CN101443705B - Positive photosensitive resin composition containing siloxane compound - Google Patents

Positive photosensitive resin composition containing siloxane compound Download PDF

Info

Publication number
CN101443705B
CN101443705B CN2007800176897A CN200780017689A CN101443705B CN 101443705 B CN101443705 B CN 101443705B CN 2007800176897 A CN2007800176897 A CN 2007800176897A CN 200780017689 A CN200780017689 A CN 200780017689A CN 101443705 B CN101443705 B CN 101443705B
Authority
CN
China
Prior art keywords
composition
organic compound
positive type
type photosensitive
photosensitive organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2007800176897A
Other languages
Chinese (zh)
Other versions
CN101443705A (en
Inventor
畑中真
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN101443705A publication Critical patent/CN101443705A/en
Application granted granted Critical
Publication of CN101443705B publication Critical patent/CN101443705B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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

Abstract

The invention provides a photosensitive resin composition from which an image coating film having high pattern surface water repellency, etc. even after a treatment with a plasma or the like and having insulating properties can be easily formed with high accuracy at a high throughput rate; and a cured film which is obtained from such positive photosensitive resin composition and is suitable for use as a film material for various displays. The method for solving the problem in the invention provides a positive photosensitive resin composition comprising ingredient (A) which is an alkali-soluble resin having a functional group enabling the resin to undergo a heat-crosslinking reaction and further having a functional group for a heat-curing reaction and for film curing, and having a number-average molecular weight of 2,000-30,000; ingredient (B) which is a siloxane compound having a number-average molecular weight of 100-2,000; ingredient (C) which is a compound having two or more vinyl ether groups per molecule; ingredient (D) which is a compound having two or more blocked isocyanate groups per molecule; ingredient (E) which is a photo-acid generator; and a solvent (F); and provides the cured film obtained by using the composition.

Description

The positive type photosensitive organic compound that contains silicone compounds
Technical field
The present invention relates to positive type photosensitive organic compound and cured film therefrom.More particularly, relate to patterned surfaces and have high water proofing property, and positive type photosensitive organic compound and the cured film thereof that can in film, make emptying aperture that can controlling dimension, and the various materials that use this cured film.Even the invention still further relates to after processing such as UV-ozone and also can form positive type photosensitive organic compound and the cured film thereof that the surface has the image of high water proofing property and high oil-proofness, and the various materials that use this cured film.The positive type photosensitive organic compound of the invention described above is especially suitable for use as interlayer dielectric in liquid crystal display cells or the EL display element, corresponding to the light screening material or the separator material of ink-jetting style.
Background technology
Generally in thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL(electroluminescence) in the display device such as element, be provided with the electrode protective membrane that forms pattern, planarization film, dielectric film etc.As the material that forms these films, in photosensitive polymer combination, just being widely used at present, those have the photosensitive polymer combination that the process number that is used to obtain required pattern is few and have characteristic such as sufficient flatness.
In addition, in the production process of display display element, use the panchromatic display base plate manufacturing technology of ink-jet also to study very actively in recent years.The making of color filter in the for example relevant liquid crystal display cells; With respect to present print process, electrodeposition process, decoration method or pigment dispersing method, the interval (below be called the edge) of the patterned pixel of regulation, in the peristome that this edge surrounded, drip color filter and the manufacturing approach (for example with reference to patent documentation 1, patent documentation 2 and patent documentation 3) thereof etc. of ink droplet have again been proposed at first in the photo-sensitive resin of blocking light, to form.In organic EL display element, also propose at first to make the edge in addition, dripped equally and become the China ink of luminescent layer again, thereby made the method (for example with reference to patent documentation 4) of organic EL display element.
Yet in ink-jet method, drip by under the situation of the ink droplet of edge encirclement, be spilled over to the situation of neighbor in order to prevent ink droplet from surpassing the edge, need on substrate, keep ink affinity (water wettability), keep water proofing property on the surface, edge.
In order to achieve the above object; Proposed to handle through continuous plasmas (ozone) such as oxygen gas plasma processing and the processing of plasma of fluorine gas body; Can on substrate, keep water wettability, and on the edge, keep water proofing property (for example with reference to patent documentation 5), but complex procedures.Also proposed on the photonasty organic film, to cooperate fluorine class surfactant or fluorine-based polymer (for example with reference to patent documentation 6) in addition; But intermiscibility or addition etc.; To consider that not only photonasty also comprises coating property, need the aspect of consideration more, be difficult to deserve to be called practical.
So to above-mentioned these films; Except requiring water proofing property; Also require anti-operability such as low-k, thermotolerance, solvent resistance excellent; Good with the adaptation of substrate; Has the wide opereating specification that under various operating conditionss, can form image according to application target; Also have ISO and high transparent, and the inhomogeneous various characteristics that waits less of film after developing.Therefore from such characteristic aspect that requires, as above-mentioned photosensitive polymer combination, the general resin that contains the naphthoquinone two azide compound at present.
, requiring in the characteristic of such photoresist material,, can enumerate light sensitivity as a characteristic of particular importance.Improve light sensitivity in commercial production such as display device, can shorten its production time significantly, therefore under the present situation that the requirement of LCD enlarges markedly, light sensitivity becomes one of desired most important characteristic of this photoresist material.
Therefore, up to the present, for the ISOization of photoresist material has been carried out many exploitations.The sense radioactivity resin combination (for example with reference to patent documentation 7) of at least one has for example been proposed to contain in alkali soluble resins and specific polyol and the derivant thereof.
On the other hand, as ISO, high-resolution photosensitive material, developed chemically amplified corrosion-resisitng agent at present.The present chemically amplified corrosion-resisitng agent of developing with resist as semiconductor; Also can adapt to light source (KrF, the ArF) shorter than i line wavelength; Can form finer image; But solidify under the high temperature that is adopted at film, also have in the presence of the anticorrosive additive stripping liquid controlling; The heat cross-linking part of the bound fraction of protection base and ehter bond is decomposed easily; Thermotolerance and chemical resistance significantly reduce, and can not use (for example with reference to patent documentation 8) basically as permanent film.In addition; For can heat curing; Even in chemically amplified corrosion-resisitng agent, import the crosslinked class of epoxy base class, amino plastics class etc.; The also influence of the acid that can produce by photoacid generator in the resist (PAG) owing to make public because of kainogenesis; Exposed portion carries out crosslinked; Therefore problems such as dissolving contrast disappearance with unexposed portion import very difficulty of so crosslinked class in chemically amplified corrosion-resisitng agent.
Patent documentation 1: the spy opens flat 10-206627 communique
Patent documentation 2: the spy opens flat 11-326625 communique
Patent documentation 3: the spy opens flat 2000-187111 communique
Patent documentation 4: the spy opens flat 11-54270 communique
Patent documentation 5: the spy opens the 2000-353594 communique
Patent documentation 6: the spy opens flat 10-197715 communique
Patent documentation 7: the spy opens flat 4-211255 communique
Patent documentation 8: No. 5075199 instructions of United States Patent (USP)
Summary of the invention
The present invention makes in view of the above fact; Its problem to be solved is to provide a kind of photosensitive polymer combination; It is suitable as the material that is used to form the pattern-like insulating film that uses in liquid crystal display cells, the organic EL display element etc.; With the pixel separation sheet material; Specifically; A kind of positive type photosensitive organic compound is provided; It can be easily forms pattern with high precision, high yield, even and processing such as UV-ozone afterwards patterned surfaces also have high waterproof even high oil-proofness.
Problem of the present invention in addition is to provide the cured film of using such positive type photosensitive organic compound to obtain; This cured film can prevent that ink droplet from exceeding the edge and being spilled over to adjacent pixels in the substrate manufacture that uses ink-jet, and the various element materials that use such cured film to make are provided.
Present inventors further investigate in order to solve above-mentioned problem, found that the present invention.
That is, the present invention's the 1st viewpoint is a kind of positive type photosensitive organic compound, contains following (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) solvent,
(A) composition: have the functional group that can carry out heat cross-linking reaction, and a functional group that film solidifies that is used for that can carry out the heat curing reaction, and number-average molecular weight is 2000～30000 alkali soluble resins with (D) component cpd with (C) component cpd,
(B) composition: number-average molecular weight is 100～2000 silicone compounds,
(C) contain the compound of 2 above vinyl ether groups in the composition :1 molecule,
(D) contain the compound of 2 above blocked isocyanate bases in the composition :1 molecule,
(E) composition: photoacid generator,
(F) solvent.
The 2nd viewpoint is the described positive type photosensitive organic compound of the 1st viewpoint; The above-mentioned functional group that can carry out heat cross-linking reaction is at least a kind that is selected from carboxyl and the phenol property hydroxyl, and above-mentioned to be used for functional group that film solidifies be at least a kind of amino that is selected from the hydroxyl except that phenol property hydroxyl and has reactive hydrogen.
The 3rd viewpoint is the described positive type photosensitive organic compound of the 1st or the 2nd viewpoint, it is characterized in that, (B) composition is a fluorine modified siloxane compound.
The 4th viewpoint is the described positive type photosensitive organic compound of the 1st or the 2nd viewpoint, it is characterized in that, (B) composition is the silicone compounds with repetitive of formula (1) expression,
Figure G2007800176897D00041
In the formula, R < > 1 <> And R < > 2 <> Be hydrogen atom, alkyl or phenyl independently of one another, p representes positive integer.
The 5th viewpoint is the described positive type photosensitive organic compound of the 4th viewpoint, it is characterized in that, (B) composition is R in the above-mentioned formula (1) < > 1 <> And/or R < > 2 <> The silicone compounds of expression fluoro-alkyl.
The 6th viewpoint is each described positive type photosensitive organic compound of the 1st～the 5th viewpoint, it is characterized in that, (B) composition is not for containing the silicone compounds of epoxy radicals.
The 7th viewpoint is each described positive type photosensitive organic compound of the 1st～the 6th viewpoint; Based on 100 mass parts (A) composition, contain (B) composition of 0.1～30 mass parts, (C) composition of 1～80 mass parts, (D) composition of 1～80 mass parts and (E) composition of 0.5～80 mass parts.
The 8th viewpoint is each described positive type photosensitive organic compound of the 1st～the 7th viewpoint; At (B) composition is in the positive type photosensitive organic compound of silicone compounds of fluorine modification, based on 100 mass parts (A) composition also contain 0.1～20 mass parts as (G) composition except that (A) the fluorine class alkali soluble resins the composition.
The 9th viewpoint is each described positive type photosensitive organic compound of the 1st～the 8th viewpoint, also contains the amines of conduct (H) composition of 0.001～5 mass parts based on 100 mass parts (A) composition.
The 10th viewpoint is each described positive type photosensitive organic compound of the 1st～the 9th viewpoint, in positive type photosensitive organic compound, also contains the surfactant of conduct (I) composition below the 0.2 quality %.
The cured film of the 11st viewpoint for using each described positive type photosensitive organic compound of the 1st～the 10th viewpoint to obtain.
The 12nd viewpoint is the separator material that organic EL display element is used, and contains the described cured film of the 11st viewpoint.
The 13rd viewpoint is a liquid crystal display cells, has the described cured film of the 11st viewpoint.
The 14th viewpoint is a LCD array planarization film, is formed by the described cured film of the 11st viewpoint.
The 15th viewpoint is an interlayer dielectric, is formed by the described cured film of the 11st viewpoint.
Positive type photosensitive organic compound of the present invention has high storage stability, and light sensitivity is high simultaneously, is suitable as the material and the pixel separation sheet material that are used to form the pattern-like insulating film that in liquid crystal display cells, organic EL display element etc., uses.
And positive type photosensitive organic compound of the present invention; Through using silicone compounds as (B) composition; Can easily form the pattern of insulativity with high precision and high yield; This pattern has high waterproof at patterned surfaces; Even its water resisting property can not reduce greatlyyer yet after ozone treatment, can form the emptying aperture of sub-micron in addition in pattern inside.
Positive type photosensitive organic compound of the present invention in addition; Particularly through using fluorine modified siloxane compound as (B) composition; This pattern patterned surfaces has after long-time ozone treatment high waterproof and high oil-proofness can easily form the pattern of insulativity, even also can not reduce bigger with high precision and high yield.
In addition; The cured film of using above-mentioned positive type photosensitive organic compound of the present invention to obtain can prevent that ink droplet from exceeding the situation that the edge is spilled over to neighbor in the substrate manufacture that uses ink-jet, and then the various element materials that use such cured film to make can be provided.
Embodiment
Positive type photosensitive organic compound of the present invention is following composition; It contains (A) composition: alkali soluble resins, (B) composition: silicone compounds, (C) composition: compound, (D) composition with vinyl ether group: compound, (E) composition with blocked isocyanate base: photoacid generator and (F) solvent; And according to required separately; Contain (G) composition: other alkali soluble resins, state (H) composition after also containing: amines or (I) composition: surfactant.Be described in detail in the face of each composition down.
(A) composition
(A) composition is to have the functional group that can carry out the heat cross-linking reaction with the compound with vinyl ether group of (C) composition in the resin structure; And the functional group that film solidifies that is used for that can carry out heat curing reaction with the compound with blocked isocyanate base of (D) composition, and the number-average molecular weight of polystyrene conversion (below be called number-average molecular weight) is 2000～30000 alkali soluble resins.
The functional group that can carry out heat cross-linking reaction be can be at high temperature with (C) component cpd in the vinyl ether radical reaction; And carry out heat cross-linking with (C) component cpd; And the group of formation resist film, its representational functional group is at least a kind that is selected from carboxyl and the phenol property hydroxyl.
In addition; Being used for functional group that film solidifies and being can be at the heat cross-linking body that is formed by above-mentioned (A) composition and (C) composition (in exposed portion; Be to take off) in the crosslinked body what the heat cross-linking body further dissociated; Under higher temperature; And (D) isocyanate group that partly dissociates by end-blocking that is situated between between the component cpd carry out cross-linking reaction; Thereby make the group that film solidifies, its representational functional group is selected from the hydroxyl except that phenol property hydroxyl and has at least a kind in the amino of reactive hydrogen.Here so-called amino with reactive hydrogen is meant primary amino radical or the secondary amino group that can emit hydrogen through reaction.Therefore, therefore amide group does not belong to the amino with reactive hydrogen owing to do not have reactive hydrogen.
(A) resin of composition is so long as have the alkali soluble resins of this structure and get final product, to the skeleton of the high polymer main chain that constitutes resin and the qualification especially of kind of side chain.
Yet (A) number-average molecular weight of composition resin is in 2000～30000 scope.If number-average molecular weight surpasses 30000 and excessive, then be easy to generate the development residue, light sensitivity reduces greatly, if number-average molecular weight less than 2000 is and too small on the other hand, the film that the unexposed portion of a great deal of then takes place when developing subtracts, and solidifies not enough sometimes.
As (A) composition alkali soluble resins, for example can enumerate acrylic resin, polycarboxylated styrene resinoid etc.Particularly because the transparency is high, so more preferably acrylic resin.
In addition in the present invention, also can use alkali soluble resins that the multipolymer that multiple monomer polymerization obtains (below be called specific copolymer) constitutes as (A) composition.At this moment, (A) alkali soluble resins of composition also can be the potpourri of multiple specific copolymer.
Promptly; Above-mentioned specific copolymer is to have the monomer of the functional group that can carry out the heat cross-linking reaction; And have be used for the functional group that film solidifies monomer as the formed copolymer of essential construction unit; Said monomer with the functional group that can carry out the heat cross-linking reaction; It is at least a kind of monomer suitably selecting in the haplometrotic colony of at least a kind of group from have carboxyl and phenol hydroxyl; Said monomer with the functional group that is used for film curing is at least a kind of monomer from the haplometrotic colony with the hydroxyl except that the phenol hydroxyl and at least a kind of group of amino with reactive hydrogen, suitably selecting, and the number-average molecular weight of said copolymer is 2000～30000.
Above-mentioned " monomer with at least a kind of group in carboxyl and the phenol property hydroxyl " comprise, have carboxyl monomer, have the monomer of phenol property hydroxyl and have carboxyl and the monomer of phenol property hydroxyl.These monomers are not limited to has 1 carboxyl or phenol property hydroxyl, also can have a plurality of carboxyls or phenol property hydroxyl.
In addition; Above-mentioned " having hydroxyl and the monomer with at least a kind of group in the amino of reactive hydrogen except that phenol property hydroxyl " comprises; Monomer with the hydroxyl except that phenol property hydroxyl; Have the monomer of the amino that contains reactive hydrogen, and have hydroxyl and monomer except that phenol property hydroxyl with amino of reactive hydrogen.These monomers be not limited to contain 1 except that phenol property hydroxyl hydroxyl or have the amino of reactive hydrogen, also can contain a plurality of except that phenol property hydroxyl hydroxyl or have the amino of reactive hydrogen.
Below enumerate the concrete example of above-mentioned monomer, but be not limited to these.
As the monomer that contains carboxyl; For example can enumerate acrylic acid, methacrylic acid, crotonic acid, phthalic acid list-2-(acryloxy) ethyl ester, phthalic acid list-2-(methacryloxy) ethyl ester, N-(carboxyl phenyl) maleimide, N-(carboxyl phenyl) Methacrylamide, N-(carboxyl phenyl) acrylamide etc.
As the monomer that contains phenol property hydroxyl, for example can enumerate hydroxy styrenes, N-(hydroxy phenyl) acrylamide, N-(hydroxy phenyl) Methacrylamide, N-(hydroxy phenyl) maleimide etc.
As the monomer that contains the hydroxyl except that phenol property hydroxyl; For example can enumerate acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, 5-acryloxy-6-hydroxyl norborene-2-carboxyl-6-lactone, 2-hydroxyethyl methacry-late, methacrylic acid-2-hydroxypropyl acrylate, 5-methacryloxy-6-hydroxyl norborene-2-carboxyl-6-lactone etc.
And then, contain the amino monomer of reactive hydrogen as having, can enumerate acrylic acid-2-amino ethyl ester, methacrylic acid-2-amino methyl etc.
In addition, specific copolymer also can be with except monomer with the functional group that can carry out heat cross-linking reaction with have the multipolymer of monomer the monomer that is used for the functional group that film solidifies (below be called other monomers) as structural unit formation.
Other monomers; Specifically; So long as can with the monomer with at least a kind of group in carboxyl and the phenol property hydroxyl; And the hydroxyl that has except that phenol property hydroxyl gets final product with the monomer copolymerization with at least a kind of group in the amino of reactive hydrogen; Only otherwise the characteristic of infringement (A) composition just limits especially.
As the object lesson of other monomers, can enumerate acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and vinyl compound 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 anthryl methyl esters; Phenyl acrylate; Acrylic acid-2, the 2-trifluoro ethyl ester; Tert-butyl acrylate; Cyclohexyl acrylate; IBOA; Acrylic acid-2-methoxyl ethyl ester; Acrylic acid methoxyl triethyleneglycol ester; Acrylic acid-2-ethoxy ethyl ester; Tetrahydrofurfuryl acrylate; Acrylic acid-3-methoxyl butyl ester; Acrylic acid 2-methyl-2-diamantane ester; Acrylic acid 2-propyl group-2-diamantane ester; Acrylic acid 8-methyl-8-three ring esters in the last of the ten Heavenly stems and acrylic acid 8-ethyl-8-three ring esters in the last of the ten Heavenly stems etc.
As methacrylate compound; Can enumerate for example methyl methacrylate; Jia Jibingxisuanyizhi; Isopropyl methacrylate; Benzyl methacrylate; Methacrylic acid naphthalene ester; Methacrylic acid anthracene ester; Methacrylic acid anthryl methyl esters; Phenyl methacrylate; Methacrylic acid-2, the 2-trifluoro ethyl ester; The metering system tert-butyl acrylate; Cyclohexyl methacrylate; Isobornyl methacrylate; Methacrylic acid-2-methoxyl ethyl ester; Methacrylic acid methoxy base triethyleneglycol ester; Methacrylic acid-2-ethoxy ethyl ester; Tetrahydrofurfuryl methacrylate; Methacrylic acid-3-methoxyl butyl ester; 2-Methacryloyloxy-2-methyladamantane; Methacrylic acid 2-propyl group-2-diamantane ester; Methacrylic acid 8-methyl-8-three ring esters in the last of the ten Heavenly stems and methacrylic acid 8-ethyl-8-three ring esters in the last of the ten Heavenly stems etc.
As vinyl compound, 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.
Restriction especially of preparation method to the specific copolymer used among the present invention; For example can be through making at least a kind of monomer that suitably is selected from the monomer with at least a kind of group in carboxyl and the phenol property hydroxyl; With at least a kind of monomer in the monomer that suitably is selected from least a kind of group in hydroxyl that has except that phenol property hydroxyl and the amino with reactive hydrogen; With the monomer except that above-mentioned monomer as required; And polymerization initiator as required etc., in solvent, under 50～110 ℃ of temperature, carry out polyreaction and obtain.At this moment employed solvent constitutes specific copolymer monomer and specific copolymer as long as can dissolve, and has no particular limits.As concrete example, state the solvent of putting down in writing in (F) solvent after can enumerating.
Thus obtained specific copolymer normally this specific copolymer is dissolved in the state of the solution in the solvent.
In addition, under agitation the solution of the specific copolymer of above-mentioned acquisition is put in ether or the water etc. and is made it to precipitate again, with the sediment that generates filter clean after, pass through normal temperature or heat drying down at normal pressure or decompression, can process the powder of specific copolymer.Through such operation, can remove the polymerization initiator and the unreacted monomer that coexist with specific copolymer, the powder of the specific copolymer that its result can obtain to make with extra care.Under the situation that single job can not fully be made with extra care, the powder that obtains can be dissolved in the solvent again, repeat aforesaid operations.
In the present invention, can directly use the powder of specific copolymer, in (F) solvent of stating after also can being dissolved in its powder for example again, use as the state of solution.
< B composition >
(B) of the present invention composition is that number-average molecular weight is 100～2000 silicone compounds.Silicone compounds described here is meant organosilicone compounds and part thereof by hydrogen atom or the substituted compound of hydroxyl, and their modifier.
Silicone compounds as this (B) composition; Preferably in form cured film (pattern film forming) process by positive type photosensitive organic compound of the present invention, carry out in a series of heat treatment step; Has the characteristic of oozing out patterned surfaces; Said heat treatment step is; Be used for (A) composition and (C) thermal treatment of composition cross-linking reaction; The exposure after-baking is used for and (D) thermal treatment of composition cross-linking reaction.
As this silicone compounds, for example can enumerate straight chain shape silicone compounds, silicone compounds, cyclic siloxane compound and their multipolymer with branched structure.In addition; Can enumerate that these silicone compounds are alkoxy-modified, polyether-modified, fluorine modification, the modification of methyl styrene base, higher fatty acid are ester modified, the special modification of water wettability, senior alkoxy-modified etc. with non-reacted group modified silicone compounds, and these silicone compounds are amino modified, epoxy radicals modification, carboxy-modified, methyl alcohol modification, methacryl modification, sulfhydryl modified, phenol modification etc. are with silicone compounds of reactive group modification etc.
As their concrete example; Can enumerate dimethyl silicone polymer; Polymethy ethylsiloxane; PSI; Gather methyl hydroxyl siloxane; Gather the methyl-propyl siloxane; Gather diphenyl siloxane; Gather straight chain shape siloxane or its multipolymers such as methyl butyl siloxane; X 2-1401; Cyclic methyl phenylpolysiloxane; Ring-type is gathered methyl hydroxyl siloxane; The ring-type polymethy ethylsiloxane; Ring-type is gathered the methyl-propyl siloxane; Ring-type is gathered annular siloxanes such as methyl butyl siloxane; Alkoxy-modified; Polyether-modified; The fluorine modification; The modification of methyl styrene base; Higher fatty acid is ester modified; The special modification of water wettability; Senior non-reacted group modified siloxane such as alkoxy-modified; Amino modified; The epoxy radicals modification; Carboxy-modified; The methyl alcohol modification; The methacryl modification; Sulfhydryl modified; The group modified siloxane of phenol modification isoreactivity, and their multipolymer etc.
The silicone compound can be easily obtained as a commercially available product, and as specific examples include, for example, L-45 (Japan Unicar - (Corp.)), SH200, 510,550,710,705,1107 (Toray · double ウ co - ni nn bag (strain) manufactured), X-22-162C, 3701E, 3710,1821,164 S, 170DX, 176DX, 164A, 4952, KF96, 50,54,99,351,618,910,700,6001,6002 , 8010, KR271, 282 (Shin-Etsu Chemical Co. (Ltd.)) and the like straight-chain siloxane compound, VS-7158 (Japan Unicar - (Corp.)), BY11-003 (produced by Toray · da ウ co - ni nn bag (Co., Ltd.) ) and cyclic siloxane compound, L-77, 720,7001,7604, Y-7006, L-9300, FZ-2101, 2110,2130,2161,3704,3711,3722,3703,3720,3736,3705 , 3760 (Japan Unicar - (strain) manufactured), SF8427, 8428,8413,8417, SH193, 194,190,192,556,3746,3749,3771,8400, SRX280A, BY16-036, -848, -828, -853B,-855B, -839, -845, -752, -750, -838,-150B, BX16-854, -866, SF8421EG, SH28PA, SH30PA, ST89PA, ST103PA (Toray · da ウ co - ni nn bag (Co., Ltd.) ), ES1001N, 1023, X-22-161, -163, -169, -162, -164, KF-860, -101, -102, -6001, -6011, -6015, -8001, -351, - 412, -910, -905 (manufactured by Shin-Etsu Chemical Co. (Ltd.)), such as modified silicone compound, FS1265 (Toray · da ウ co - ni nn bag (Corp.)), FL-5, FL-10, X-22-820 , X-22-821, X-22-822, FL100 (Shin-Etsu Chemical Co. (Ltd.)) and the like fluorine-modified silicone compound, FZ-2203, 2207,2222 (Japan Unicar - (Co.)) and the like polysilicate Siloxane copolymers with polyalkylene oxide.
In aforesaid silicone compounds, especially preferably has the silicone compounds of the repetitive of structure shown in the following formula (1).
(in the formula, R < > 1 <> And R < > 2 <> Be hydrogen atom, alkyl or phenyl independently of one another, p representes positive integer.)
In the present invention, get final product so long as have the silicone compounds of the repetitive of structure shown in the above-mentioned formula (1), modification or unmodified all can.
In addition, contain at above-mentioned silicone compounds under the situation of epoxy radicals and since when exposure by after state sour composition that the photoacid generator of (E) composition produces probably can and this epoxy reaction, therefore preferably do not have the silicone compounds of epoxy radicals.
As the silicone compounds that does not have epoxy radicals; Can enumerate unmodified silicone compounds; Alkoxy-modified, polyether-modified, fluorine modification, the modification of methyl styrene base, higher fatty acid are ester modified, the special modification of water wettability, senior non-reacted group modified silicone compounds such as alkoxy-modified, and the group modified silicone compounds of amino modified, carboxy-modified, methyl alcohol modification, methylpropenyl modification, sulfhydryl modified, phenol-modified isoreactivity etc.
In the silicone compounds of above-mentioned (B) composition, the silicone compounds of unmodified silicone compounds and methyl alcohol modification obtains easily and (A) intermiscibility of composition, in addition because the silicone compounds of fluorine modification can obtain oil-proofness, so preferred.
Fluorine modified siloxane compound described here is meant with above-mentioned organosilicone compounds and partly by hydrogen atom or the substituted compound of hydroxyl and their modifiers, further uses the compound of fluorine modification.
So-called this fluorine modified siloxane compound specifically, is in above-mentioned formula (1), the R in the formula < > 1 <> And/or R < > 2 <> It is the silicone compounds of fluoro-alkyl.
Here the import volume of fluoroalkyl is preferably 10～100%, and more preferably 20～80%.Fluoroalkyl import volume oil-proofness after a little while reduces, and UV-ozone treatment patience reduced when the fluoroalkyl import volume was too much.
(B) composition silicone compounds that uses among the present invention; The more preferably silicone compounds of methyl alcohol modification or fluorine modified siloxane compound in above-claimed cpd; And the silicone compounds of only using the fluorine modification; Preferred especially with the fluorine modified siloxane compound of unmodified silicone compounds with the fluorine modification, promptly do not implement the silicone compounds of the modification beyond the defluorination modification.
As (B) composition silicone compounds that uses among the present invention; From following viewpoint; Promptly in the solution of positive type photosensitive organic compound of the present invention; Good with the intermiscibility of each composition; Particularly the intermiscibility with (A) composition alkali-soluble copolymer is good; And this positive type photosensitive organic compound has good stable property; Dissolubility in this external developer solution; And the remaining pattern upper part water resisting property of giving as territory, non-exposed area (shading light part) also has oil-proofness, and preferred number average molecular weight is 100～2000 compound.
As the usage ratio of the silicone compounds of (B) composition, the alkali-soluble copolymer with respect to 100 weight portions (A) composition is preferably 0.1～30 mass parts, and more preferably 1～20 mass parts is preferably 3～15 mass parts especially.
(B) consumption of component cpd is if the amount of the lower limit of not enough above-mentioned scope, and then the water resisting property on the patterned surfaces becomes insufficient sometimes.Sometimes the inner emptying aperture that forms of pattern is undersized in addition.In addition when using fluorine modified siloxane compound as (B) composition, on patterned surfaces sometimes not only water resisting property also have oil-proofness to become insufficient, and UV-ozone treatment patience also becomes insufficient.
The consumption of (B) component cpd is if surpass the amount of the upper limit of above-mentioned scope on the other hand, when formation is filmed whiting takes place then sometimes or film inhomogeneous.
So in the present invention, through suitable kind and the consumption of selecting as the silicone compounds of (B) composition, also can control resulting film and cured film in the size of the emptying aperture that forms.
(C) composition
(C) composition is the compound that contains 2 above vinyl ether groups in 1 molecule.So long as can be under habitual prebake temperature with 1 molecule of (A) the alkali soluble resins heat cross-linking of composition in contain 2 above vinyl ether groups compound get final product, to its kind and qualification especially of structure.
Be somebody's turn to do the compound of (C) composition; With the alkali soluble resins heat cross-linking of (A) composition after; The acid that produces through exposure in the presence of photoacid generator separates (taking off crosslinked) from the alkali soluble resins of (A) composition, through using alkaline developer to develop, can remove with the alkali soluble resins of (A) composition then.Therefore as this compound, generally can use the vinyl ethers compound that uses in the vinyl ether type chemically amplified corrosion-resisitng agent composition etc.Under the situation of using this compound, have through the use level that changes this compound and adjust heat cross-linking density, can control the advantage of the shape that forms film.
And the compound of conduct (C) composition, in above-mentioned vinyl ethers compound, development this respect under the state that exposed portion, does not have residual film or residue, special preferred formula (2) and the represented compound of formula (3).
formula (2)
(in the formula, n is 2～10 integer, and k is 1～10 integer, R < > 3 <> Expression n valency organic group.)
Figure G2007800176897D00141
formula (3)
(in the formula, m representes 2～10 integer.)
The n of formula (2) representes the number of 1 vinyl ether group in the molecule, as more preferably 2～4 integer of n.And the m of formula (3) also representes the number of 1 vinyl ether group in the molecule, as more preferably 2～4 integer of m.
As the object lesson of the compound of formula (2) and formula (3) expression, can enumerate two (4-(ethyleneoxy methyl) cyclohexyl methyl) glutarate, three (monoethylene glycol) divinyl ether, hexane diacid divinyl ester, diethylene glycol divinyl ether, three (4-ethyleneoxy) butyl trimellitate, two (4-(ethyleneoxies) butyl) terephthalate, two (4-(ethyleneoxies) butyl isophthalic acid ester and cyclohexanedimethanol divinyl ether etc.
In addition, (C) usage ratio of the compound of composition with respect to the alkali soluble resins of 100 mass parts (A) composition, is 1～80 mass parts, preferred 5～40 mass parts.(C) consumption of component cpd is if the too small amount of not enough above-mentioned scope lower limit, and then the film in the unexposed portion subtracts significantly and the undulations of pattern appearance becomes bad.On the other hand, if (C) consumption of component cpd is the mistake volume that surpasses the upper limit of above-mentioned scope, then the light sensitivity of film reduces greatly, develops can produce residue between the pattern of back.
< D composition >
(D) composition is the compound that contains 2 above blocked isocyanate bases in 1 molecule.It is so long as contain the compound of 2 above blocked isocyanate bases in 1 molecule; With respect to (C) component cpd heat cross-linking or and then take off the formed film of alkali soluble resins of crosslinked (A) composition with it; Can under for example habitual back bake out temperature, heat curing get final product, its kind and structure are not promptly limited especially.
Be somebody's turn to do the compound of (D) composition; In 1 molecule, has 2 above NCOs (NCO) blocked isocyanate base by due care base end-blocking; And one expose under the high temperature when heat cure; Protection base (end-blocking part) breaks away from regard to thermal dissociation; Jie is by the NCO that generates; Carry out cross-linking reaction each other with the functional group that is used for heat cure in the alkali soluble resins of (A) composition (for example hydroxyl beyond the phenol hydroxyl and amino) with reactive hydrogen; For example can enumerate, have 2 compounds (this group can be the same or different) in 1 molecule with the group of following formula (4) expression.
Figure G2007800176897D00151
formula (4)
(in the formula, R < > 4 <> The organic group of expression end-blocking part.)
(D) component cpd that contains 2 above blocked isocyanate bases in 1 molecule for example can obtain the compound effects that contains 2 above isocyanate group in 1 molecule through making suitable end-capping reagent.
As the compound that contains 2 above isocyanate group in 1 molecule; Can enumerate for example isophorone diisocyanate, 1; 6-hexamethylene diisocyanate, methylene two (4-cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate etc.; Perhaps their dipolymer, trimer, or the reactant of they and glycols, three alcohols, two amines, three amines.
As end-capping reagent; For example can enumerate; Methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, 2-ethoxy hexanol, 2-N; Alcohols such as N-dimethylaminoethanol, cellosolvo, cyclohexanol; Phenols such as phenol, o-nitrophenol, parachlorophenol, orthoresol, metacresol or paracresol; Lactams such as epsilon-caprolactams; Oximes such as acetoxime, methyl ethyl ketoxime, methylisobutylketone oxime, cyclohexanone oxime, acetophenone oxime, diphenyl-ketoxime; Pyrazoles, 3; Pyrazoleses such as 5-dimethyl pyrazole, 3-methylpyrazole, thio-alcohols such as dodecyl mercaptans, benzenethiol.
For the compound that makes (D) composition in the back the such high temperature of bake out temperature down Jie leave the isocyanate group that is produced and carry out cross-linking reaction by the end-blocking partial thermal decomposition; And under the such low temperature of prebake temperature, do not carry out crosslinked through isocyanate group; Compound as (D) composition; The thermal dissociation temperature compound more much higher than prebake temperature of preferred especially end-blocking part, for example the thermal dissociation temperature of end-blocking part is 120 ℃～230 ℃ a compound.
As the compound of this (D) composition, for example can enumerate following object lesson.
In the formula, from thermotolerance, filming property aspect, more preferably isocyanate compound is listed below as such compound by isophorone diisocyanate (D) component cpd of deriving.R in the following formula representes organic group.
Figure G2007800176897D00162
Figure G2007800176897D00171
Among the present invention, (D) compound of composition can use a kind separately, also can make up more than 2 kinds and use.
The usage ratio of (D) component cpd in addition is 1～80 mass parts with respect to the alkali soluble resins of 100 mass parts (A) composition, preferred 5～40 mass parts.(D) if the consumption of component cpd is the too small amount of not enough above-mentioned scope lower limit; Then heat curing is insufficient, can not get satisfied cured film, if on the other hand (D) consumption of component cpd for surpassing the mistake volume of above-mentioned range limit; Then developing becomes insufficient, can produce the development residue.
(E) composition
(E) composition is photoacid generator (PAG).It is the material that directly or indirectly produces acid (sulfonic acid class, carboxylic acids etc.) through the rayed of using in the exposure, as long as have this character, to not restriction especially such as its kind and structure.
Photoacid generator as (E) composition; For example can enumerate diazomethane compound, salt compound, sulfimide, two sulfone compounds, sulfonic acid compound, nitrobenzene compound, benzoin tosylate compound, iron-aromatic hydrocarbons complex compound, halogen-containing triaizine compounds, acetophenone derivs compound and contain oxime sulfonates compound of cyanic acid etc.Any all goes for the present invention, restriction especially the photoacid generator of at present known or present use.In addition, in the present invention, (E) photoacid generator of composition can use a kind separately, and perhaps combination is used more than 2 kinds.
Object lesson as photoacid generator is listed below.Certainly these compounds are the examples in extremely most photoacid generators that can be suitable for, and are not limited to these.
Figure G2007800176897D00201
formula (5)
Figure G2007800176897D00202
formula (8)
Figure G2007800176897D00204
formula (9)
Diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium methanesulfonate, p-toluenesulfonic acid diphenyl iodonium salts, diphenyl iodonium bromide, diphenyl yl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate salt, diphenyl iodonium hexafluoro arsenate, di (t-butylphenyl) iodonium hexafluorophosphate, di (p-tert- butylphenyl) iodonium methanesulfonate, bis (p-tert-butylphenyl) iodonium p-toluenesulfonate, di (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert- butylphenyl) iodonium tetrafluoroborate, di (tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate salts, triphenyl sulfonium chloride, triphenyl sulfonium bromide, triphenyl sulfonium trifluoromethanesulfonate, tris (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl ) sulfonium hexafluorophosphate salt of phosphonic acid, tris (p-ethoxyphenyl) sulfonium tetrafluoroborate salts, triphenyl phosphonium chloride, triphenyl phosphonium bromide, tris (p-methoxyphenyl) phosphonium tetrafluoroborate salt, tris (p-methoxyphenyl) phosphonium hexafluorophosphate salt of phosphonic acid, tris (p-ethoxyphenyl) phosphonium tetrafluoroborate salt,
Figure G2007800176897D00211
Figure G2007800176897D00212
formula (17)
Figure G2007800176897D00213
style (18)
Figure G2007800176897D00214
formula (19)
Figure G2007800176897D00215
Figure G2007800176897D00216
Figure G2007800176897D00217
style (22)
Figure G2007800176897D00221
Figure G2007800176897D00222
style (24)
Figure G2007800176897D00223
formula (25)
Figure G2007800176897D00224
style (26)
Figure G2007800176897D00225
formula (27)
Figure G2007800176897D00226
style (28)
Figure G2007800176897D00227
formula (29)
Figure G2007800176897D00229
formula (31)
Figure G2007800176897D002210
style (32)
Figure G2007800176897D002211
Figure G2007800176897D00231
Figure G2007800176897D00241
formula (50)
Figure G2007800176897D00242
formula (51)
Figure G2007800176897D00243
Figure G2007800176897D00251
The usage ratio of (E) composition photoacid generator in addition is 0.5～80 mass parts with respect to the alkali soluble resins of 100 mass parts (A) composition, is preferably 1～30 mass parts.(E) consumption of the photoacid generator of composition is if the too small amount of not enough above-mentioned scope lower limit; (C) component cpd of heat cross-linking can not be fully dissociates from the alkali soluble resins of (A) composition when then making public; Be difficult to obtain the fluctuating of desirable pattern appearance; On the other hand; If (E) consumption of the photoacid generator of composition is the mistake volume that surpasses above-mentioned range limit, then the storage stability variation of positive type photosensitive organic compound.
(F) solvent
Positive type photosensitive organic compound of the present invention contains (A) composition, (B) composition, (C) composition, (D) composition and (E) composition, and they exist with the state that is dissolved in (F) solvent.
Thereby (F) solvent that uses among the present invention is dissolving (A) composition～(E) composition, and dissolving add as required after state the solvent of (G) composition～(I) become to grade, as long as have such solubility property, to qualification especially such as its kind and structure.
As such (F) solvent; For example can enumerate; Glycol monoethyl ether; Ethylene glycol monoethyl ether; Acetic acid methyl cellosolve; The acetate ethyl cellosolve; 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; The 2-heptanone; Gamma-butyrolacton; The 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; The 3-ethoxyl ethyl propionate; 3-ethoxy-propionic acid methyl esters; Methyl pyruvate; Ethyl pyruvate; Ethyl acetate; Butyl acetate; Ethyl lactate; Butyl lactate; N; Dinethylformamide, N-dimethyl acetamide and N-Methyl pyrrolidone etc.
These solvents can use a kind separately, perhaps make up more than 2 kinds and use.
In these (F) solvents, from the good and safe viewpoint of filming property, preferred propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, ethyl lactate, butyl lactate etc.These solvents are general to be used as the solvent that is used for photo anti-corrosion agent material.
(G) composition
In positive type photosensitive organic compound of the present invention, in the limit of not damaging effect of the present invention, can also cooperate other alkali soluble resinss conduct (G) compositions the composition except (A).Not good from the development of easy inhibition positive type photosensitive organic compound of the present invention when developing, and can give aspect such as multiple functional characteristic and set out preferred (G) composition that cooperates.
As such (G) composition; For example can enumerate; Except that (A) acrylic resin and hydroxy styrenes resinoid, phenol novolac resin, polyamide, polyimide precursor, the polyimide resin the composition, and contain on the side chain in these alkali soluble resinss for example by fluorine class alkali soluble resins of the substituted organic group of fluorine atom etc.
In the present invention in other alkali soluble resinss of (G) composition of Shi Yonging, be under the situation of silicone compounds of fluorine modification at above-mentioned (B) composition, preferably adopt above-mentioned fluorine class alkali soluble resins.
In above-mentioned fluorine class alkali soluble resins, as the substituted organic group of fluorine atom, not restriction especially, but preferred especially perfluoroalkyl.
And as above-mentioned fluorine class alkali soluble resins, monomer and other monomers that preferably will contain the substituted organic group of fluorine atom share the acrylic copolymer (following simply be called " fluorine analog copolymer ") that carries out copolymerization and obtain.
Object lesson as the monomer that contains the substituted organic group of fluorine atom; Can enumerate acrylic acid five fluoropropyl esters; Acrylic acid seven fluorine butyl esters; Acrylic acid 15 fluorine octyl group esters; Acrylic acid 17 fluorine decyl ester; Acrylic acid 2-(nine fluorine butyl) ethyl ester; Acrylic acid 2-(perfluor decyl) ethyl ester; Acrylic acid 2-(perfluoro hexyl) ethyl ester; Acrylic acid trifluoroethyl ester; Methacrylic acid five fluoropropyl esters; Methacrylic acid seven fluorine butyl esters; Methacrylic acid 15 fluorine octyl group esters; Methacrylic acid 17 fluorine decyl ester; Methacrylic acid 2-(nine fluorine butyl) ethyl ester; Methacrylic acid 2-(perfluor decyl) ethyl ester; Methacrylic acid 2-(perfluoro hexyl) ethyl ester; Methacrylic acid trifluoroethyl ester etc.
The monomer that especially preferably contains perfluoroalkyl in these, for example acrylic acid 2-(perfluor decyl) ethyl ester, acrylic acid 2-(perfluoro hexyl) ethyl ester, acrylic acid trifluoroethyl ester, methacrylic acid 2-(perfluor decyl) ethyl ester, methacrylic acid 2-(perfluoro hexyl) ethyl ester, methacrylic acid trifluoroethyl ester etc.
Above-mentioned fluorine analog copolymer can carry out copolymerization as long as will constitute the monomer component and the above-mentioned fluorine class monomer of specific copolymer this moment through obtaining with obtaining the same method of (A) composition specific copolymer.
In the present invention, (G) the common content of other alkali soluble resinss of composition can be, is 1 mass parts～90 mass parts based on 100 mass parts (A) composition.
But use fluorine modified siloxane compound as above-mentioned (B) composition and fluorine class alkali soluble resins as under the situation of (G) composition; Owing in above-mentioned scope, can damage effect of the present invention sometimes; Therefore the content of fluorine class alkali soluble resins for example is 0.1～20 mass parts based on 100 mass parts (A) composition; And then according to circumstances be 0.5～15 mass parts, more preferably 1～10 mass parts.The consumption of above-mentioned fluorine class alkali soluble resins is if the too small amount of not enough above-mentioned scope lower limit; Sometimes it is not good to take place when then developing to develop; On the other hand, if the consumption of above-mentioned fluorine class alkali soluble resins is the mistake volume that surpasses above-mentioned range limit, then UV-ozone patience reduces sometimes.
(H) composition
(H) composition is an amines.In positive type photosensitive organic compound of the present invention,, in the limit of not damaging effect of the present invention, can also contain amines in order to improve its storage stability.
Amines as (H) composition; Not restriction especially; For example can enumerate; Tertiary amines such as triethanolamine, three butanolamines, triisopropanolamine, trimethylamine, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, three tert-butylamines, trioctylamine, triphenylamine and diazabicyclooctane; Aromatic amine such as pyridine and 4-dimethylaminopyridine; Can also enumerate primary amine such as benzylamine and n-butylamine, secondary amine such as diethylamine and di-n-butylamine in addition.
(H) amines of composition can use a kind separately, perhaps makes up more than 2 kinds and uses.
Under the situation of using amines, its content for example is 0.001～5 mass parts with respect to the alkali soluble resins of 100 mass parts (A) composition, and then according to circumstances is 0.005～1 mass parts, more preferably 0.01～0.5 mass parts.(H) consumption of the amines of composition is if the too small amount of not enough above-mentioned scope lower limit; Then can not fully improve the storage stability of positive type photosensitive organic compound; On the other hand; If (H) consumption of the amines of composition is the mistake volume that surpasses above-mentioned range limit, then the light sensitivity of positive type photosensitive organic compound reduces sometimes.
< I composition >
(I) composition is a surfactant.In order to improve screening characteristics, in the limit of not damaging effect of the present invention, in positive type photosensitive organic compound of the present invention, can also contain surfactant.
As the surfactant of (I) composition, restriction especially for example can not enumerated fluorine class surfactant, silicone surfactant, nonionic class surfactant etc.As this surfactant, for example can use the commercially available article of Sumitomo ス リ-エ system (strain) manufacturing, big Japanese イ Application キ chemical industry (strain) manufacturing or Asahi Glass (strain) manufacturing etc.Therefore these commercially available article all are fit to owing to obtain easily.As its concrete example, can enumerate エ Off ト Star プ EF301, EF303, EF352((strain) ジ エ system コ (make)), メ ガ Off ア Star Network F171, the big Japanese イ Application キ chemical industry of 173((strain) make), Off ロ ラ-De C430, FC431(Sumitomo ス リ-エ system (strain) make), ア サ ヒ ガ-De G710, サ-Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106(Asahi Glass (strain) make) etc. fluorine class surfactant.
(I) surfactant of composition can use a kind separately, perhaps makes up more than 2 kinds and uses.
Under the situation of using surfactant, its content is generally below the 0.2 quality % in 100 quality % positive type photosensitive organic compounds, is preferably below the 0.1 quality %.Even the amount of surfactant of (I) composition is set at the amount that surpasses 0.2 quality %, the improved effect of above-mentioned screening characteristics is also not obvious, becomes uneconomical.
< other adjuvants >
In the limit of not damaging effect of the present invention, as required, can also contain bonding assistants such as rheology control agent, silane coupling agent in the positive type photosensitive organic compound of the present invention; Pigment, dyestuff, preserving stabilizer; Defoamer, perhaps cosolvent such as polyhydric phenol, polybasic carboxylic acid etc.
< positive type photosensitive organic compound >
Positive type photosensitive organic compound of the present invention is following composition; It contains the photoacid generator and (F) solvent of the compound that contains the blocked isocyanate base, (E) composition of the compound that contains vinyl ether group, (D) composition of silicone compounds, (C) composition of alkali soluble resins, (B) composition of (A) composition; And according to required separately, can also contain in surfactant and other adjuvant of amines, (I) composition of alkali soluble resins, (H) composition of (G) composition more than a kind.
Wherein, the preferred example of positive type photosensitive organic compound of the present invention is as described below.
: based on 100 mass parts (A) composition, contain 0.1～30 mass parts (B) composition, 1～80 mass parts (C) composition, 1～80 mass parts (D) composition and 0.5～80 mass parts (E) composition, these compositions are dissolved in the positive type photosensitive organic compound in (F) solvent.
: in the composition of above-mentioned [1] (wherein (B) composition is under the situation of fluorine modified siloxane compound), also contain the positive type photosensitive organic compound of 0.1～20 mass parts (G) composition (fluorine class alkali soluble resins) based on 100 mass parts (A) composition.
: in the composition of above-mentioned [1] or [2], also contain the positive type photosensitive organic compound of 0.001～5 mass parts (H) composition based on 100 mass parts (A) composition.
: in the positive type photosensitive organic compound of above-mentioned [1], [2] or [3], also contain the positive type photosensitive organic compound of following (I) composition of 0.2 quality %.
The ratio of solid constituent in the positive type photosensitive organic compound of the present invention does not promptly limit as long as each composition is dissolved in the solvent equably especially, for example is 1～80 quality %, for example is 5～60 quality % in addition, perhaps is 10～50 quality %.Here so-called solid constituent is meant the composition of from whole compositions of positive type photosensitive organic compound, removing (F) solvent.
Modulator approach to positive type photosensitive organic compound of the present invention does not limit especially; As its modulator approach; For example can enumerate; (A) composition (alkali soluble resins) is dissolved in (F) solvent; According to the rules mixed (B) composition (silicone compounds) in this solution) contain the compound of 2 above vinyl ether groups in the composition (1 molecule)) contain the compound of 2 above blocked isocyanate bases in the composition (1 molecule)) composition (photoacid generator) and (I) composition (surfactant); Form the method for homogeneous solution; Perhaps in the suitable stage of this modulation method, adding (H) composition (amines) as required again) composition (alkali soluble resins) and/or other adjuvant carry out method of mixing.
In the modulation of positive type photosensitive organic compound of the present invention; Can directly use the solution of the specific copolymer that obtains through the polyreaction in (F) solvent; At this moment when in the solution of this (A) composition, becoming to grade to form homogeneous solution with above-mentioned same adding (B) composition, (C) composition, (D); In order to regulate concentration, additional input again (F) solvent.At this moment, (F) solvent that uses in the specific copolymer forming process and modulation are used to regulate (F) solvent of concentration during positive type photosensitive organic compound can be identical, also can be different.
And the solution of the positive type photosensitive organic compound that is modulated into is the filtration back uses such as filtrator about 0.2 μ m using the aperture preferably.
< filming and cured film >
On semiconductor substrate (for example silicon/silicon dioxide coats substrate, silicon nitride substrate, the metal for example substrate that coats such as aluminium, molybdenum, chromium, glass substrate, quartz base plate, ito substrate etc.); Apply positive type photosensitive organic compound of the present invention through then spin coating, ink-jet coating etc. after spin coating, flow coat, roller coat, slit coating, the slot coated; Predrying through hot plate or baking oven etc. then, can form and film.This is filmed through heat treated then, and forms the normal Photosensitive resin film.
As the condition of this heat treated, adopt heating-up temperature and the heat time heating time for example from the scope of 70 ℃～160 ℃ of temperature, 0.3～60 minute time, suitably selected.Are preferably heating-up temperature and heat time heating time 80 ℃～140 ℃, 0.5～10 minute.
In addition, the thickness of the normal Photosensitive resin film that is formed by positive type photosensitive organic compound for example is 0.1～30 μ m, for example is 0.2～10 μ m in addition, and then for example is 0.2～5 μ m.
And the heat treated when the normal Photosensitive resin film of formation passes through to form because (C) compound that contains vinyl ether group of composition is crosslinked on the resin of (A) composition, forms the film that is insoluble in alkaline developer.At this moment, be lower than in the heat treated temperature under the situation of said temperature scope lower limit, heat cross-linking becomes insufficient sometimes, subtracts thereby in unexposed portion, produce film.Exceed the said temperature range limit and under the too high situation, the heat cross-linking part that once forms is sometimes cut off once more in the heat treated temperature in addition, thereby cause that in unexposed portion film subtracts.
By the normal Photosensitive resin film that positive type photosensitive organic compound of the present invention forms, the mask that has predetermined pattern when use is through ultraviolet ray, ArF, KrF, F < > 2 <> When light such as laser made public, through the acid effect that the photoacid generator (PAG) by (E) composition that contains in the positive type photosensitive organic compound produces, exposed portion dissolved in the alkaline developer solution in this film.
Then, to the back heating (PEB) that makes public of eurymeric photosensitive resin film.As heating condition at this moment, can adopt heating-up temperature and heat time heating time in the scope that suitably is selected from 80 ℃～150 ℃ of temperature, 0.3～60 minute time.
Then, use alkaline-based developer to develop.Remove the part of having made public in the normal Photosensitive resin film thus, form the fluctuating of pattern appearance.
As operable alkaline-based developer; For example can enumerate; The aqueous solution of alkali metal hydroxide such as potassium hydroxide, NaOH; The aqueous solution of quaternary ammonium hydroxides such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, alkaline aqueous solutions such as amine aqueous solution such as monoethanolamine, propylamine, ethylenediamine.In addition, can also add surfactant etc. in these developer solutions.
The aqueous solution of in above-mentioned～2.38 quality % tetraethyl ammonium hydroxides is generally used as the developer solution of photoresist; In positive type photosensitive organic compound of the present invention, also use this alkaline-based developer, can not cause problems such as expansion, can develop well.
In addition, as developing method, can use liquid contain method, infusion process, shake infusion process etc. any one.At this moment development time is generally 15～180 seconds.
After the development, use flowing water that the eurymeric photosensitive resin film is carried out for example 20～90 seconds washing, then use pressurized air or compressed nitrogen or air-dry, remove the moisture on the substrate, thereby obtained forming the film of pattern through rotation.
Then; To such pattern film forming, through being used for the back oven dry of heat curing, specifically through using hot plate, baking oven etc. to heat; Thereby obtain excellences such as thermotolerance, the transparency, smooth voltinism, low water absorbable, chemical resistance, and have the film of good fluctuating pattern.
As the back oven dry, the general employing is selected from 140 ℃～250 ℃ heating-up temperatures in the temperature range, handles 5～30 minutes in the time of on hot plate, handles 30～90 minutes method in the time of in baking oven.
And, through so back oven dry, can obtain having the target cured film of good pattern form.
As mentioned above, through positive type photosensitive organic compound of the present invention, can be formed with sufficient ISO and when developing the film of unexposed portion subtract very little, filming of having fine pattern.
In addition, this cured film is the structure that has the thin emptying aperture of sub-micro in the film.
Characteristic as this cured film; Thermotolerance and solvent resistance are excellent; The film surface has high waterproof, under the situation of employing fluorine modified siloxane compound as above-mentioned (B) composition, also has high oil-proofness in addition, can suppress to reduce through water resisting property after the oxygen plasma treatment and oil-proofness.
Therefore, be applicable in the purposes such as edge that for example the division pixel of organic EL is used that perhaps various films in array planarization film, liquid crystal or the OLED display of TFT type liquid crystal cell are for example in the purposes such as interlayer dielectric, diaphragm, dielectric film.
Embodiment
The present invention will be described in more detail to enumerate embodiment below, but the present invention is not limited to these embodiment.
[dummy suffix notation that uses among the embodiment]
The dummy suffix notation meaning of using among the following embodiment as follows.
MAA: methacrylic acid
MMA: methyl methacrylate
HEMA: 2-hydroxyethyl methacry-late
CHMI:N-cyclohexyl maleimide
FMA: perfluoroalkyl methacrylate
TMSSMA: methacrylic acid-3-[three (trimethylsiloxy) silicyl] propyl diester
IBN: azoisobutyronitrile
PGMEA: propylene glycol methyl ether acetate
MAK: methyl amyl ketone (2-heptanone)
AG1: oxime sulfonates class photoacid generator: チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) makes the CGI1397(trade name)
PVE1:1,4-cyclohexanedimethanol divinyl ether
The compound that contains 2 blocked isocyanate bases in the NCO1:1 molecule: デ グ サ AG makes VESTAGON(registered trademark)B1065(trade name)
R30: big Japanese イ Application キ chemical industry (strain) is made メ ガ Off ア Star Network R-30(trade name)
PDMS1: dimethyl silicone polymer C-terminal number-average molecular weight (below be called Mn) :550
PDMS2: dimethyl silicone polymer-gather diphenyl siloxane multipolymer C-terminal Mn:1000
PDMS3: dimethyl silicone polymer Mn:580
PDMS4: the terminal Mn:5600 of dimethyl silicone polymer dihydroxy alkyl
PDMS5: the terminal Mn:250000 of dimethyl silicone polymer divinyl
PDMS6: dimethyl silicone polymer C-terminal Mn:8000
PDFS1:50% fluorine modified dimethyl polysiloxane Mn:1000
PDFS2:100% fluorine modified dimethyl polysiloxane Mn:1000
[mensuration of number-average molecular weight and weight-average molecular weight]
Use Japanese beam split (strain) to make GPC device (Shodex(registered trademark) post KF803L and KF804L); The flow that (40 ℃ of column temperature) divides with 1ml/ in post flows through the stripping solvents tetrahydrofurane to carry out under the condition of wash-out, measures the number-average molecular weight and the weight-average molecular weight of the specific copolymer that obtains according to following synthetic example.Following in addition number-average molecular weight (below be called Mn) and weight-average molecular weight (below be called Mw) are used the polystyrene conversion value representation.
< synthetic example 1 >
Use 15.5g MAA, 35.3g CHMI, 25.5g HEMA, 23.7g MMA as the monomer that constitutes specific copolymer; Use 5g AIBN as radical polymerization initiator; Through making them in 200g solvent GMEA, under 60 ℃～100 ℃ of temperature, carry out polyreaction, obtain solution (the specific copolymer concentration: 27.5 quality %) of (A) composition (specific copolymer) of Mn4100, Mw7600.(P1)
< synthetic example 2 >
Use 8.0g MAA, 12.0g CHMI, 12.0g HEMA, 8.0g PFMA as the monomer that constitutes specific copolymer; Use 0.88g AIBN as radical polymerization initiator; Through making them in 95.4g solvent GMEA, under 60 ℃～100 ℃ of temperature, carry out polyreaction, obtain solution (the specific copolymer concentration: 30.0 quality %) of (A) composition (specific copolymer) of Mn6400, Mw10500.(P2)
< embodiment 1～6 and comparative example 1～5 >
According to the composition shown in following table 1; Through according to the rules mixed (B) composition, (C) composition, (D) composition, (E) composition in the solution of (A) composition with (F) solvent, also have (I) composition; At room temperature stir and formed uniform solution in 3 hours, modulate the positive type photosensitive organic compound of each embodiment and each comparative example.
[table 1]
(A) solution of composition (g) (B) composition (g) (C) composition (g) (D) composition (g) (E) composition (g) (F) solvent (g) (I) composition (g)
Embodiment 1 P1 15 PDMS1 ?0.21? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Embodiment 2 P1 15 PDMS1 ?0.41? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Embodiment 3 P1 15 PDMS2 ?0.21? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Embodiment 4 P1 15 PDMS2 ?0.41? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Embodiment 5 P1 15 PDMS3 ?0.21? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Embodiment 6 P1 15 PDMS3 ?0.41? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Comparative example 1 P1 15 PDMS4 ?0.21? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Comparative example 2 P1 15 PDMS4 ?0.41? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Comparative example 3 P1 15 PDMS5 ?0.21? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Comparative example 4 P1 15 PDMS6 ?0.21? PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? -
Comparative example 5 P1 15 - PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? R30 ?0.0028
Comparative example 6 P1/P2 ?14.3/0.7 - PVE1 0.62 NCO1 ?0.41 PAG1 0.21 PGMEA ?5.75? R30 ?0.0028
Various compositions in the embodiment 1～embodiment 6 that obtains and the comparative example 1～comparative example 6 subtract (in the unexposed portion), contact angle, emptying aperture, MEA patience and thermotolerance to stability of solution, light sensitivity, film with acryl resin respectively and estimate.
[stability of solution evaluation]
For the above-mentioned positive type photosensitive organic compound that obtains, after the modulation said composition, with transparent and uniform dissolution be labeled as zero, gonorrhoea appears or separate out being labeled as of insolubles *.
[evaluation of light sensitivity]
After using spinner to apply positive type photosensitive organic compound on the silicon wafer, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.Thickness uses FILMETRICS to make F20 and measures., this makes that light intensity is 5.5mW/cm under the 65nm of ultraviolet lamp PLA-600FA irradiation certain hour on filming through キ ヤ ノ Application (strain) < > 2 <> Ultraviolet ray, then under 110 ℃ of temperature, on hot plate, make public back heating (PEB)120 second.After dipping developed in 60 seconds in 0.4 quality % tetramethyl ammonium hydroxide (below be called MAH) aqueous solution then, carry out 20 second flow water washings with ultrapure water.There is not the required lowest exposure amount (mJ/cm of molten slag with making in the exposed portion < > 2 <> ) as light sensitivity.
[evaluation that film subtracts]
After using spinner to apply positive type photosensitive organic compound on the silicon wafer, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This film carries out 20 second flow water washings with ultrapure water after in 0.4 quality TMAH aqueous solution, flooding for 60 seconds.Then measure the thickness of this film, the film of the unexposed portion that estimating develops produces subtracts degree.The F20 that thickness during this is estimated uses FILMETRICS to make measures.
[evaluation of contact angle]
After using spinner to apply positive type photosensitive organic compound on the quartz base plate, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This is filmed and carried out the back oven dry in 30 minutes through heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.The water on this cured film of Drop Master mensuration that use consonance interface science (strain) is made and the contact angle of diiodomethane.
[evaluation of Cement Composite Treated by Plasma patience]
After using spinner to apply positive type photosensitive organic compound on the silicon wafer, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This is filmed and carried out the back oven dry in 30 minutes through heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.The UV-312 of use (strain) テ Network ノ PVC ジ ヨ Application manufacturing films to this and carries out 5 minutes ozone washing.Use Drop Master that consonance interface science (strain) makes according to measuring the contact angle of the water on the film that ozone washing handled with above-mentioned [evaluation of contact angle] same method.
[evaluation of emptying aperture]
After using spinner to apply positive type photosensitive organic compound on the silicon wafer, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This is filmed and carried out the back oven dry in 30 minutes through heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.Use scanning electron microscope (below be called SEM) to confirm that this section of filming has or not the size in emptying aperture and emptying aperture footpath.In addition, in the following table 2 " < 100 " mark representes to exist the emptying aperture of the not enough 100nm of diameter.
The evaluation of [MEA patience]
After using spinner to apply positive type photosensitive organic compound on the quartz base plate, under 120 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This film flooded for 60 seconds in 0.4 quality TMAH aqueous solution after, carry out flowing water washing in 20 seconds with ultrapure water.Then the back oven dry was carried out in heating in 30 minutes under 230 ℃ of temperature, and forming thickness is the cured film of 1.9 μ m.Under 60 ℃ of temperature the heating this film and in monoethanolamine the dipping 20 minutes after, washed for 20 seconds with pure water.Then after on the hot plate of 180 ℃ of temperature dry 10 minutes, measure thickness.With the thickness after the back oven dry handle with MEA, dried thickness not variation be labeled as MEA patience zero, reduced being labeled as *.
[stable on heating evaluation]
Evaluation in above-mentioned [MEA patience] in, except substrate is changed to the silicon wafer by quartz base plate, form the cured film of 1.9 μ m with same method.Cut and get this cured film, measure DTA-TG as sample.The temperature that sample mass is reduced 5 quality % is as " 5% quality reduces temperature ".
[evaluation result]
The result who carries out above evaluation is presented in the following table 2.
[table 2]
< > * <> So-called " not having film to subtract " is illustrated in to measure and do not observe film among the result and subtract (film that does not become in other words, practical problems subtracts).
To embodiment 1～6, behind the modulation positive type photosensitive organic compound, can obtain not having the homogeneous solution of gelation or separation.
The positive type photosensitive organic compound of embodiment 1～6 all is ISO in addition, does not observe the film that becomes practical problems in the unexposed portion and subtracts, and all has high waterproof in the Cement Composite Treated by Plasma front and rear surfaces, in film, forms emptying aperture in addition.
On the other hand, comparative example 1～4, the stability of solution of positive type photosensitive organic compound is low, can not obtain uniform solution.
In addition, the positive type photosensitive organic compound of comparative example 5, the water resisting property on film surface is low, does not also form emptying aperture in the film.
The positive type photosensitive organic compound that also has comparative example 6, the water resisting property on surface is high, but UV plasma patience is low, does not also form emptying aperture in the film.
< synthetic example 3 >
Use 15.5g MAA, 35.3g CHMI, 25.5g HEMA, 23.7g MMA as the monomer that constitutes specific copolymer; Use 5g AIBN as radical polymerization initiator; Through they are carried out polyreaction under 60 ℃～100 ℃ of temperature in 185g solvent GMEA, obtain solution (the specific copolymer concentration: 35.0 quality %) of (A) composition (specific copolymer) of Mn4100, Mw7600.(P3)
< synthetic example 4 >
Use 7.5g MAA, 20.0g MMA, 10.0g HEMA, 12.5g PFMA as the monomer that constitutes specific copolymer; Use 1.59g AIBN as radical polymerization initiator; Through they are carried out polyreaction under 60 ℃～100 ℃ of temperature in 154.7g solvent GMEA, obtain solution (the specific copolymer concentration: 25.0 quality %) of (A) composition (specific copolymer) of Mn12600, Mw20300.(P4)
< synthetic example 5 >
Use 3.0g MAA, 3.0g MMA, 4.0g HEMA, 9.0g TMSSMA as the monomer that constitutes specific copolymer; Use 0.96g AIBN as radical polymerization initiator; Through they are carried out polyreaction under 60 ℃～100 ℃ of temperature in 59.9g solvent GMEA, obtain solution (the specific copolymer concentration: 25.0 quality %) of (A) composition (specific copolymer) of Mn8200, Mw12900.(P5)
< embodiment 7～10 and comparative example 7～11 >
According to the composition shown in following table 3; Through according to the rules mixed (B) composition, (C) composition, (D) composition, (E) composition and (F) solvent in the solution of (A) composition; Also has fluorine class alkali soluble resins among the embodiment 7 as (G) composition; At room temperature stir and formed uniform solution in 3 hours, modulate the positive type photosensitive organic compound of each embodiment and each comparative example.
[table 3]
(A) solution of composition (g) (B) composition (g) (C) composition (g) (D) composition (g) (E) composition (g) (F) solvent (g) (I) composition (g)
Embodiment 7 P3 11.8 PDFS1 0.21? PVE1 0.62 NCO1 0.41 PAG1 0.21 MAK 5.04 P4 0.83
Embodiment 8 P3 11.8 PDFS1 0.21? PVE1 0.62 NCO1 0.41 PAG1 0.21 MAK 5.33 ?-
Embodiment 9 P3 11.8 PDFS1 0.41? PVE1 0.62 NCO1 0.41 PAG1 0.21 MAK 6.03 ?-
Embodiment 10 P3 11.8 PDFS2 0.41? PVE1 0.62 NCO1 0.41 PAG1 0.21 MAK 6.03 ?-
Comparative example 7 P3 11.8 PDMS6 0.21? PVE1 0.62 NCO1 0.41 PAG1 0.21 PGMEA 5.33? ?-
Comparative example 8 P3 11.8 PDMS6 0.31? PVE1 0.62 NCO1 0.41 PAG1 0.21 PGMEA 5.63? ?-
Comparative example 9 P3/P4 5.9/8.2 ?- PVE1 0.62 NCO1 0.41 PAG1 0.21 PGMEA 2.54?
Comparative example 10 P3 11.8 ?- PVE1 0.62 NCO1 0.41 PAG1 0.21 PGMEA 4.50?
Comparative example 11 P3/P5 5.9/8.2 ?- PVE1 0.62 NCO1 0.41 PAG1 0.21 PGMEA 2.54?
Various compositions in embodiment 7～embodiment 10 and the comparative example 7～comparative example 11 subtract (in the unexposed portion), contact angle, Cement Composite Treated by Plasma patience and thermotolerance to stability of solution, light sensitivity, film with acryl resin respectively and estimate.
[stability of solution evaluation]
For the above-mentioned positive type photosensitive organic compound that obtains, after said composition modulation, with transparent and uniform dissolution be labeled as zero, with gonorrhoea appears or separate out being labeled as of insolubles *.
[evaluation of light sensitivity]
After using spinner to apply positive type photosensitive organic compound on the silicon wafer, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.The F20 that thickness uses FILMETRICS to make measures.Light intensity is 5.5mW/cm under the 65nm of the ultraviolet lamp PLA-600FA irradiation certain hour of on this is filmed, making through キ ヤ ノ Application (strain) < > 2 <> Ultraviolet ray, then under 110 ℃ of temperature, on hot plate, make public back heating (PEB)120 second.After dipping developed in 60 seconds in the tetramethyl ammonium hydroxide of 0.4 quality % (below be called MAH) aqueous solution then, carry out 20 second flow water washings with ultrapure water.There is not the required lowest exposure amount (mJ/cm of molten slag with making in the exposed portion < > 2 <> ) as light sensitivity.
[evaluation that film subtracts]
After using spinner to apply positive type photosensitive organic compound on the silicon wafer, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This film flooded for 60 seconds in 0.4 quality TMAH aqueous solution after, carry out flowing water washing in 20 seconds with ultrapure water.Then measure the thickness of this film, the film of the unexposed portion that estimating develops produces subtracts degree.The F20 that thickness during this is estimated uses FILMETRICS to make measures.
[evaluation of contact angle]
After using spinner to apply positive type photosensitive organic compound on the quartz base plate, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This is filmed and carried out the back oven dry in 30 minutes through heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.The Drop Master that uses consonance interface science (strain) to make measures water and dodecyl benzene (DB on this cured film) contact angle.
[plasma (ozone) is handled the evaluation of patience]
After using spinner to apply positive type photosensitive organic compound on the quartz base plate, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.5 μ m.This is filmed and carried out the back oven dry in 30 minutes through heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.The UV-312 of use (strain) テ Network ノ PVC ジ ヨ Application manufacturing films to this and carries out 15 minutes ozone washing.Use the contact angle of the Drop Master of consonance interface science (strain) manufacturing according to the water on the film after handling with above-mentioned [evaluation of contact angle] same method mensuration ozone washing.
In addition, [Fig. 1 water) and [Fig. 2 dodecyl benzene) in shown that the cured film that the positive type photosensitive organic compound by the foregoing description 7 forms handled afterwards (5 minute, 10 minutes, 15 minutes with ozone washing before ozone washing is handled) measurement of contact angle result.
[stable on heating evaluation]
In above-mentioned [evaluation of contact angle],, form the cured film of 1.9 μ m with same method except substrate is changed to the silicon wafer by quartz base plate.Cut and get this cured film, measure DTA-TG as sample.The temperature that sample mass is reduced 5 quality % reduces temperature as 5% quality.
[evaluation result]
Above evaluation result is presented in the following table 4.
[table 4]
Figure G2007800176897D00411
< > * <> So-called " not having film to subtract " is illustrated in to measure and do not observe film among the result and subtract (film that does not become in other words, practical problems subtracts).
Among embodiment 7～embodiment 10, behind the modulation positive type photosensitive organic compound, can obtain not having the homogeneous solution of gelation or separation.
In addition, embodiment 7～embodiment 10 all is ISO, does not observe the film that becomes practical problems in the unexposed portion and subtracts, and shows good thermotolerance.And after the UV ozone treatment, the reduction of cured film surface high waterproof and high oil-proofness also is suppressed.
In addition; Handle front and back measurement of contact angle result if observe the cured film that the positive type photosensitive organic compound by embodiment 7 forms in ozone washing; Then find in water (figure 1), dodecyl benzene (figure 2); All reductions of the contact angle that changes less than the time of taking place to handle along with ozone washing, on the contrary along with carrying out washing treatment through showing that together contact angle becomes big tendency.
On the other hand, comparative example 7 and comparative example 8, the stability of solution of positive type photosensitive organic compound is low, can not obtain uniform solution, can not obtain to film and cured film.
The surperficial water resisting property of comparative example 9 and oil-proofness are high, but ozone treatment patience is low.
Water resisting property, oil-proofness and ozone treatment patience are all low in the comparative example 10.
In the comparative example 11, surperficial water resisting property is high, but ozone treatment patience is poor, and oil-proofness is also low.
The industry utilizability
Positive type photosensitive organic compound of the present invention; Be suitable as the material of cured film such as diaphragm in the various displays such as forming thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL, planarization film, dielectric film; Be particularly suitable for the material of the embossed film of the reflectance coating downside of protection mould, array planarization film, reflective display, the dielectric film of organic EL etc., also be suitable as various electronic materials such as microlens material in addition as the interlayer dielectric that forms TFT type liquid crystal cell, color filter.
The simple declaration of accompanying drawing
[figure 1] be show cured film that the positive type photosensitive organic compound by embodiment 7 forms before ozone washing is handled with processing after (5 minute, 10 minutes, 15 minutes) water contact angle θ (°) figure.
[figure 2] be show cured film that the positive type photosensitive organic compound by embodiment 7 forms before ozone washing is handled with processing after (5 minute, 10 minutes, 15 minutes) dodecyl benzene contact angle θ (°) figure.

Claims (13)

1. positive type photosensitive organic compound contains following (A) composition, (B) composition, (C) composition, (D) composition, (E) composition and (F) solvent,
(A) composition: have the functional group that can carry out heat cross-linking reaction, and a functional group that film solidifies that is used for that can carry out the heat curing reaction, and number-average molecular weight is 2000～30000 alkali soluble resins with (D) component cpd with (C) component cpd,
(B) composition: number-average molecular weight is 100～2000 silicone compounds,
(C) contain the compound of 2 above vinyl ether groups in the composition :1 molecule,
(D) contain the compound of 2 above blocked isocyanate bases in the composition :1 molecule,
(E) composition: photoacid generator,
(F) solvent,
The above-mentioned functional group that can carry out heat cross-linking reaction is a carboxyl, and above-mentionedly is used for the functional group that film solidifies and is the hydroxyl except that phenol property hydroxyl,
Based on 100 mass parts (A) composition, contain (B) composition of 0.1～30 mass parts, (C) composition of 1～80 mass parts, (D) composition of 1～80 mass parts and (E) composition of 0.5～80 mass parts.
2. positive type photosensitive organic compound as claimed in claim 1 is characterized in that (B) composition is the silicone compounds of fluorine modification.
3. positive type photosensitive organic compound as claimed in claim 1 is characterized in that, (B) composition is the silicone compounds with repetitive of formula (1) expression,
Figure FSB00000702354300011
In the formula, R < > 1 <> And R < > 2 <> Be hydrogen atom, alkyl or phenyl independently of one another, p representes positive integer.
4. positive type photosensitive organic compound as claimed in claim 3 is characterized in that, (B) composition is R in the above-mentioned formula (1) < > 1 <> And/or R < > 2 <> The silicone compounds of expression fluoro-alkyl.
5. positive type photosensitive organic compound as claimed in claim 1 is characterized in that, (B) composition is not for containing the silicone compounds of epoxy radicals.
6. positive type photosensitive organic compound as claimed in claim 1; At (B) composition is in the positive type photosensitive organic compound of silicone compounds of fluorine modification, also contain based on 100 mass parts (A) composition 0.1～20 mass parts conduct (G) composition except that (A) the fluorine class alkali soluble resins the composition.
7. positive type photosensitive organic compound as claimed in claim 1 also contains the amines of conduct (H) composition of 0.001～5 mass parts based on 100 mass parts (A) composition.
8. positive type photosensitive organic compound as claimed in claim 1 also contains the surfactant of conduct (I) composition below the 0.2 quality % in positive type photosensitive organic compound.
9. the cured film of using each described positive type photosensitive organic compound of claim 1～8 to obtain.
10. the separator material that organic EL display element is used has the described cured film of claim 9.
11. liquid crystal display cells has the described cured film of claim 9.
12. LCD array planarization film is formed by the described cured film of claim 9.
13. interlayer dielectric is formed by the described cured film of claim 9.
CN2007800176897A 2006-05-16 2007-05-16 Positive photosensitive resin composition containing siloxane compound Active CN101443705B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2006136797 2006-05-16
JP136797/2006 2006-05-16
JP2007011413 2007-01-22
JP011413/2007 2007-01-22
PCT/JP2007/060042 WO2007132892A1 (en) 2006-05-16 2007-05-16 Positive photosensitive resin composition containing siloxane compound

Publications (2)

Publication Number Publication Date
CN101443705A CN101443705A (en) 2009-05-27
CN101443705B true CN101443705B (en) 2012-05-30

Family

ID=38693981

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800176897A Active CN101443705B (en) 2006-05-16 2007-05-16 Positive photosensitive resin composition containing siloxane compound

Country Status (5)

Country Link
JP (1) JP5071686B2 (en)
KR (1) KR101309252B1 (en)
CN (1) CN101443705B (en)
TW (1) TWI411884B (en)
WO (1) WO2007132892A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1904736B (en) 2005-07-25 2012-06-13 日产化学工业株式会社 Positive-type photosensitive resin composition and cured film manufactured therefrom
WO2008090827A1 (en) * 2007-01-22 2008-07-31 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition
WO2009093706A1 (en) * 2008-01-24 2009-07-30 Asahi Kasei E-Materials Corporation Photosensitive resin laminate
EP2312394B1 (en) 2008-08-01 2012-12-05 Asahi Glass Company, Limited Negative working photosensitive composition, partition walls for an optical element using the negative working photosensitive composition, and optical element comprising the partition walls
TW201024871A (en) * 2008-12-26 2010-07-01 Chunghwa Picture Tubes Ltd Bubble-free packaging method
JP5533232B2 (en) * 2009-06-29 2014-06-25 Ｊｓｒ株式会社 Positive radiation sensitive composition, cured film, interlayer insulating film, method for forming interlayer insulating film, display element, and siloxane polymer for forming interlayer insulating film
TWI505034B (en) * 2010-02-02 2015-10-21 Nissan Chemical Ind Ltd Positive type photosensitive resin composition and liquid-repellent coating
CN103238111B (en) 2010-12-10 2016-12-07 旭硝子株式会社 Negative light-sensitive resin combination, spaced walls used for optical elements and manufacture method thereof, there is the manufacture method of the optical element of this spaced walls and refuse ink agent solution
CN104160336B (en) * 2012-03-09 2017-09-05 旭硝子株式会社 Positive type photosensitive organic compound, partition wall and optical element
JP6739224B2 (en) * 2016-04-27 2020-08-12 株式会社カネカ Positive photosensitive composition for forming barrier ribs
JP6984539B2 (en) * 2018-05-21 2021-12-22 信越化学工業株式会社 Photosensitive resin composition, pattern forming method, and manufacturing method of optical semiconductor device
KR102331157B1 (en) * 2019-10-23 2021-11-26 (주)휴넷플러스 Polysiloxane copolymer, method for preparing the same and resin composition comprising the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5075199A (en) * 1988-05-19 1991-12-24 Basf Aktiengesellschaft Radiation sensitive mixture and production of relief patterns
CN1479173A (en) * 2002-04-15 2004-03-03 夏普株式会社 Radiation sensitive resin composite, method for forming insulating film having pattern, active matrix plate and panel display equipped with the film and method for producing panel display device

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06230574A (en) * 1993-02-05 1994-08-19 Fuji Photo Film Co Ltd Positive type photosensitive composition
US5496678A (en) * 1993-04-16 1996-03-05 Kansai Paint Co., Ltd. Photosensitive compositions containing a polymer with carboxyl and hydroxyphenyl groups, a compound with multiple ethylenic unsaturation and a photo-acid generator
JP2824209B2 (en) * 1993-04-16 1998-11-11 関西ペイント株式会社 Photosensitive composition and pattern forming method
JP3518158B2 (en) * 1996-04-02 2004-04-12 信越化学工業株式会社 Chemically amplified positive resist material
JP4424630B2 (en) * 1999-07-13 2010-03-03 三菱レイヨン株式会社 Chemically amplified resist composition and resist pattern forming method
JP2005115249A (en) * 2003-10-10 2005-04-28 Fuji Photo Film Co Ltd Photosensitive polymide composite and pattern forming method using same
JP4131864B2 (en) * 2003-11-25 2008-08-13 東京応化工業株式会社 Chemical amplification type positive photosensitive thermosetting resin composition, method for forming cured product, and method for producing functional device
JP4415737B2 (en) * 2004-04-08 2010-02-17 旭硝子株式会社 Photosensitive resin composition and cured film thereof
JP4301115B2 (en) * 2004-08-25 2009-07-22 Ｊｓｒ株式会社 Active energy ray-curable resin composition and antireflection film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5075199A (en) * 1988-05-19 1991-12-24 Basf Aktiengesellschaft Radiation sensitive mixture and production of relief patterns
CN1479173A (en) * 2002-04-15 2004-03-03 夏普株式会社 Radiation sensitive resin composite, method for forming insulating film having pattern, active matrix plate and panel display equipped with the film and method for producing panel display device

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JP特开2005-181976A 2005.07.07
JP特开平6-230574A 1994.08.19
JP特开平7-146552A 1995.06.06

Also Published As

Publication number Publication date
TW200804984A (en) 2008-01-16
WO2007132892A1 (en) 2007-11-22
KR20090008326A (en) 2009-01-21
JPWO2007132892A1 (en) 2009-09-24
JP5071686B2 (en) 2012-11-14
CN101443705A (en) 2009-05-27
KR101309252B1 (en) 2013-09-17
TWI411884B (en) 2013-10-11

Similar Documents

Publication Publication Date Title
CN101443705B (en) Positive photosensitive resin composition containing siloxane compound
JP5083568B2 (en) Positive photosensitive resin composition
CN1904736B (en) Positive-type photosensitive resin composition and cured film manufactured therefrom
CN102741752B (en) Positive photosensitive resin composition and liquid-repellent film
CN101331157B (en) Fluorine-containing polymer, negative photosensitive composition and partition wall
CN101467100B (en) Positive photosensitive resin composition containing polymer having ring structure
TWI411883B (en) Positive type photosensitive resin composition and cured coating prepared therefrom
CN101443704A (en) Positive photosensitive resin composition and porous film obtained therefrom
CN1954264B (en) Positive photosensitive resin composition, and interlayer dielectrics and micro lenses made therefrom
JP4753036B2 (en) Positive photosensitive resin composition and cured film obtained therefrom
KR101285640B1 (en) Positive Type Photosensitive Resin Composition And Cured Film Manufactured Therefrom
CN101517492A (en) Method for manufacturing transparent cured film using positive-working photosensitive resin layer for half exposure
JP2008256974A (en) Positive photosensitive resin composition
JP5293937B2 (en) Photosensitive resin composition
JP5339034B2 (en) Photosensitive resin composition containing sulfonic acid compound

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant