartz base plate positive type photosensitive organic compound solution, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form filming of thickness 3.0 μ m.With this proofing 60 seconds of filming in 0.4% the TMAH WS, carry out flowing water washing 20 seconds with ultrapure water then.The ultraviolet lamp PLA-600FA that uses キ ヤ ノ Application (strain) manufacturing through this is filmed is with exposure 800mJ/cm
2The light intensity of irradiation 365nm is 5.5mW/cm
2Ultraviolet ray (photobleaching), next carried out back baking in 30 minutes 230 ℃ of heating, thus the cured film of formation thickness 2.4 μ m.This cured film is measured the initial stage transmissivity with ultraviolet visible spectrophotometer ((strain) Tianjin, island is made and made manufacturing SHIMADZU UV-2550 model) with the 400nm wavelength.And then this is filmed 250 ℃ of heating 30 minutes, likewise measure heating back transmissivity then with the 400nm wavelength.The F20 that thickness uses FILMETRICS to make in this evaluation measures.
[evaluation that sensitivity and film subtract]
< embodiment 1～4 >
Lower floor is used positive type photosensitive organic compound, uses spinner to be coated on the silicon wafer, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form thickness 2.0 μ m film (muting sensitivity layer).Then use spinner on above-mentioned filming, to be coated with the upper strata and use positive type photosensitive organic compound, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form thickness 1.0 μ m film (high sensitivity).The F20 that thickness uses FILMETRICS to make measures.This is filmed use ultraviolet lamp PLA-600FA that キ ヤ ノ Application (strain) makes to be 5.5mW/cm with the light intensity of various exposures irradiation 365nm
2Ultraviolet ray, next under 110 ℃ of temperature, back heating 120 seconds makes public on electric hot plate.Developed in 60 seconds through dipping in 0.4% the TMAH WS then, carry out flowing water washing 20 seconds with ultrapure water then.Lowest exposure amount (mJ/cm when the exposed portion dissolution residual substance is disappeared
2) be sensitivity.In addition, the reduction of unexposed portion thickness is that film subtracts.
< comparative example 1 >
With positive type photosensitive organic compound, use spinner to be coated on the silicon wafer, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form filming of thickness 3.0 μ m.The F20 that thickness uses FILMETRICS to make measures.This is filmed use ultraviolet lamp PLA-600FA that キ ヤ ノ Application (strain) makes to be 5.5mW/cm with the light intensity of various exposures irradiation 365nm
2Ultraviolet ray, next in the back heating 120 seconds that on electric hot plate, makes public of 110 ℃ of temperature.Developed in 60 seconds through dipping in 0.4% the TMAH WS then, carry out flowing water washing 20 seconds with ultrapure water then.Lowest exposure amount (mJ/cm during with the residual disappearance of exposure portion dissolving
2) as sensitivity.In addition, the reduction of unexposed portion thickness is that film subtracts.
< comparative example 2 and 3 >
Use spinner to be coated on the silicon wafer positive type photosensitive organic compound solution, then under 110 ℃ of temperature, on electric hot plate, carried out preliminary drying 120 seconds, thereby form filming of thickness 3.0 μ m.The F20 that thickness uses FILMETRICS to make measures.This is filmed use ultraviolet lamp PLA-600FA that キ ヤ ノ Application (strain) makes to be 5.5mW/cm with the light intensity of various exposures irradiation 365nm
2Ultraviolet ray.Developed in 60 seconds through dipping in 0.4% the TMAH WS then, carry out flowing water washing 20 seconds with ultrapure water then.Lowest exposure amount (mJ/cm during with the residual disappearance of exposure portion dissolving
2) as sensitivity.In addition, the reduction of unexposed portion thickness is that film subtracts.
[evaluation of the allowance of partly making public]
Use and above-mentioned [evaluation that sensitivity and film subtract] same operation, on the muting sensitivity layer, form high sensitivity, carry out irradiation ultraviolet radiation, the heating of exposure back, develop, wash.At this moment, the residual-film amount of exposure portion is that the exposure range of 2 μ m ± 5% is half exposure allowances.
[result of evaluation]
The result that will carry out above evaluation is shown in following table 2.
[table 2]
*Heating back transmissivity is 250 ℃, the value of heating after 30 minutes.
Among the embodiment 1～4, use high sensitivity, lower floor to use the muting sensitivity layer, can keep high-transmission rate, and under high sensitivity and the state that do not have film to subtract, develop, and then can when partly making public, obtain broad exposure allowance through the upper strata.
On the other hand, can under high sensitivity and the state that does not have film to subtract, develop in the comparative example 1, but the allowance of partly making public is significantly low.
In addition, comparative example 2 with 3 any one compare with embodiment 1～embodiment 4 and be muting sensitivity and unexposed and have film to subtract, the result from both can know in addition, in these individual layer systems, high more allowance, the transmissivity of then partly making public of sensitivity is low more.
The industry utilizability
The transparent cured film of the manufacturing approach gained through transparent cured film of the present invention; Be suitable as the material that when the TFT planarization film in making liquid crystal display element of semi-transmission type, to use, particularly be suitable as and be formed for forming contact hole and the material of reflection simultaneously with concavo-convex transparent cured film through half exposure.
Claims (8)
1. the manufacturing approach of a transparent cured film; This manufacturing approach comprises following operation: at the different two-layer positive-working photosensitive resin layer of base material superimposed layer exposure sensitivity, make the operation of positive-working photosensitive resin layer between said base material and highly sensitive positive-working photosensitive resin layer of muting sensitivity; The operation that two-layer positive-working photosensitive resin layer behind this lamination is made public; With the make public operation of back heating of this two-layer positive-working photosensitive resin layer; With the operation that this two-layer positive-working photosensitive resin layer develops, the operation of this two-layer positive-working photosensitive resin layer being carried out the back baking
Wherein, said exposure is half exposure,
The manufacturing approach of this transparent cured film is characterised in that, the positive-working photosensitive resin layer of this muting sensitivity is to contain following (A) composition, (B) composition, (C) composition and (D) positive-working photosensitive resin layer of composition,
(A) composition is an alkali soluble resins,
(B) composition is the compound that has two above vinyl ether groups in 1 molecule,
(C) composition is the compound that toasts through the back and (A) composition carries out cross-linking reaction, is the compound that has two above blocked isocyanate bases in 1 molecule,
(D) composition is a photoacid generator.
2. the manufacturing approach of transparent cured film according to claim 1, heating is carried out under 80 ℃～140 ℃ of temperature after the said exposure, and the baking of said back is carried out under 150 ℃～270 ℃ of temperature.
3. the manufacturing approach of transparent cured film according to claim 1, said highly sensitive positive-working photosensitive resin layer are to contain following (A) composition, (B) composition, (C) composition and (D) positive-working photosensitive resin layer of composition,
(A) composition is an alkali soluble resins,
(B) composition is the compound that has two above vinyl ether groups in 1 molecule,
(C) composition is the compound that toasts through the back and (A) composition carries out cross-linking reaction,
(D) composition is a photoacid generator.
4. the manufacturing approach of transparent cured film according to claim 1; In the positive-working photosensitive resin layer of said muting sensitivity; Based on 100 mass parts (A) composition, contain 1～80 mass parts said (B) composition, said (C) composition of 3～70 mass parts and 0.5～50 mass parts said (D) composition.
5. the manufacturing approach of transparent cured film according to claim 1, base material is the base material that has formed the TFT element.
6. tft array planarization film comprises the transparent cured film that each the described manufacturing approach by claim 1～4 obtains.
7. display element has the transparent cured film that each the described manufacturing approach by claim 1～4 obtains.
8. liquid crystal display cells has the transparent cured film that each the described manufacturing approach by claim 1～4 obtains.
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| JP5293937B2 (en) * | 2008-05-22 | 2013-09-18 | 日産化学工業株式会社 | Photosensitive resin composition |
| CN101807553B (en) * | 2010-03-18 | 2013-05-01 | 信利半导体有限公司 | Preparation method of TFT ARRAY plate having OC material |
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| JP2004020667A (en) * | 2002-06-13 | 2004-01-22 | Kyocera Chemical Corp | Photosensitive resin composition and forming method of positive type pattern |
| WO2005052688A2 (en) * | 2003-11-25 | 2005-06-09 | Tokyo Ohka Kogyo Co., Ltd. | Chemically amplified positive photosensitive thermosetting resin composition method of forming cured article and method of producing functional device |
| JP2005316117A (en) * | 2004-04-28 | 2005-11-10 | Kansai Paint Co Ltd | Photosensitive resin composition |
| JP2006030971A (en) * | 2004-06-15 | 2006-02-02 | Techno Network Shikoku Co Ltd | Photolithographic method |
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| JP4173413B2 (en) * | 2003-08-28 | 2008-10-29 | 東京応化工業株式会社 | Method for forming resist pattern for lift-off |
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| JP2004020667A (en) * | 2002-06-13 | 2004-01-22 | Kyocera Chemical Corp | Photosensitive resin composition and forming method of positive type pattern |
| WO2005052688A2 (en) * | 2003-11-25 | 2005-06-09 | Tokyo Ohka Kogyo Co., Ltd. | Chemically amplified positive photosensitive thermosetting resin composition method of forming cured article and method of producing functional device |
| JP2005316117A (en) * | 2004-04-28 | 2005-11-10 | Kansai Paint Co Ltd | Photosensitive resin composition |
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