CN101443704A - Positive photosensitive resin composition and porous film obtained therefrom - Google Patents
Positive photosensitive resin composition and porous film obtained therefrom Download PDFInfo
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- CN101443704A CN101443704A CNA2007800175606A CN200780017560A CN101443704A CN 101443704 A CN101443704 A CN 101443704A CN A2007800175606 A CNA2007800175606 A CN A2007800175606A CN 200780017560 A CN200780017560 A CN 200780017560A CN 101443704 A CN101443704 A CN 101443704A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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Abstract
The invention provides a photosensitive resin composition from which a coating film pattern having high pattern surface water repellency 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 obtained by copolymerizing (i) an unsaturated carboxylic acid with (ii) at least one compound selected from the group consisting of acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds; ingredient (B) which is a siloxane compound having a number-average molecular weight of 100-2,000; ingredient (C) which is a 1,2-quinonediazide compound; ingredient (D) which is a crosslinking compound; and a solvent (E); and also provides the cured film obtained by using the composition.
Description
Technical field
The present invention relates to positive type photosensitive organic compound and cured film therefrom, and the various materials that use this cured film.This positive type photosensitive organic compound is especially suitable for use as edge in liquid crystal display cells or the EL display element or interlayer dielectric, corresponding to the light screening material or the separator material of ink-jetting style.
Background technology
Generally in display devices such as thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL (electroluminescence) 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 be extensive use of those at present and having the photosensitive polymer combination that the process number that is used to obtain required pattern is few and have feature 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.For example, the making of color filter in the relevant liquid crystal display cells, with respect to present print process, electrodeposition process, decoration method or pigment dispersing method, proposed at first in the photo-sensitive resin of blocking light, to form stipulate structure by the interval of the pixel of figure (hereinafter referred to as the edge), in the peristome that this edge surrounded, the drip color filter of ink droplet and manufacture method (for example with reference to patent documentation 1, patent documentation 2 and patent documentation 3) thereof etc. again.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 under the situation of the ink droplet that the edge surrounded that in ink-jet method, drips, 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 repellency on the surface, edge.
In order to achieve the above object,, can on substrate, keep water wettability, and on the edge, keep water repellency by continuous Cement Composite Treated by Plasma, but complex procedures.The example that cooperates fluorine class surfactant or fluorine-based polymer in the photonasty organic film is arranged in addition, but intermiscibility or addition etc. to consider that not only photonasty also comprises coating, need the aspect of consideration more, be difficult to deserve to be called practical.
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
Summary of the invention
The present invention makes in view of the above fact, its problem to be solved provides a kind of photosensitive polymer combination, it can easily form film figure with high precision and high yield, its patterned surfaces has high water repellency, handling its water repellency of back through plasma etc. can be than macrolesion yet, and has insulativity.
Problem of the present invention in addition provides the cured film of using such positive type photosensitive organic compound to obtain, this cured film is in the substrate manufacture that uses ink-jet, can prevent that ink droplet from exceeding the edge and being spilled over to adjacent pixels, and the various element materials that use such cured film to make are provided.
The present inventor has carried out wholwe-hearted research in order to solve above-mentioned problem, found that the present invention.
Be that the present invention's the 1st viewpoint is a kind of positive type photosensitive organic compound, contain following (A) composition, (B) composition, (C) composition, (D) composition and (E) solvent,
(A) composition: (i) alkali soluble resins that obtains with (ii) copolymerization, (i) unsaturated carboxylic acid, (ii) be selected from the compound more than a kind in acrylate compounds, methacrylate compound, maleimide, vinyl cyanide, maleic anhydride, distyryl compound and the vinyl compound
(B) composition: number-average molecular weight is 100～2000 silicone compounds,
(C) composition: 1, the 2-quinone di-azido compound,
(D) composition: cross-linked compound,
(E) solvent.
The 2nd viewpoint is the described positive type photosensitive organic compound of the 1st viewpoint, and wherein the number-average molecular weight of the alkali soluble resins of (A) composition is 2000～30000 by polystyrene conversion,
The 3rd viewpoint is the described positive type photosensitive organic compound of the 1st or the 2nd viewpoint, it is characterized in that, (D) cross-linked compound of composition is the compound that contains the above epoxy radicals of 2 officials energy,
The 4th viewpoint is each described positive type photosensitive organic compound of the 1st～the 3rd viewpoint, and wherein the cross-linked compound of (D) composition is the compound of formula (1) expression,
In the formula, k is 2～10 integer, and m represents 0～4 integer, and R represents the organic group of k valency.
The 5th viewpoint is each described positive type photosensitive organic compound of the 1st～the 4th viewpoint, wherein (E) solvent contains at least a kind of solvent that is selected from propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, ethyl lactate and the butyl lactate
The 6th viewpoint is each described positive type photosensitive organic compound of the 1st～the 5th viewpoint, it is characterized in that, based on 100 mass parts (A) composition, contain (B) composition of 0.1～30 mass parts, (C) composition of 5～100 mass parts and (D) composition of 1～80 mass parts
The 7th viewpoint is each described positive type photosensitive organic compound of the 1st～the 6th viewpoint, wherein also contains the surfactant of (G) composition of conduct below the 0.2 quality % in positive type photosensitive organic compound,
The cured film of the 8th viewpoint for using each described positive type photosensitive organic compound of the 1st～the 7th viewpoint to obtain,
The 9th viewpoint is the separator material that organic EL display element is used, and has the described cured film of the 8th viewpoint,
The 10th viewpoint is a liquid crystal display cells, has the 8th viewpoint described cured film,
The 11st viewpoint is a LCD array planarization film, forms by the described cured film of the 8th viewpoint,
The 12nd viewpoint is an interlayer dielectric, is formed by the described cured film of the 8th viewpoint.
Positive type photosensitive organic compound of the present invention has high storage stability, be 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, it can easily form the multiple aperture plasma membrane pattern of insulativity with high precision and high yield, patterned surfaces has high water repellency, also can not reduce much through its water repellency after the ozone treatment.
The cured film of using above-mentioned positive type photosensitive organic compound of the present invention to obtain in addition, in the substrate manufacture that uses ink-jet, can prevent ink droplet from exceeding the edge and be spilled over to the situation of neighbor, 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: 1,2-quinone di-azido compound, (D) composition: cross-linked compound, (E) solvent, and according to required separately (F) composition that also contains: other alkali soluble resins, (G) composition: surfactant or (H) composition: adhesion promotor.Below each composition is described in detail.
＜A composition 〉
(A) composition that uses in the positive type photosensitive organic compound of the present invention is a unsaturated carboxylic acid and be selected from the polymkeric substance that at least a kind of compound copolymerization in acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and the vinyl compound obtains (below be called particular polymers), is alkali soluble resins.
Being (A) composition that uses among the present invention, is to have the composition that dissolves in the such character of alkaline solution in the above-mentioned particular polymers.Therefore, (A) composition can use and be selected from a kind or the multiple alkali soluble resins that has in the specific copolymer that this what is called dissolves in alkaline SOLUTION PROPERTIES.
This specific copolymer is necessary for 2000～30000 according to the number-average molecular weight (hereinafter referred to as number-average molecular weight) of polystyrene conversion.Be preferably 2500～15000, more preferably 3000～10000.
Under the situation of number-average molecular weight less than 2000, the pattern form that obtains sometimes is not good, or the decline of the residual film ratio of pattern, or the thermotolerance of pattern descends.On the other hand, under number-average molecular weight surpassed 30000 situation, the coating of positive type photosensitive organic compound became not good sometimes, or development decline and phenomenon occurs peeling off, the pattern form that also obtains sometimes is not good sometimes, or the decreased solubility in organic solvent.In addition, surpass under 40000 the situation, have residue and resolution decline between the pattern below the 50 μ m sometimes in number-average molecular weight.
Unsaturated carboxylic acid as the monomer component that is used for obtaining this specific copolymer, not restriction especially, can enumerate acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric 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 object lesson.
With the monomer component of this unsaturated carboxylic acid copolymerization is to be selected from least a kind of compound in acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and the vinyl compound.Thereby both can use a kind separately, also can several merging use.
Under the situation that several merging are used, wherein under the situation that contains methacrylate compound and maleimide compound at least,, therefore preferred owing to giving cured film higher thermotolerance.The object lesson of these compounds is listed below.
As acrylate compounds, for example can enumerate, methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, glycidyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthryl methyl esters, phenyl acrylate, acrylic acid-2,2, the 2-trifluoro ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 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, 2-hydroxyethyl methacry-late, methacrylic acid-2-hydroxypropyl acrylate, glycidyl methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthryl methyl esters, phenyl methacrylate, methacrylic acid-2,2, 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 vinyl naphthalene, 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.
In the present invention, based on the total amount of the monomer component that is used to obtain specific copolymer, the ratio of unsaturated carboxylic acid is preferably 1～30 quality %, and more preferably 3～25 quality % most preferably are 5～20 quality %.Under the situation of less than 1 quality %, the dissolubility in alkaline-based developer is insufficient sometimes, is surpassing under the situation of 30 quality %, because the dissolubility in alkaline-based developer is too high, therefore causes the dissolving of unexposed portion sometimes and causes residual film ratio to descend.
Restriction especially of preparation method to the specific copolymer used among the present invention, for example, can be by will suitably being selected from least a kind of monomer in the above-mentioned unsaturated carboxylic acid, with at least a kind of monomer that is selected from aforesaid propylene ester compound, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and the vinyl compound, with above-mentioned monomer monomer in addition as required, and polymerization initiator as required etc., in solvent, under 50～110 ℃ temperature, carry out polyreaction and obtain.At this moment employed solvent as long as can dissolve monomer and the specific copolymer that constitutes specific copolymer, has no particular limits.As concrete example, can enumerate the solvent of putting down in writing in aftermentioned (E) solvent.
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, under normal pressure or decompression,, can make the powder of specific copolymer by normal temperature or heat drying.By 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, also its powder can be dissolved in the such solvent of (E) for example described later solvent again, as the state use of solution.
＜B composition 〉
(B) composition is to be 100～2000 polysiloxane compound according to the polystyrene conversion number-average molecular weight.
As this silicone compounds, for example can enumerate straight chain shape polydimethylsiloxaneresins resins, side chain polydimethylsiloxaneresins resins, X 2-1401 resin, modified dimethyl polysiloxane resin, polydimethylsiloxanecopolymer copolymer etc.
As their concrete example; can enumerate; dimethyl silicone polymer; polymethy ethylsiloxane; PSI; poly-hydrogenated methyl siloxane; poly-methyl-propyl siloxane; poly-diphenyl siloxane; straight chain shape siloxane or its multipolymers such as poly-methyl butyl siloxane; X 2-1401; cyclic methyl phenylpolysiloxane; ring-type is gathered the hydrogenated methyl siloxane; the ring-type polymethy ethylsiloxane; ring-type is gathered the methyl-propyl siloxane; annular siloxanes such as the poly-methyl butyl siloxane of ring-type; 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 dimethyl silicone polymer such as alkoxy-modified, amino modified; the epoxy radicals modification; carboxy-modified; the methyl alcohol modification; the methacryl modification; sulfhydryl modified; dimethyl silicone polymer that phenol-modified isoreactivity is group modified and their multipolymer etc.
Commercially available product as above-mentioned siloxane, for example can enumerate, L-45 (Japanese ユ ニ カ-(strain) made), SH200,510,550,710,705,1107 (East レ ダ ウ コ-ニ Application グ (strain) makes), X-22-162C, 3701E, 3710,1821,164S, 170DX, 176DX, 164A, 4952, KF96,50,54,99,351,618,910,700,6001,6002,8010, KR271,282 straight chain shape silicone resins such as (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturings), VS-7158 (Japanese ユ ニ カ-(strain) made), BY11-003 (East レ ダ ウ コ-ニ Application グ (strain) makes) etc. the annular siloxane resin, L-77,720,7001,7604, Y-7006, L-9300, FZ-2101,2110,2130,2161,3704,3711,3722,3703,3720,3736,3705,3760 (Japanese ユ ニ カ-(strain) made), 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 (East レ ダ ウ コ-ニ Application グ (strain) makes), ES1001N, 1023, X-22-161,-163,-169,-162,-164, KF-860,-101,-102,-6001,-6011,-6015,-8001,-351,-412,-910,-905 modified siloxane resins such as (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturings), FS1265 (East レ ダ ウ コ-ニ Application グ (strain) makes), X-22-820, FL100 fluorine modified siloxane resins such as (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturings), FZ-2203,2207, the multipolymer of 2222 polysiloxane such as (Japanese ユ ニ カ-(strain) made) and polyalkylene oxide.
In the above-mentioned silicone compounds, particularly aspect the water repellency that is remaining pattern upper part with the intermiscibility of (A) composition (alkali soluble resins), dissolubility developer solution and territory, non-exposed area (shading light part), be compound below 2000 preferably according to several mean molecular weight (hereinafter referred to as Mn) of polystyrene conversion.Under the little situation of Mn, because surface, territory, non-exposed area (shading light part) can not fully obtain water repellency sometimes, so Mn is preferably more than 100 on the other hand.Wherein more preferably viscosity is the compound of 5～100cst.
In the present invention also can be also with multiple such silicone compounds.
(B) consumption of the silicone compounds of composition is preferably 0.1～30 mass parts with respect to 100 mass parts (A) compositions (alkali soluble resins), 1～20 mass parts more preferably, preferred especially 3～15 mass parts.(B) consumption of component cpd is if the amount of the lower limit of not enough above-mentioned scope, and the water repellency on the patterned surfaces becomes insufficient easily sometimes, and the emptying aperture of Xing Chenging is undersized in addition.On the other hand, (B) consumption of component cpd is if surpass the amount of above-mentioned scope, and it is inhomogeneous that whiting or film then take place when formation is filmed sometimes.
In the present invention, by the kind and the usage ratio thereof of suitable selection (B) composition, can control the size of the emptying aperture that forms in filming.
＜(C) composition 〉
As 1 of (C) composition, the 2-quinone di-azido compound, can use the compound that contains any or two kinds in hydroxyl or the amino, can use these hydroxyls or amino (contain hydroxyl and amino both the time be its total amount) in, preferred 10～100 moles of %, preferred especially 20～95 moles of % are with 1, and 2-quinone two nitrine sulfonic acid have carried out esterification or amidated compound.
As the above-mentioned compound that contains hydroxyl, for example can enumerate, phenol, orthoresol, metacresol, paracresol, quinhydrones, resorcinol, catechol, gallicin, progallin A, 1,3,3-three (4-hydroxy phenyl) butane, 4,4-isopropylidene xenol, 2,2-two (4-hydroxy phenyl) propane, 1,1-two (4-hydroxy phenyl) cyclohexane, 4,4 '-dihydroxy phenyl sulfone, 4,4-hexafluoro isopropylidene xenol, 4,4 '; 4 "-trihydroxy phenyl ethane, 1,1,1-trihydroxy phenyl ethane, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 2, the 4-dihydroxy benaophenonel, 2,3, the 4-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,2 ', 3,4,4 '-pentahydroxybenzophenone, 2, phenolic compounds such as 5-two (2-hydroxy-5-methyl base benzyl) methyl, ethanol, the 2-propyl alcohol, the 4-butanols, cyclohexanol, ethylene glycol, propylene glycol, diglycol, dipropylene glycol, 2-methyl cellosolve, butoxy ethanol, the 2-methoxypropanol, 2-butoxy propyl alcohol, ethyl lactate, aliphatics alcohols such as butyl lactate.
In addition, as the above-mentioned compound that contains amino, can enumerate, aniline, ortho-aminotoluene, meta-aminotoluene, para-totuidine, 4-ADP methylmethane, 4-ADP base, o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), 4,4 '-tetramethyl triaminotriphenyl methane NH2,4, phenyl aminess such as 4 '-diamino-diphenyl ether, aminocyclohexane.
Also have, as containing hydroxyl and both compounds of amino, for example can enumerate, o-aminophenol, m-aminophenol, para-aminophenol, the 4-aminoresorcinol, 2, the 3-diaminophenol, 2, the 4-diaminophenol, 4,4 '-diamido-4 "-the hydroxyl triphenyl methane; 4-amino-4 '; 4 "-dihydroxy triphenyl methane, two (4-amino-3-carboxyl-5-hydroxy phenyl) ether, two (4-amino-3-carboxyl-5-hydroxy phenyl) methane, 2,2-two (4-amino-3-carboxyl-5-hydroxy phenyl) propane, 2, amino phenols such as 2-two (4-amino-3-carboxyl-5-hydroxy phenyl) HFC-236fa, the 2-ethylaminoethanol, the 3-aminopropanol, alkanolamine such as 4-aminocyclohexanol.
These 1, the 2-quinone di-azido compound can be used singly or in combination of two or more thereof.
The content of (C) composition in the positive type photosensitive organic compound of the present invention with respect to 100 mass parts (A) composition, is preferably 5～100 mass parts, 8～50 mass parts more preferably, and then be preferably 10～40 mass parts.Under the situation of less than 5 mass parts, the exposed portion of positive type photosensitive organic compound and the unexposed portion dissolution velocity difference in developer solution diminishes, and forms the pattern difficulty sometimes by developing.If surpass 100 mass parts in addition, because the exposure of short time can not make 1, the 2-quinone di-azido compound fully decomposes, and therefore light sensitivity reduces sometimes, and perhaps (C) composition absorbing light causes the transparency of cured film to reduce.
＜D composition 〉
(D) composition is the compound that (A) composition is had bridging property.As such compound with bridging property, can enumerate and contain methylol, methoxy etc. and be cross-linked to form substituent melamine based compound or replace the urea based compound, contain epoxy radicals or oxetanyl etc. and be cross-linked to form substituent compound, and contain compound of end-blocking isocyanates etc.The cross-linked compound of (D) composition is to have at least 2 to be cross-linked to form substituent compound in addition, from the viewpoint of thermotolerance, storage stability, preferably contains the compound of epoxy radicals or oxetanyl.
As such compound, for example can enumerate, three (2, the 3-epoxypropyl) isocyanuric acid ester, 1, the 4-butanediol diglycidyl ether, 1,2-epoxy radicals-4-(epoxy radicals ethyl) cyclohexane, T 55, the diglycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-three [right-(2,3-epoxy radicals propoxyl group) phenyl] propane, 1,2-cyclohexane dicarboxylic acid 2-glycidyl ester, 4,4 '-methylene, two (N, the N-diglycidylaniline), 3,4-epoxy radicals cyclohexyl methyl-3,4-epoxy-cyclohexane carboxylate, trimethylolethane trimethacrylate glycidol ether and bisphenol-A-diglycidyl ether, and the pentaerythrite polyglycidyl ether etc.
In addition, as the compound that contains at least two epoxy radicals, can use the polymkeric substance that contains epoxy radicals.As such polymkeric substance, promptly can use so long as have the polymkeric substance of epoxy radicals, not restriction especially.
Such polymkeric substance can be made by the addition polymerization that use contains the addition polymerization monomer of epoxy radicals, and the compound that contains epoxy radicals such as macromolecular compound that also can be by containing hydroxyl and chloropropylene oxide, toluenesulfonic acid glycidyl esters reacts and makes in addition.For example can enumerate, the polyaddition polymers such as multipolymer of the multipolymer of poly epihydric alcohol base acrylate, methyl propenoic acid glycidyl base ester and Jia Jibingxisuanyizhi, methyl propenoic acid glycidyl base ester and styrene and 2-hydroxyethyl methacry-late, polycondensation polymers such as epoxy radicals novolaks.As the weight-average molecular weight of this polymkeric substance, for example be 300～200000.
The compound that contains 2 above epoxy radicals of wherein preferred following formula (1) expression.
(in the formula, k is 2～10 integer, and m represents 0～4 integer, and R represents the organic group of k valency)
In addition, has amino epoxy resin simultaneously as having at least 2 epoxy radicals, can enumerate YH-434, YH434L (Dongdu changes into (strain) and makes), as epoxy resin with cyclohexene oxide structures, can enumerate エ Port リ-De GT-401, エ Port リ-De GT-403, エ Port リ-De GT-301, エ Port リ-De GT-302, セ ロ キ サ イ De 2021, セ ロ キ サ イ De 3000 (ダ イ セ Le chemical industry (strain) manufacturing), as bisphenol A type epoxy resin, can enumerate エ ピ コ-ト (now being jER) 1001, エ ピ コ-ト 1002, エ ピ コ-ト 1003, エ ピ コ-ト 1004, エ ピ コ-ト 1007, エ ピ コ-ト 1009, エ ピ コ-ト 1010, (above be ジ to エ ピ コ-ト 828
ヤパ Application エ Port キ シ レ ジ Application (strain) is made) etc., as bisphenol f type epoxy resin, can enumerate エ ピ コ-ト (now being jER) 807 (ジ
ヤパ Application エ Port キ シ レ ジ Application (strain) is made) etc., as phenol novolak type epoxy resin, can enumerate エ ピ コ-ト (now being jER) 152, エ ピ コ-ト 154 (above ジ of being
ヤパ Application エ Port キ シ レ ジ Application (strain) manufacturing), EPPN201, EPPN 202 (above is Japanese chemical drug (strain) manufacturing) etc., as the cresols phenolic resin varnish type epoxy resin, can enumerate EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above is Japanese chemical drug (strain) manufacturing), エ ピ コ-ト (now being jER) 180S75 (ジ
ヤパ Application エ Port キ シ レ ジ Application (strain) is made), as alicyclic epoxy resin, can enumerate デ Na コ-Le EX-252 (Na ガ セ ケ system テ
StarNetwork ス (strain) manufacturing), CY175, CY177, CY179 (the above CIBA-GEIGYA.G of being makes), ア ラ Le ダ イ ト CY-182, ア ラ Le ダ イ ト CY-192, ア ラ Le ダ イ ト CY-184 (the above CIBA-GEIGY A.G of being makes), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (above is big Japanese イ Application キ industry (strain) manufacturing), エ ピ コ-ト (now being jER) 871, エ ピ コ-ト 872 (above ジ
ヤパ Application エ Port キ シ レ ジ Application (strain) manufacturing), ED-5661, ED-5662 (above セ ラ ニ-ズ コ-テ
イApplication グ (strain) makes) etc., as the aliphatic poly glycidol ether, can enumerate デ Na コ-Le EX-611, デ Na コ-Le EX-612, デ Na コ-Le EX-614, デ Na コ-Le EX-622, デ Na コ-Le EX-411, デ Na コ-Le EX-512, デ Na コ-Le EX-522, デ Na コ-Le EX-421, デ Na コ-Le EX-313, デ Na コ-Le EX-314, デ Na コ-Le EX-321 (Na ガ セ ケ system テ
StarNetwork ス (strain) makes) etc.
These cross-linked compounds can use separately or be used in combination more than 2 kinds.
The consumption of (D) component cpd is 1～80 mass parts with respect to the alkali soluble resins of 100 mass parts (A) composition in addition, preferred 5～40 mass parts.(D) consumption of component cpd is if not enough above-mentioned scope lower limit a small amount of excessively, and then heat curing is insufficient, can not get satisfied cured film, on the other hand, if (D) consumption of component cpd is the mistake volume that surpasses above-mentioned range limit, then developing becomes insufficient, can produce the development residue.
＜(E) solvent 〉
(E) solvent that uses among the present invention is dissolving (A) composition～(C) composition and (D) composition, and the solvent of aftermentioned (F) composition that dissolving is added as required～(H) become to grade, get final product so long as have the solvent of such solubility property, to not restriction especially such as its kind and structure.
As such (E) solvent, for example can enumerate, glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, 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,N-dimethylacetamide and N-Methyl pyrrolidone etc.
These solvents can use separately more than a kind or 2 kinds and be used in combination.
In these (E) 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.
＜F composition 〉
(F) composition is other alkali soluble resins except (A) composition.In the positive type photosensitive organic compound of the present invention, in the limit of not damaging effect of the present invention, can also contain based on 100 mass parts (A) composition is other alkali soluble resins except that (A) composition of 1～90 mass parts.
As such (F) composition, for example can enumerate acrylic resin except that (A) composition and hydroxy styrenes resinoid, phenol novolac resin, polyamide, polyimide precursor, polyimide resin etc.
＜G composition 〉
(G) 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 (G) 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 product 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 products 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 (manufacturing)), メ ガ Off
The ア StarNetwork F171, F173 (big Japanese イ Application キ chemical industry (strain) manufacturing), Off ロ ラ-De FC430, FC431 (Sumitomo ス リ-エ system (strain) is made), ア サ ヒ ガ-De AG710, サ-Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 fluorine class surfactants such as (Asahi Glass (strain) manufacturings).
(G) surfactant of composition can use separately more than a kind or 2 kinds and be used in combination.
Under the situation of using surfactant, its content is generally below the 0.2 quality % in positive type photosensitive organic compound 100 quality %, is preferably below the 0.1 quality %.Even the consumption of the surfactant of (G) 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.
＜H composition 〉
(H) composition is an adhesion promotor.For improve with develop after the cohesive of substrate, positive type photosensitive organic compound of the present invention can also add adhesion promotor.Object lesson as such adhesion promotor, can enumerate, trimethyl chlorosilane, the dimethyl vinyl chlorosilane, methyldiphenyl base chlorosilane, chlorosilane classes such as CMDMCS chloromethyl dimethyl chlorosilane, the trimethyl methoxy silane, dimethyldiethoxysilane, methyl dimethoxysilane, dimethyl vinyl Ethoxysilane, dimethoxydiphenylsilane, alkoxyl silicone alkanes such as phenyl triethoxysilane, hexamethyldisilazane, N, N '-two (trimethyl silyl) urea, dimethyl trimethyl silyl amine, silazane classes such as trimethyl-silyl-imidazole, vinyl trichlorosilane, γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl triethoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-silanes such as (N-piperidyl) propyl-triethoxysilicane, benzotriazole, benzimidazole, indazole, imidazoles, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, the 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, heterocycle shape compounds such as mercaptopyrimidine, and 1, the 1-dimethyl urea, 1, urea or thiourea compounds such as 3-dimethyl urea.
Above-mentioned adhesion promotor for example can use, the commercially available product compound of SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing, the シ リ of GE Toshiba コ-Application (strain) Zhi Zao He East レ ダ ウ コ-ニ Application グ (strain) manufacturing etc., and these commercially available products can easily obtain.
As (H) composition, can use being used in combination more than a kind or 2 kinds in the above-mentioned adhesion promotor.
The addition of these adhesion promotors with respect to 100 mass parts (A) composition, is generally below 20 mass parts, is preferably 0.01～10 mass parts, more preferably 0.5～10 mass parts.If use more than 20 mass parts, the thermotolerance of then filming reduces sometimes, if less than 0.1 mass parts in addition then can not obtain the abundant effect of adhesion promotor sometimes.
＜other adjuvant 〉
In addition, in the limit of not damaging effect of the present invention, as required, can also contain cosolvents such as rheology control agent, pigment, dyestuff, preserving stabilizer, defoamer or polyhydric phenol, polybasic carboxylic acid etc. in the positive type photosensitive organic compound of the present invention.
＜positive type photosensitive organic compound 〉
Positive type photosensitive organic compound of the present invention is following composition, its contain alkali soluble resins, (B) composition of (A) composition silicone compounds, (C) composition 1, cross-linked compound of 2-quinone di-azido compound, (D) composition and (E) solvent, and according in the adhesion promotor of the surfactant of required other alkali soluble resins that can also contain (F) composition, (G) composition separately, (H) composition and other adjuvant more than a kind.
Wherein, the preferred example of positive type photosensitive organic compound of the present invention is as described below.
[1]: based on 100 mass parts (A) composition, contain 0.1～30 mass parts (B) composition, 5～100 mass parts (C) composition and 1～80 mass parts (D) composition, these compositions are dissolved in the positive type photosensitive organic compound in (E) solvent.
[2]: in the composition of above-mentioned [1], also contain the positive type photosensitive organic compound of 1～90 mass parts (F) composition based on 100 mass parts (A) composition.
[3]: in the composition of above-mentioned [1] or [2], also contain the positive type photosensitive organic compound of following (G) composition of 0.2 quality % based on 100 mass parts (A) composition.
[4]: in the composition of above-mentioned [1], [2] or [3], also contain the positive type photosensitive organic compound of 0.5～10 mass parts (H) composition based on 100 mass parts (A) composition.
The ratio of solid constituent in the positive type photosensitive organic compound of the present invention does not promptly limit especially as long as each composition is dissolved in the solvent equably, 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 removing behind (E) solvent from whole compositions of positive type photosensitive organic compound.
Not restriction especially of modulator approach to positive type photosensitive organic compound of the present invention, as its modulator approach, for example can enumerate, (A) composition (alkali soluble resins) is dissolved in (E) solvent, according to the rules ratio is mixed (B) composition (silicone compounds) in this solution, (C) composition (1, the 2-quinone di-azido compound) and (D) composition (cross-linked compound) forms the method for homogeneous solution, perhaps in the suitable stage of this modulation method, add (F) composition (other alkali soluble resins) as required again, (G) composition (surfactant), (H) composition (adhesion promotor) and other adjuvant method of mixing.
When modulation positive type photosensitive organic compound of the present invention, can directly use the solution of the specific copolymer that obtains by polyreaction in (E) solvent, at this moment when in the solution of this (A) composition, becoming to grade to form homogeneous solution, in order to regulate concentration additional input again (E) solvent with above-mentioned same adding (B) composition, (C) composition, (D).At this moment, (E) solvent that uses in the specific copolymer forming process is used to regulate (E) solvent of concentration when modulating with 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 preferably is that use the filtration backs such as filtrator about 0.2 μ m in the use aperture.
＜film 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.), by coating positive type photosensitive organic compounds of the present invention such as spin coating after spin coating, flow coat, roller coat, slit coating, the slot coated, ink-jet coatings, predrying by hot plate or baking oven etc. then, can form and film.This is filmed by heat treated then, forms the normal Photosensitive resin film.
As the condition of this heat treated, adopt heating-up temperature and heat time heating time in the scope that for example suitably is selected from 70 ℃～160 ℃ of temperature, 0.3～60 minute time.Are preferably heating-up temperature and heat time heating time 80 ℃～140 ℃, 0.5～10 minute.
In addition, the thickness of the normal Photosensitive resin film that is formed by positive type photosensitive organic compound for example is 0.1～30 μ m, 0.2～10 μ m for example in addition, and then for example be 0.2～5 μ m.
By light such as the mask with predetermined pattern, and irradiation ultraviolet radiation are installed on above-mentioned filming of obtaining, in alkaline developer, develop, the flushing exposed portion can obtain the sharp fluctuating pattern of end face.
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.
In above-mentioned, the aqueous solution of 0.1～2.38 quality % tetraethyl ammonium hydroxide is generally used as the developer solution of photoresist, also uses this alkaline-based developer in photosensitive polymer combination of the present invention, 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 obtain forming the film of pattern by rotation.
Then, such pattern is formed film, by being used for the back oven dry of heat curing, specifically by 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 on hot plate 5～30 minutes, handles 30～90 minutes method in baking oven.
And, by so back oven dry, can obtain having the target cured film of good pattern form.
As mentioned above, by 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, as to have fine pattern porous matter and film.
In addition, be porous matter by this cured film that obtains of filming, have following characteristics: thermotolerance, solvent resistance excellence, the film surface has high water repellency, handles its water repellency of back through continuumpiston and also can not be subjected to bigger infringement.Therefore, can be applicable to the various films in LCD or the OLED display, for example divide edge that pixel uses, interlayer dielectric, diaphragm, dielectric film etc., also be applicable to the purposes such as array planarization film of TFT type liquid crystal cell simultaneously.
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 that uses among the following embodiment is as follows.
MAA: methacrylic acid
MMA: methyl methacrylate
HEMA: methacrylic acid-2-hydroxyethyl ester
CHMI:N-cyclohexyl maleimide
PFMA: perfluoroalkyl methacrylate
GMA: methyl propenoic acid glycidyl base ester
DCM: methacrylic acid two cyclopentyl esters
AIBN: azoisobutyronitrile
PGMEA: propylene glycol methyl ether acetate
QD: by 1 mole 1,3,3-three (4-hydroxy phenyl) butane and 2 mole 1, the compound that 2-naphthoquinones-2-diazido-5-sulfonic acid chloride condensation reaction is synthetic
CL1: ダ イ セ Le chemical industry (strain) is made エ Port リ-De GT-401: the 6-caprolactone that epoxidation butanetetra-carboxylic acid four (3-cyclohexenyl group methyl) is modified
CL2: ダ イ セ Le chemical industry (strain) is made セ ロ キ サ イ De 2021P:3,4-epoxy radicals cyclohexenyl group-3 ', 4 '-epoxy radicals cyclohexene carboxylate ester
MPTS: γ-methacryloxypropyl trimethoxy silane
R30: big Japanese イ Application キ chemical industry (strain) is made メ ガ Off
The ア StarNetwork R-30 (trade name)
PDMS1: dimethyl silicone polymer C-terminal Mn:550
PDMS2: dimethyl silicone polymer-poly-diphenyl siloxane multipolymer C-terminal Mn:
1000
PDMS3: dimethyl silicone polymer Mn:580
PDMS4: dimethyl silicone polymer diglycidyl ether terminal M n:980
PDMS5: dimethyl silicone polymer dihydroxy alkyl terminal M n:5600
PDMS6: dimethyl silicone polymer divinyl terminal M n:250000
PDMS7: dimethyl silicone polymer C-terminal Mn:8000
PDMS8: East レ ダ ウ コ-ニ Application グ (strain) makes SH3771
[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 specific copolymer that obtains according to following synthesis example and the number-average molecular weight and the weight-average molecular weight of specific crosslinked body.Following in addition number-average molecular weight (hereinafter referred to as Mn) and weight-average molecular weight (hereinafter referred to as Mw) are used the polystyrene conversion value representation.
＜synthesis 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, by making them in 200g solvent PGMEA, 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)
＜synthesis example 2 〉
Use 10.9g MAA, 35.3g CHMI, 25.5g HEMA, 28.3g MMA as the monomer that constitutes specific copolymer, use 5g AIBN as radical polymerization initiator, by making them in 200g solvent PGMEA, under 60 ℃～100 ℃ of temperature, carry out polyreaction, obtain solution (the specific copolymer concentration: 27.5 quality %) of (A) composition (specific copolymer) of Mn4100, Mw7100.(P2)
＜synthesis example 3 〉
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, by making them in 95.4g solvent PGMEA, 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.(P3)
＜synthesis example 4 〉
Use 23.0g MAA, 40.0g GMA, 37.0g DCM as the monomer that constitutes specific copolymer, use 5g AIBN as radical polymerization initiator, by making them in 200g solvent PGMEA, under 60 ℃～100 ℃ of temperature, carry out polyreaction, obtain solution (the specific copolymer concentration: 27.5 quality %) of (A) composition (specific copolymer) of Mn4300, Mw9600.(P4)
＜embodiment 1～4 and comparative example 1～7 〉
According to the composition as shown in following table 1, by according to the rules ratio in the solution of (A) composition mix (B) composition, (C) composition, (D) composition and (E) solvent, also have (G) composition and (H) 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) solvent (g) | (G) composition (g) | (H) composition (g) | |
| Embodiment 1 | P1/P2 7.5/7.5 | PDMS1 0.41 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
| Embodiment 2 | P1/P2 7.5/7.5 | PDMS2 0.41 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
| Embodiment 3 | P1/P2 7.5/7.5 | PDMS3 0.41 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
| Embodiment 4 | P1/P2 7.5/7.5 | PDMS4 0.21 | QD 0.50 | CL1/CL2 0.49 | PGMEA 5.75 | - | MPTS 0.19 |
| Comparative example 1 | P1/P2 7.5/7.5 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 4.75 | R30 0.0028 | MPTS 0.19 | |
| Comparative example 2 | P1/P2 7.5/7.5 | PDMS5 0.41 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
| Comparative example 3 | P1/P2 7.5/7.5 | PDMS6 0.41 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
| Comparative example 4 | P1/P2 7.5/7.5 | PDMS7 0.41 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
| Comparative example 5 | P1/P3 14.3/0.7 | - | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 4.75 | MPTS 0.19 | |
| Comparative example 6 | P4 15.0 | PDMS1 0.21 | QD 1.25 | - | PGMEA 5.70 | MPTS 0.19 | |
| Comparative example 7 | P1/P2 7.5/7.5 | PDMS8 0.21 | QD 0.50 | CL1/CL2 0.41/0.29 | PGMEA 5.75 | - | MPTS 0.19 |
Each positive type photosensitive organic compound for embodiment 1～4 that obtains and comparative example 1～7, measure the contact angle, emptying aperture footpath and the specific inductive capacity that subtract (in the unexposed portion), water and diiodomethane with intermiscibility, light sensitivity, the film of acryl resin respectively, carried out following evaluation.
[stability of solution evaluation]
For the above-mentioned positive type photosensitive organic compound that obtains, in said composition modulation back and after at room temperature preserving 1 month all transparent and uniform dissolution be labeled as zero, occurring gonorrhoea after the modulation or after preserving 1 month or separating out insolubles or being labeled as of gelation *.
[evaluation of light sensitivity]
After using spinner coating 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.On filming, this makes that light intensity is 5.5mW/cm under the 365nm of ultraviolet lamp PLA-600FA irradiation certain hour by キ ヤ ノ Application (strain)
2Ultraviolet ray.After dipping develops for 60 seconds in 0.4 quality % tetramethyl ammonium hydroxide (hereinafter referred to as TMAH) aqueous solution then, carry out flowing water washing in 20 seconds 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 coating 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 coating 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 by 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 the water on this cured film and the contact angle of diiodomethane.
[evaluation of Cement Composite Treated by Plasma patience]
After using spinner coating 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 by heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.Use (strain) テ Network ノ PVC ジ
ヨThe UV-312 of Application manufacturing films to this and carries out 5 minutes ozone washing.The contact angle of the water on the film that the Drop Master mensuration ozone washing of using consonance interface science (strain) to make was handled.
[evaluation of emptying aperture]
After using spinner coating 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 by heating under 230 ℃, and forming thickness is the cured film of 1.9 μ m.Use scanning electron microscope (hereinafter referred to as SEM) to estimate the size that this section of filming has or not emptying aperture and emptying aperture footpath."＜100 " mark represents to exist the emptying aperture of the not enough 100nm of diameter in the following table 2 in addition.
[evaluation of specific inductive capacity]
After using spinner coating positive type photosensitive organic compound on the ito substrate, under 110 ℃ of temperature, on hot plate, carry out 120 seconds of prebake, forming thickness is filming of 2.0 μ m.This is filmed and carried out the back oven dry in 30 minutes by heating under 230 ℃, and forming thickness is the cured film of 1.5 μ m.Vacuum evaporation 0.28cm on this is filmed
2The Al pattern.Use the specific inductive capacity under this basal lamina determination 100kHz.
[evaluation result]
Carry out following evaluation, the result is presented in the following table 2.
[table 2]
As can judging from the result shown in the table 2, the positive type photosensitive organic compound of embodiment 1～4 all is ISO, film in the unexposed portion subtracts very little, all has high water repellency in UV Cement Composite Treated by Plasma front and rear surfaces, in film, form emptying aperture in addition, show low-k.
For comparative example 2～4, the stability of solution of positive type photosensitive organic compound is low, can not obtain uniform solution.In addition for comparative example 6, though gelation has taken place in room temperature preservation the homogeneous solution that has obtained.
Though the positive type photosensitive organic compound of comparative example 1 has ISO, the film in the unexposed portion subtracts also little, and the water repellency on film surface and Cement Composite Treated by Plasma patience are low, does not also form emptying aperture in addition in the film.
Though the positive type photosensitive organic compound of comparative example 5 and 7 has ISO, the film in the unexposed portion subtracts also little, can obtain high water repellency in addition, and UV plasma patience is low, does not form emptying aperture in the film in addition, does not also observe specific inductive capacity and reduces.
Industrial utilizability
Positive type photosensitive organic compound among the present invention is suitable as the material of the 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 as the material of embossed film, the dielectric film of organic EL etc. of reflectance coating downside of protection mould, array planarization film, the reflective display of the interlayer dielectric that forms TFT type liquid crystal cell, colour filter, also be suitable as in addition the various electronic materials such as microlens material.
Claims (12)
1. positive type photosensitive organic compound contains following (A) composition, (B) composition, (C) composition, (D) composition and (E) solvent,
(A) composition: (i) alkali soluble resins that obtains with (ii) copolymerization, (i) unsaturated carboxylic acid, (ii) be selected from the compound more than a kind in acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound and the vinyl compound
(B) composition: number-average molecular weight is 100～2000 silicone compounds,
(C) composition: 1, the 2-quinone di-azido compound,
(D) composition: cross-linked compound,
(E) solvent.
2. positive type photosensitive organic compound as claimed in claim 1, (A) number-average molecular weight of the alkali soluble resins of composition is 2000～30000 by polystyrene conversion.
3. photosensitive polymer combination as claimed in claim 1 or 2, the cross-linked compound that it is characterized in that (D) composition are the compounds that contains the above epoxy radicals of 2 officials energy.
4. as each described positive type photosensitive organic compound of claim 1～3, (D) cross-linked compound of composition is the compound of formula (1) expression,
In the formula, k is 2～10 integer, and m represents 0～4 integer, and R represents the organic group of k valency.
5. as each described positive type photosensitive organic compound of claim 1～4, (E) solvent contains and is selected from least a kind of solvent in propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, ethyl lactate and the butyl lactate.
6. as each described positive type photosensitive organic compound of claim 1～5, it is characterized in that,, contain (B) composition of 0.1～30 mass parts, (C) composition of 5～100 mass parts and (D) composition of 1～80 mass parts based on 100 mass parts (A) composition.
7. as each described positive type photosensitive organic compound of claim 1～6, in positive type photosensitive organic compound, also contain the surfactant of (G) composition of conduct below the 0.2 quality %.
8. the cured film of using each described positive type photosensitive organic compound of claim 1～7 to obtain.
9. the separator material that organic EL display element is used has the described cured film of claim 8.
10. liquid crystal display cells has the described cured film of claim 8.
11. LCD array planarization film is formed by the described cured film of claim 8.
12. interlayer dielectric is formed by the described cured film of claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP136798/2006 | 2006-05-16 | ||
| JP2006136798 | 2006-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101443704A true CN101443704A (en) | 2009-05-27 |
Family
ID=38693979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800175606A Pending CN101443704A (en) | 2006-05-16 | 2007-05-16 | Positive photosensitive resin composition and porous film obtained therefrom |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2007132890A1 (en) |
| KR (1) | KR20090010044A (en) |
| CN (1) | CN101443704A (en) |
| TW (1) | TW200813635A (en) |
| WO (1) | WO2007132890A1 (en) |
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| CN102472833A (en) * | 2009-08-24 | 2012-05-23 | 日产化学工业株式会社 | Photosensitive resin composition for microlens |
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| CN107561863A (en) * | 2016-06-30 | 2018-01-09 | 奇美实业股份有限公司 | Positive photosensitive resin composition and application thereof |
| CN108139672A (en) * | 2015-11-06 | 2018-06-08 | 罗门哈斯电子材料韩国有限公司 | Photosensitive polymer combination and cured film prepared therefrom |
| CN110537147A (en) * | 2017-04-21 | 2019-12-03 | 日产化学株式会社 | Photosensitive polymer combination |
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| JP3484808B2 (en) * | 1995-03-24 | 2004-01-06 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition for forming interlayer insulating film, interlayer insulating film and method of manufacturing the same |
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-
2007
- 2007-05-16 WO PCT/JP2007/060038 patent/WO2007132890A1/en active Application Filing
- 2007-05-16 TW TW96117392A patent/TW200813635A/en unknown
- 2007-05-16 JP JP2008515588A patent/JPWO2007132890A1/en not_active Withdrawn
- 2007-05-16 KR KR1020087026934A patent/KR20090010044A/en not_active Application Discontinuation
- 2007-05-16 CN CNA2007800175606A patent/CN101443704A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2007132890A1 (en) | 2007-11-22 |
| JPWO2007132890A1 (en) | 2009-09-24 |
| KR20090010044A (en) | 2009-01-28 |
| TW200813635A (en) | 2008-03-16 |
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Application publication date: 20090527 |