CN102047181B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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CN102047181B
CN102047181B CN200980119560.6A CN200980119560A CN102047181B CN 102047181 B CN102047181 B CN 102047181B CN 200980119560 A CN200980119560 A CN 200980119560A CN 102047181 B CN102047181 B CN 102047181B
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methoxy
compound
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CN102047181A (en
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丹羽基博
涩井智史
金田隆行
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Asahi Chemical Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Abstract

Disclosed is a novel photosensitive resin composition having positive lithographic properties, which has excellent storage stability, while exhibiting high sensitivity and excellent long-term stability of sensitivity after exposure. A method for producing a cured relief pattern using the composition and a semiconductor device having the cured relief pattern are also disclosed. The photosensitive resin composition is characterized by containing (A) 100 parts by mass of a hydroxypolyamide containing a structure represented by general formula (1) (wherein X1, X2, Y1, Y2, l and m are as defined in claims), (B) 0.01-30 parts by mass of an alkoxyalkyl group-containing compound represented by general formula (2) (wherein k, X, R1, R2, n, p and q are as defined in claims), and (C) 1-100 parts by mass of a diazoquinone compound.

Description

Photosensitive polymer combination
Technical field
The present invention relates to the photosensitive polymer combination that surface protection film, interlayer dielectric as semiconductor device use, use the manufacture method with stable on heating cured relief pattern of this photosensitive polymer combination and have this cured relief pattern and the semiconductor device that forms.
Background technology
Up to now, the surface protection film of semiconductor device, interlayer dielectric use the polyimide resin that has excellent thermotolerance and electrical characteristics, mechanical property etc. concurrently.This polyimide resin is generally supplied with the form of photosensitive polyimide precursor composition at present; by the coating on substrate, the patterning that utilizes active ray, development, hot-imide processing etc.; can be set up at semiconductor device and easily form surface protection film, interlayer dielectric etc.; compare with present non-photosensitive polyimide precursor composition, have the feature that can significantly shorten operation.
Yet the photosensitive polyimide precursor composition needs to use a large amount of organic solvents such as METHYLPYRROLIDONE as developer solution in its developing procedure, because the aggravation of environment in recent years problem etc. are seeking to take off the organic solvent countermeasure always.In view of this requirement, proposed recently multiple and photoresist thermotolerance photoresist material same, that in alkaline aqueous solution, can develop.
Wherein, use PBO precursor composition that the photolytic activity compositions such as hydroxypolyamide such as the polybenzoxazole of alkaline aqueous solution solubility (below be also referred to as " PBO ") precursor and diazonium naphtoquinone compounds are mixed to receive concern (for example following patent documentation 1 of reference) in recent years as the method for positive type photosensitive organic compound.
The development mechanism of this normal Photosensitive resin is to have utilized following mechanism: the diazonium naphtoquinone compounds of unexposed section is insoluble in alkaline aqueous solution, in contrast, since exposure, this diazonium naphtoquinone compounds generation chemical change, form indene carboxylic acid's compound, it is solvable to become in alkaline aqueous solution.Utilize the different of the dissolution velocity in developer solution between this exposure section and the unexposed section, can make the only embossing pattern of unexposed section.
Above-mentioned PBO precursor composition is by exposure and utilize the development of alkaline aqueous solution and can form positive relief pattern.Further by heating (below be also referred to as " curing ") Sheng Cheng oxazole ring, PBO film after the curing has the heat cured film characteristic equal with polyimide film, therefore, has been subject to gazing at as the promising replacement material of organic solvent developable polyimide precursor.
When using this photosensitive polymer combination to make semiconductor, the light sensitivity of photosensitive polymer combination particularly importantly.In the exposure process when the manufacturing of semiconductor device, main use the i ray that utilizes mercury lamp be called i ray ledex (being designated hereinafter simply as " ledex (stepper) ") reduced projection exposure machine.This ledex is very expensive instrument, and therefore, if when photosensitive polymer combination is low speed, it is elongated to form the required time shutter of embossing pattern, and the number of units of needed ledex increases, and causes the cost of exposure technology to increase.
As one of method of the light sensitivity that improves positive type photosensitive organic compound, known have a technology of adding the compound with heat cross-linking group in composition.When the compound with heat cross-linking group adds in photosensitive polymer combination, produce addition reaction during curing and between the aromatic rings of polymkeric substance, have the effect of the contraction of the contraction that suppresses decomposition or thermal relaxation by polymkeric substance and cause, the film when control is solidified.If can control the contraction when solidifying, with the initial stage coating film thickness of identical composition, just can obtain thicker final thickness.In other words, just can obtain identical final thickness with thin initial stage coating film thickness.The coating film thickness at initial stage is thinner, and ISO as the positive type photosensitive organic compound that there is opening in exposure section, can be realized in the just easier arrival film of the luminous energy in exposure process bottom.
As the at present known technology of adding the heat cross-linking group in composition, what for example proposed to add methylol bridging property hot in nature in alkali soluble resin has the technology that urea is the compound of the organic group claim 2 of patent documentation 1 (for example with reference to), adds the technology (for example with reference to following patent documentation 2) of the compound with epoxy radicals, the technology (for example with reference to following patent documentation 2) of adding the compound with benzoxazinyl group in alkali soluble resin in alkali soluble resin.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-328472 communique
Patent documentation 2: TOHKEMY 2004-093816 communique
Patent documentation 3: TOHKEMY 2000-305268 communique
Patent documentation 4: TOHKEMY 2006-178437 communique
Patent documentation 5: TOHKEMY 2005-037925 communique
Patent documentation 6: TOHKEMY 2007-016214 communique
Patent documentation 7: Japanese kokai publication hei 06-27654 communique
Summary of the invention
The problem that invention will solve
Although above-mentioned thermal cross-linking agent demonstrates high efficiency and high cross-linking effect polymer reaction, but because this high response, composition is coated on heating in the operation that forms photo-sensitive resin on the substrate (below be also referred to as " prebake ") thus may be so that also crosslinked infringement resolution of unexposed section; Thereby the acid that produces owing to exposure in the exposure section may damage light sensitivity so that thermal cross-linking agent reacts; The rough sledding such as the storage stability of composition is impaired perhaps might appear.In addition, developed in alkali soluble resin the technology of adding the methylol cross-linked compound hot in nature with phenol hydroxyl and be known claim 1, patent documentation 3, the patent documentation 4 of patent documentation 1 (for example with reference to), because these compounds contain the phenol hydroxyl, therefore improved the alkali dissolubility of composition, if increase addition, until reach the amount of the contraction when being enough to suppress to solidify, then damaged the dissolution velocity poor (contrast) of exposure section and unexposed section, light sensitivity reduces on the contrary.Adding the technology do not contain the phenol hydroxyl but to contain the compound of methylol in alkali soluble resin also is known (for example with reference to patent documentation 5), compound with methylol reacts (dark reaction) lentamente in composition, have the bad shortcoming of storage stability (viscosity stability) of photosensitive polymer combination.In addition, the composition (with reference to patent documentation 2, patent documentation 6) that adds the heat cross-linking compound with alkoxy methyl more stable than methylol in alkali soluble resin is disclosed, also see the record that to use the compound that does not contain the phenol hydroxyl, but in fact do not provided the embodiment of the compound that contains alkoxy methyl that does not contain the phenol hydroxyl.
Problem in view of above-mentioned prior art, problem to be solved by this invention provides novel photosensitive polymer combination with eurymeric lithography performance, use the manufacture method of cured relief pattern of said composition and the semiconductor device with this cured relief pattern, and described photosensitive polymer combination excellent storage stability, the ageing stability with the light sensitivity after ISO and the exposure are excellent.
For the scheme of dealing with problems
The inventor furthers investigate repeatedly in order to solve above-mentioned problem, found that, by heat cross-linking low molecular compound and the polybenzoxazole resin combination of precursors that will have ad hoc structure, do not damage storage stability (viscosity stability), obtained the photosensitive polymer combination with eurymeric photolithographic characteristics of ISO.Further also find, by making up with the heat cross-linking low molecular compound with ad hoc structure, obtained that rheological parameters' change with time after the exposure of photolithographic characteristics of ISO is little, the photosensitive polymer combination of the ageing stability excellence of light sensitivity, thereby finished the present invention.
That is, the present invention is as described below.
[1] a kind of photosensitive polymer combination is characterized in that, comprises:
100 mass parts (A) contain the hydroxypolyamide of structure shown in the following general formula (1),
[Chemical formula 1]
In the formula (1), X 14 valency organic groups with carbon atom, X 2, Y 1And Y 2Be the divalent organic group with 2 above carbon atoms independently of one another, l is 2～1000 integer, and m is 0～500 integer, l/ (l+m)＞0.5, and contain X 1And Y 1L dihydroxy diamides unit and contain X 2And Y 2Putting in order of m diamides unit be arbitrarily,
0.01 the compound that contains alkoxyalkyl shown in the following general formulas of～30 mass parts (B) (2),
[Chemical formula 2]
Figure BPA00001259067700052
In the formula (2), k is 1～4 integer, and (i) during k=1, X is C nH 2nOR 1Or R 2, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2It is the 1 valency organic group that is selected from the group that the alkoxy by the carbamate groups of the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10, carbon number 2～10 and carbon number 1～10 forms, n is 1～3 integer, p is 1～5 integer, q is 0～4 integer, and (p+q)=5, (ii) k=2～4 o'clock, X is singly-bound or 2～4 valency organic groups, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, and p is 1～5 integer, q is 0～4 integer, and (p+q)=5, wherein, at C nH 2nOR 1And R 2There are in a plurality of situations n, p, q, R 1And R 2Can be the same or different each other; And
1～100 mass parts (C) diazonium naphtoquinone compounds.
[2] according to above-mentioned [1] described photosensitive polymer combination, wherein (B) compound of containing alkoxyalkyl is with following general formula (3) expression,
[chemical formula 3]
Figure BPA00001259067700061
In the formula (3), k is 1 or 2, and (i) during k=1, X is C nH 2nOR 1Or R 2, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2It is the 1 valency organic group that is selected from the group that the alkoxy by the carbamate groups of the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10, carbon number 2～10 and carbon number 1～10 forms, n is 1～3 integer, (ii) during k=2, X is singly-bound or is selected from 2～4 valency organic groups in the group shown in the following general formula (4), R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, and p is 1～5 integer, q is 0～4 integer, and (p+q)=5, wherein, at C nH 2nOR 1And R 2There are in a plurality of situations n, p, q, R 1And R 2Can be the same or different each other.
[chemical formula 4]
Figure BPA00001259067700071
[3] according to above-mentioned [1] or [2] described photosensitive polymer combination, wherein, the compound that (B) contains alkoxyalkyl represents with following general formula (5),
[chemical formula 5]
Figure BPA00001259067700072
In the formula (5), R 1Be the 1 valency organic group that is selected from the group that is comprised of methyl, ethyl, n-pro-pyl and isopropyl, n is 1～3 integer, and p is 1～5 integer, and k is 1 or 2, and (i) during k=1, X is hydrogen atom or C nH 2nOR 1, (ii) during k=2, X is singly-bound or is selected from 2～4 valency organic groups in the group shown in the following general formula (6), wherein, and at (C nH 2nOR 1) there are in a plurality of situations n and R 1Can be the same or different each other.
[chemical formula 6]
Figure BPA00001259067700073
[4] according to each described photosensitive polymer combinations of above-mentioned [1]～[3], wherein, the compound that (B) contains alkoxyalkyl is selected from the group that is comprised of two (methoxy) benzene, three (methoxy) benzene, four (methoxy) benzene, five (methoxy) benzene, six (methoxy) benzene, three (methoxy) trimethoxy-benzene, methoxy biphenyl, two (methoxy) biphenyl, two (methoxy) diphenyl ether and two (methoxy) diphenyl methanes.
[5] according to above-mentioned [1] described photosensitive polymer combination, wherein, the compound that (B) contains alkoxyalkyl is with following general formula (7) expression,
[chemical formula 7]
In the formula (7), Z 1Be the substituting group that is selected from the group shown in the following general formula (8), k is 1～4 integer, (i) during k=1, and Z 2C nH 2nOR 1Or R 2, R is methyl or ethyl independently of one another, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the alkyl by hydrogen atom and carbon number 1～4 forms, n is 1～3 integer, (ii) k=2～4 o'clock, Z 2Singly-bound or 2～4 valency organic groups, Z 1There is in a plurality of situations Z 1Can be the same or different,
[chemical formula 8]
Figure BPA00001259067700091
In the formula (8), R 3～R 5The organic group of carbon number 1～9 independently of one another, R 6The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, and R 7～R 10The organic group of carbon number 1～12 independently of one another.
[6] according to above-mentioned [5] described photosensitive polymer combination, wherein, the compound that (B) contains alkoxyalkyl is with following general formula (9) expression,
[chemical formula 9]
Figure BPA00001259067700092
In the formula (9), R is methyl or ethyl independently of one another, Z 1The substituting group that is selected from the group shown in the following general formula (10) independently of one another, Z 3Be singly-bound or be selected from substituting group in the group shown in the following general formula (11),
[Chemical formula 1 0]
Figure BPA00001259067700101
In the formula (10), R 3～R 5The organic group of carbon number 1～9 independently of one another, R 6The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, and R 7～R 10The organic group of carbon number 1～12 independently of one another,
[Chemical formula 1 1]
[7] according to above-mentioned [6] described photosensitive polymer combination, wherein, in general formula (9), Z 3Singly-bound, Z 1The substituting group that is selected from the group shown in the following general formula (12) independently of one another,
[Chemical formula 1 2]
Figure BPA00001259067700103
In the formula (12), R 3And R 5The organic group of carbon number 1～9 independently of one another, and, R 7It is the organic group of carbon number 1～12.
[8] according to above-mentioned [6] described photosensitive polymer combination, wherein, in general formula (9), Z 3Singly-bound, Z 1The substituting group that is selected from the group shown in the following general formula (13) independently of one another,
[Chemical formula 1 3]
Figure BPA00001259067700111
[9] a kind of manufacture method of cured relief pattern, this manufacture method comprises following operation: the operation that forms the photo-sensitive resin that is made of each described photosensitive polymer combination of above-mentioned [1]～[8] at substrate; Expose with active ray or the operation of direct irradiation light, electron beam or ion line across mask; Developing procedure; And the operation of heating gained embossing pattern.
[10] a kind of semiconductor device, it has by above-mentioned [9] the cured relief pattern layer that described method obtains.
The effect of invention
According to the present invention, excellent storage stability is provided and have the eurymeric lithography performance of ISO novel photosensitive polymer combination, use said composition cured relief pattern manufacture method and have this cured relief pattern and the semiconductor device that forms.
Embodiment
＜photosensitive polymer combination 〉
Below specifically describe the various compositions that consist of photosensitive polymer combination of the present invention.
(A) hydroxypolyamide
Hydroxypolyamide as the base polymer of photosensitive polymer combination of the present invention comprises the structure shown in the following general formula (1).
[Chemical formula 1 4]
Figure BPA00001259067700121
In the formula, X 14 valency organic groups with carbon atom, X 2, Y 1And Y 2Be the divalent organic group with 2 above carbon atoms independently of one another, l is 2～1000 integer, and m is 0～500 integer, l/ (l+m)＞0.5, and contain X 1And Y 1L dihydroxy diamides unit and contain X 2And Y 2Putting in order of m diamides unit be arbitrarily.}。
In the general formula (1), X 1Preferably have more than 2 and 4 valency organic groups of the carbon atom below 30, and, X 2, Y 1And Y 2Preferably have independently of one another more than 2 and the divalent organic group of the carbon atom below 30.
The dihydroxy diamides unit that this hydroxypolyamide has has by containing Y 1(COOH) 2Structure dicarboxylic acid and contain X 1(NH 2) 2(OH) 2The structure that forms of two amino-phenol polycondensations of structure.Here, 2 groups of amino of this pair amino-phenol are at the ortho position with hydroxyl separately each other, and by these hydroxypolyamides of heating under about 280～400 ℃, this dihydroxy diamides unit closed loop is changed to the benzoxazole unit as heat-resistant resin.L is in 2～1000 scope, 2～200th, and preferred, more preferably 3～50 scope, more preferably 3～20 scope.
As required, diamides unit that can a condensation m aforementioned formula (1) on this hydroxypolyamide.This diamides unit has by containing X 2(NH 2) 2Structure diamines and contain Y 2(COOH) 2The structure that forms of the dicarboxylic acid polycondensation of structure.M is 0～500 scope, is preferably 0～10 scope.The ratio of the hydroxypolyamide unit in the hydroxypolyamide is higher, dissolubility in the alkaline aqueous solution that uses as developer solution is higher, and the required time of developing is shorter, so the value of l/ (l+m) is more than 0.5, be preferably more than 0.7, more preferably more than 0.8.
As having X 1(NH 2) 2(OH) 2Two amino-phenols of structure, for example can list 3,3 '-dihydroxybiphenyl amine, 3,3 '-diamido-4,4 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxybiphenyl, 3,3 '-diamido-4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-diamido-3,3 '-dihydroxy-diphenyl sulfone, two-(3-amino-4-hydroxyphenyl) methane, 2,2-pair-(3-amino-4-hydroxyphenyl) propane, 2,2-pair-(3-amino-4-hydroxyphenyl) HFC-236fa, 2,2-pair-(4-amino-3-hydroxyphenyl) HFC-236fa, two (4-amino-3-hydroxyphenyl) methane, 2,2-pair-(4-amino-3-hydroxyphenyl) propane, 4,4 '-diamido-3,3 '-dihydroxy benaophenonel, 3,3 '-diamido-4,4'-Dihydroxybenzophenone, 4,4 '-diamido-3,3 '-dihydroxydiphenyl ether, 3,3 '-diamido-4,4 '-dihydroxydiphenyl ether, 1,4-diamido-2, the 5-dihydroxy benzenes, 1,3-diamido-2, the 4-dihydroxy benzenes, 1,3-diamido-4,6-dihydroxy benzenes etc.These pairs amino-phenol can be used alone or as a mixture.
In the middle of these pairs amino-phenol, particularly preferably be X 1It is the aromatic group that is selected among following.
[Chemical formula 1 5]
Figure BPA00001259067700131
As having X 2(NH 2) 2The diamines of structure, aromatic diamine and silicon diamines etc. can be used as preferred example and enumerates.
In the middle of this, as aromatic diamine, for example can list m-phenylene diamine, p-phenylenediamine (PPD), 2, the 4-toluene diamine, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diamino-diphenyl ketone, 4,4 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, 2,2 '-two (4-aminophenyl) propane, 2,2 '-two (4-aminophenyl) HFC-236fa, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4-methyl-2, two (4-the aminophenyl)-1-amylenes of 4-, 4-methyl-2, two (4-the aminophenyl)-2-amylenes of 4-, 1, two (the α of 4-, alpha-alpha-dimethyl-4-aminobenzyl) benzene, imino group-di P phenylene diamine, 1, the 5-diaminonaphthalene, 2, the 6-diaminonaphthalene, 4-methyl-2, two (4-aminophenyl) pentanes of 4-, 5 (or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethyl indane, two (p-aminophenyl) phosphine oxide, 4,4 '-chrysoidine, 4,4 '-diamino-diphenyl urea, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] benzophenone of 2-, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfone, 4,4 '-two [4-(α, alpha-alpha-dimethyl-4-aminobenzyl) phenoxy group] benzophenone, 4,4 '-two [4-(α, alpha-alpha-dimethyl-4-aminobenzyl) phenoxy group] diphenyl sulfone, 4,4 '-benzidine, 4,4 '-diaminobenzophenone, the phenyl indan diamines, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, the ortho-aminotoluene sulfone, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, two (4-amino-benzene oxygen phenyl) sulfone, two (4-amino-benzene oxygen phenyl) thioether, 1,4-(4-amino-benzene oxygen phenyl) benzene, 1,3-(4-amino-benzene oxygen phenyl) benzene, 9, two (4-aminophenyl) fluorenes of 9-, 4,4 '-two-(3-amino-benzene oxygen) diphenyl sulfones and 4,4 '-diaminobenzene anilid, and the selected free chlorine atom of the hydrogen atom of the aromatic proton of these aromatic diamines, fluorine atom, bromine atoms, methyl, methoxyl, the compound that at least a group in the group that cyano group and phenyl form or atom replace.
In addition, in order to improve the cohesiveness with base material, can select the silicon diamines, as its example, can list two (4-aminophenyl) dimethylsilane, two (4-aminophenyl) tetramethyl silica alkane, two (4-aminophenyl) tetramethyl disiloxane, two (gamma-amino propyl group) tetramethyl disiloxane, Isosorbide-5-Nitrae-two (gamma-amino propyl-dimethyl silicyl) benzene, two (4-aminobutyl) tetramethyl disiloxane, two (gamma-amino propyl group) tetraphenyl disiloxane etc.
As having Y 1(COOH) 2Or Y 2(COOH) 2The dicarboxylic acid of structure can list Y 1, Y 2To have the aliphatic group of straight chain, side chain, ring texture or the dicarboxylic acid of aromatic group.Wherein, Y 1, Y 2During for aromatic group, as preferred structure example as listing following structure.
[Chemical formula 1 6]
{ in the formula, A represents to be selected from by-CH 2-,-O-,-S-,-SO 2-,-CO-,-NHCO-,-C (CF 3) 2-and the group that forms of singly-bound in the divalent group, R represents to be selected from the group in the group that is comprised of hydrogen atom, alkyl, alkenyl and halogen atom independently of one another, and k represents 0～4 integer.}。
In addition, above-mentioned have a Y 1(COOH) 2Or Y 2(COOH) 2Part or all of the dicarboxylic acid of structure be the preferred derivant that uses the amino m-phthalic acid of 5-also.
As the particular compound of reacting with the amino m-phthalic acid of 5-in order to obtain this derivant, can list 5-norborene-2, the 3-dicarboxylic anhydride, outward-3,6-epoxy radicals-1,2,3, the 6-tetrabydrophthalic anhydride, 3-ethinyl-1, the 2-phthalic anhydride, 4-ethinyl-1, the 2-phthalic anhydride, suitable-4-cyclohexene-1, the 2-dicarboxylic anhydride, 1-cyclohexene-1, the 2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, Nadic anhydride, the methyl Nadic anhydride, methyl tetrahydrophthalic anhydride, the allyl succinic anhydride, the methacrylic acid isocyanato ethyl, isocyanic acid 3-isopropenyl-α, alpha-alpha-dimethyl benzyl ester, 3-cyclohexene-1-carboxyl acyl chloride, 2-furans carboxyl acyl chloride, crotonyl chloride, cinnamoyl chloride, methacrylic chloride, acryloyl chloride, the propine acyl chlorides, the butine acyl chlorides, thiophene-2-acetyl chloride, to the styrene sulfonic acid chloride, glycidyl methacrylate, allyl glycidyl ether, methylchloroformate, ethyl chloroformate, the chloro-carbonic acid n-propyl, isopropyl chlorocarbonate, isobutyl chlorocarbonate, chloro-carbonic acid 2-ethoxylated ester, sec-butyl chloroformate, carbobenzoxy chloride, chloro-carbonic acid 2-ethylhexyl, allyl chlorocarbonate, phenyl chloroformate, chloro-carbonic acid 2,2, the 2-trichloro ethyl ester, chloro-carbonic acid-2-butoxyethyl, chloro-carbonic acid-p-p-Nitrobenzyl, chloro-carbonic acid-p-methoxy benzyl ester, chloro-carbonic acid isobornyl benzyl ester, chloro-carbonic acid-p-biphenyl isopropyl benzyl ester, 2-tertbutyloxycarbonyl-oxyimino group-2-phenylacetonitrile, S-tertbutyloxycarbonyl-4,6-dimethyl-sulphur pyrimidine, two dimethyl dicarbonate butyl esters, N-ethoxy carbonyl phthalimide, ethyl two sulfo-phosgenes, formyl chloride, chlorobenzoyl chloride, paratoluensulfonyl chloride, mesyl chloride, acetyl chloride, trityl chloride, trimethyl chlorosilane, hexamethyldisilazane, N, two (trimethyl silyl) acetamides of O-, two (trimethyl silyl) trifluoroacetamide, (N, the N-dimethylamino) trimethyl silane, (dimethylamino) trimethyl silane, the trimethyl silyl diphenyl urea, two (trimethyl silyl) urea, phenyl isocyanate, n-butyl isocyanate, isocyanic acid n-octadecane base ester, the isocyanic acid o-toluene ester, 1, the 2-phthalic anhydride, suitable-1,2-cyclohexane cyclohexanedimethanodibasic acid anhydride, glutaric anhydride.
In addition, as having Y 1(COOH) 2Or Y 2(COOH) 2The dicarboxylic acid of structure can also use and use monohydroxy alcohol, monoamine etc. with tetracarboxylic dianhydride's open loop and the compound that gets.Here, as the example of this monohydroxy alcohol, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol, benzylalcohol etc. can be listed, as the example of this monoamine, butylamine, aniline etc. can be enumerated.As this tetracarboxylic dianhydride's example, can list following material etc.,
[Chemical formula 1 7]
Figure BPA00001259067700171
{ in the formula, B represents to be selected from by-CH 2-,-O-,-S-,-SO 2-,-CO-,-NHCO-and-C (CF 3) 2Divalent group in the group of-composition.}。
In addition, make trimellitic acid chloride (Trimellitic acid chloride) and the reaction of the aforementioned pair of amino-phenol, generate the tetracarboxylic dianhydride, the open loop that uses the same method also can be used as and has Y 1(COOH) 2Or Y 2(COOH) 2The dicarboxylic acid of structure uses.Tetracarboxylic dianhydride as here obtaining can list following material,
[Chemical formula 1 8]
Figure BPA00001259067700172
In the formula, X 3Expression X 1(OH) 2(NH-) 2, and X 1Identical with the definition in the above-mentioned general formula (1).}。
Perhaps, make aforesaid tetracarboxylic dianhydride and aforesaid pair of amino-phenol reaction, also the carboxylic acid residues that generates can be become ester or acid amides by monohydroxy alcohol or monoamine.
Y 1, Y 2In the situation for aliphatic group, can list the substituting groups such as alkyl chain, cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, dicyclo.As having the Y that contains aliphatic group 1(COOH) 2Or Y 2(COOH) 2The dicarboxylic acid of structure, for example can list malonic acid, methylmalonic acid, dimethyl malonic acid, succinic acid, glutaric acid, hexane diacid, itaconic acid, maleic acid, diethylene glycol acid, 1, the 2-cyclobutane dicarboxylic acid, 1, the 3-cyclobutane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1, the 2-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, 1,3-diamantane dicarboxylic acid, octahydro-1H-4,7-benzofulvene dicarboxylic acid (octahydro-1H-4,7-methanoindene dicarboxylic acid) etc., as the dicarboxylic acid with aliphatic group, using octahydro-1H-4, during 7-benzofulvene dicarboxylic acid, owing to can have high transparent and the highly dissoluble in solvent concurrently, be preferred therefore.
To have Y as being used for 1(COOH) 2The dicarboxylic acid of structure with have an X 1(NH 2) 2(OH) 2Two amino-phenol polycondensations of structure and generate the method for dihydroxy diamides unit can list and use thionyl chloride to be generated after the diacid chloride method that two amino-phenols are worked by dicarboxylic acid; By dicyclohexyl carbodiimide with the method for dicarboxylic acid and two amino-phenol polycondensations etc.In the method for using dicyclohexyl carbodiimide, also can hydroxybenzotriazole be worked.In aforementioned (A) hydroxypolyamide, also preferably with organic group (hereinafter referred to as " end-capping group ") this end group end-blocking is used.
In the polycondensation of hydroxypolyamide, when using the dicarboxylic acid composition with respect to two amino-phenol compositions and two amine component sums with the molal quantity of surplus, as end-capping group, the preferred compound with amino or hydroxyl that uses.As the example of this compound, can list aniline, acetylenylaniline, norborneol enamine, butylamine, propargyl amine, ethanol, propargyl alcohol, benzylalcohol, hydroxyethyl methylacrylate and hydroxy-ethyl acrylate etc.
On the contrary, use two amino-phenol compositions and two amine component sums with respect to the situation of dicarboxylic acid composition for superfluous molal quantity under, as end-capping group, preferred use has the compound of acid anhydrides, carboxylic acid, acyl chlorides, isocyanate groups etc.As the example of this compound, can list chlorobenzoyl chloride, norbornene dicarboxylic acids acid anhydride, norborene carboxylic acid, ethinyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride, methylcyclohexane dicarboxylic anhydride, cyclohexene dicarboxylic anhydride, methacrylic acid methyl acryloxy ethyl ester, phenyl isocyanate, mesyl chloride, toluene sulfochloride etc.
(A) the polystyrene conversion weight-average molecular weight of measuring with gel permeation chromatography (hereinafter referred to as " GPC ") of hydroxypolyamide is preferably 3,000～50, and 000, more preferably 6,000～30,000.Consider that from the viewpoint of the physical property of cured relief pattern weight-average molecular weight is preferably more than 3,000.Consider that from the viewpoint of resolution weight-average molecular weight is preferably below 50,000.As the developing solvent of GPC, recommendation tetrahydrofuran (following also be expressed as " THF "), METHYLPYRROLIDONE (below be also referred to as " NMP ").In addition, molecular weight is obtained by the calibration curve of Application standard monodisperse polystyrene making.As the standard monodisperse polystyrene, recommending from organic solvent clear and that electrician company makes is to select the standard test portion STANDARD SM-105.
(B) contain the compound of alkoxyalkyl
Contain (B) in the photosensitive polymer combination and be selected from least a compound that contains alkoxyalkyl in the group that is formed by the compound shown in the following general formula (2).
[Chemical formula 1 9]
Figure BPA00001259067700191
{ in the formula, k is 1～4 integer, and (i) during k=1, X is C nH 2nOR 1Or R 2, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2It is the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkoxy of the alkyl of hydrogen atom, carbon number 1～4, carbon number 1～10, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, p is 1～5 integer, q is 0～4 integer, and (p+q)=5, (ii) k=2～4 o'clock, X is singly-bound or 2～4 valency organic groups, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, and n is 1～3 integer.Wherein, at C nH 2nOR 1And R 2There are in a plurality of situations n, p, q, R 1And R 2Can be the same or different each other.}。
The inventor finds, by in the photosensitive polymer combination that contains (A) hydroxypolyamide, adding the compound that (B) contains alkoxyalkyl, not only do not damage storage stability, brought into play the lithography performance of ISO, and the rheological parameters' change with time of the light sensitivity after the exposure is little, and light sensitivity stability also is excellent.That is, crosslinked on the aromatic rings of hydroxypolyamide during curing by in photosensitive polymer combination, adding (B) compound, can suppress because the thermal decomposition of hydroxypolyamide or the contraction that thermal relaxation causes suppress owing to solidify the contraction of the thickness that causes.Therefore, add the photosensitive polymer combination of (B) compound owing to can reduce coating film thickness, can make the luminous energy of exposure process effectively arrive the film bottom, form ISO.Since have alkoxyalkyl as crosslinkable groups, the excellent storage stability of varnish, and owing to do not have the phenol hydroxyl, do not reduce the dissolution velocity poor (contrast) of exposure section and unexposed section, therefore formed ISO.The details of the reason that the rheological parameters' change with time of the light sensitivity after the exposure is little is indefinite, in addition, do not wish to be subjected to the constraint of particular theory, it is believed that, even at exposure section diazonium naphtoquinone compounds generation chemical change, produce the indene carboxylic acid and form acid condition, the compound that (B) of the present invention contains alkoxyalkyl can not cause the chemical reaction that reduces light sensitivity yet.
The compound that (B) of the present invention contains alkoxyalkyl synthesizes with known method, for example can list: after haloalkyl being added on the compound with aromatic rings, with the alcohol reaction, thereby acquisition contains the method for the compound of alkoxyalkyl; Make have alkyl, the method for aromatic series alkyl alcohol compound that the aromatic redox compound of carboxyl obtains obtains to contain alkoxyalkyl with the alcohol reaction compound; After adding to haloalkyl on the phenolic compound, with the alcohol reaction, then the phenol that contains alkoxyalkyl of gained is carried out the method for acyl group.
Preferred example for the compound that contains alkoxyalkyl shown in the above-mentioned general formula (2), as the compound with an alkoxyalkyl, can list methoxy benzene, ethoxyl methyl benzene, methoxy ethyl benzene, ethoxyl methyl benzene, 2-methoxy toluene, 3-methoxy toluene, 4-methoxy toluene, 2-methoxy biphenyl, 3-methoxy biphenyl, 4-methoxy biphenyl etc., as the compound with two alkoxyalkyls, can list 1, two (methoxy) benzene of 2-, 1, two (methoxy) benzene of 3-, 1, two (methoxy) benzene of 4-, 1, two (ethoxyl methyl) benzene of 2-, 1, two (ethoxyl methyl) benzene of 3-, 1, two (ethoxyl methyl) benzene of 4-, 2,4 '-two (methoxy) biphenyl, 3,4 '-two (methoxy) biphenyl, 4,4 '-two (methoxy) biphenyl, 2,4 '-two (methoxy) diphenyl ether, 3,4 '-two (methoxy) diphenyl ether, 4,4 '-two (methoxy) diphenyl ether, 2,4 '-two (methoxy) diphenyl methane, 3,4 '-two (methoxy) diphenyl methane, 4,4 '-two (methoxy) diphenyl methane, 2,4 '-two (methoxy) diphenyl sulfone, 3,4 '-two (methoxy) diphenyl sulfone, 4,4 '-two (methoxy) diphenyl sulfone, 2,4 '-two (methoxy) diphenyl propane, 3,4 '-two (methoxy) diphenyl propane, 4,4 '-two (methoxy) diphenyl propane, 2,4 '-two (methoxy) diphenyl HFC-236fa, 3,4 '-two (methoxy) diphenyl HFC-236fa, 4,4 '-two (methoxy) diphenyl HFC-236fa etc.; As the compound with the alkoxyalkyl more than three, can list following compound,
[Chemical formula 2 0]
Figure BPA00001259067700221
{ in the formula, L can be the same or different each other, expression methoxy, ethoxyl methyl, propoxyl group methyl, methoxy ethyl, ethoxyethyl group, methoxy-propyl or methoxyl isopropyl.}。
In addition, the viewpoint of the dissolution time (development time) when developing from alkali is considered, contain the compound of alkoxyalkyl as (B) of the present invention, at least a compound that contains alkoxyalkyl that is selected from the group that is comprised of the compound shown in the following general formula (3) is preferred
[Chemical formula 2 1]
Figure BPA00001259067700231
In the formula, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2It is the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, p is 1～5 integer, q is 0～4 integer, (p+q)=5, k is 1 or 2, and (i) during k=1, X is C nH 2nOR 1Or R 2, (ii) during k=2, X is singly-bound or is selected from 2～4 valency organic groups in the group shown in the following general formula (4), wherein, and at C nH 2nOR 1And R 2There are in a plurality of situations n, p, q, R 1And R 2Can be the same or different each other.}。
[Chemical formula 2 2]
Figure BPA00001259067700241
As object lesson, can list methoxy benzene, ethoxyl methyl benzene, methoxy ethyl benzene, ethoxyl methyl benzene, 2-methoxy toluene, 3-methoxy toluene, 4-methoxy toluene, 2-methoxy biphenyl, 3-methoxy biphenyl, 4-methoxy biphenyl, 1, two (methoxy) benzene of 2-, 1, two (methoxy) benzene of 3-, 1, two (methoxy) benzene of 4-, 1, two (ethoxyl methyl) benzene of 2-, 1, two (ethoxyl methyl) benzene of 3-, 1, two (ethoxyl methyl) benzene of 4-, 2,4 '-two (methoxy) biphenyl, 3,4 '-two (methoxy) biphenyl, 4,4 '-two (methoxy) biphenyl, 2,4 '-two (methoxy) diphenyl ether, 3,4 '-two (methoxy) diphenyl ether, 4,4 '-two (methoxy) diphenyl ether, 2,4 '-two (methoxy) diphenyl methane, 3,4 '-two (methoxy) diphenyl methane, 4,4 '-two (methoxy) diphenyl methane, 2,4 '-two (methoxy) diphenyl sulfone, 3,4 '-two (methoxy) diphenyl sulfone, 4,4 '-two (methoxy) diphenyl sulfone, 2,4 '-two (methoxy) diphenyl propane, 3,4 '-two (methoxy) diphenyl propane, 4,4 '-two (methoxy) diphenyl propane, 2,4 '-two (methoxy) diphenyl HFC-236fa, 3,4 '-two (methoxy) diphenyl HFC-236fa, 4,4 '-two (methoxy) diphenyl HFC-236fa etc. and following compound
[Chemical formula 2 3]
Figure BPA00001259067700251
{ in the formula, L can be the same or different each other, expression methoxy, ethoxyl methyl, propoxyl group methyl, methoxy ethyl, ethoxyethyl group, methoxy-propyl or methoxyl isopropyl.}。
In addition, the stable on heating viewpoint of the cross-linked structure that causes from curing considers, contains the compound of alkoxyalkyl as (B) of the present invention, and at least a compound that contains alkoxyalkyl that is selected from the compound shown in the following general formula (5) is preferred,
[Chemical formula 2 4]
In the formula, R 1Be the 1 valency organic group that is selected from the group that is comprised of methyl, ethyl, n-pro-pyl and isopropyl, n is 1～3 integer, and p is 1～5 integer, and k is 1 or 2, and (i) during k=1, X is hydrogen atom or C nH 2nOR 1, (ii) during k=2, X represents singly-bound or is selected from 2～4 valency organic groups in the group shown in the following general formula (6), wherein, and at (C nH 2nOR 1) there are in a plurality of situations n and R 1Can be the same or different each other.}。
[Chemical formula 2 5]
Figure BPA00001259067700262
As object lesson, can list methoxy benzene, ethoxyl methyl benzene, methoxy ethyl benzene, ethoxyl methyl benzene, 2-methoxy toluene, 3-methoxy toluene, 4-methoxy toluene, 2-methoxy biphenyl, 3-methoxy biphenyl, 4-methoxy biphenyl, 1, two (methoxy) benzene of 2-, 1, two (methoxy) benzene of 3-, 1, two (methoxy) benzene of 4-, 1, two (ethoxyl methyl) benzene of 2-, 1, two (ethoxyl methyl) benzene of 3-, 1, two (ethoxyl methyl) benzene of 4-, 2,4 '-two (methoxy) biphenyl, 3,4 '-two (methoxy) biphenyl, 4,4 '-two (methoxy) biphenyl, 2,4 '-two (methoxy) diphenyl ether, 3,4 '-two (methoxy) diphenyl ether, 4,4 '-two (methoxy) diphenyl ether, 2,4 '-two (methoxy) diphenyl methane, 3,4 '-two (methoxy) diphenyl methane, 4,4 '-two (methoxy) diphenyl methane, 2,4 '-two (methoxy) diphenyl sulfone, 3,4 '-two (methoxy) diphenyl sulfone, 4,4 '-two (methoxy) diphenyl sulfone, 2,4 '-two (methoxy) diphenyl propane, 3,4 '-two (methoxy) diphenyl propane, 4,4 '-two (methoxy) diphenyl propane, 2,4 '-two (methoxy) diphenyl HFC-236fa, 3,4 '-two (methoxy) diphenyl HFC-236fa, 4,4 '-two (methoxy) diphenyl HFC-236fa etc. and following compound
[Chemical formula 2 6]
Figure BPA00001259067700271
{ in the formula, L can be the same or different each other, expression methoxy, ethoxyl methyl, propoxyl group methyl, methoxy ethyl, ethoxyethyl group, methoxy-propyl or methoxyl isopropyl.}。
In addition, the viewpoint of the effect that the thickness that is caused by curing from inhibition shrinks is considered, contain the compound of alkoxyalkyl as (B) of the present invention, at least a compound that is selected from the group that is comprised of methoxy biphenyl, two (methoxy) benzene, two (methoxy) biphenyl, two (methoxy) diphenyl ether and two (methoxy) diphenyl methanes is particularly preferred.
In addition, consider that from the viewpoint of the chemical-resistant of cured film at least a compound that is selected from the group that is comprised of three (methoxy) benzene, four (methoxy) benzene, five (methoxy) benzene, six (methoxy) benzene, three (methoxy) trimethoxy-benzenes and four (methoxy) dimethoxy benzene is particularly preferred.
In photosensitive polymer combination of the present invention, residual film ratio and the high viewpoint of light sensitivity are considered during curing when improve forming the cyclisation resin, preferably (B) is selected from least a compound that contains alkoxyalkyl in the group that is comprised of the compound shown in the following general formula (7)
[Chemical formula 2 7]
Figure BPA00001259067700281
In the formula, Z 1Be the substituting group that is selected from the group shown in the following general formula (8), k is 1～4 integer, (i) during k=1, and Z 2C nH 2nOR 1Or R 2, R is methyl or ethyl independently of one another, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the alkyl by hydrogen atom and carbon number 1～4 forms, n is 1～3 integer, (ii) k=2～4 o'clock, Z 2Singly-bound or 2～4 valency organic groups, Z 1There is in a plurality of situations Z 1Can be the same or different,
[Chemical formula 2 8]
Figure BPA00001259067700291
(in the formula, R 3～R 5The organic group of carbon number 1～9 independently of one another, R 6The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, and R 7～R 10The organic group of carbon number 1～12 independently of one another.)。}
The compound that contains alkoxyalkyl can obtain by making to react in suitable solvent corresponding to the phenol that contains alkoxyalkyl shown in the following general formula (14) and isocyanate compound, carboxyl acyl chloride, sulphonic acid anhydride and sulfonic acid chloride, chlorosilane etc.
[Chemical formula 2 9]
Figure BPA00001259067700292
In the formula, k is 1～4 integer, and (i) during k=1, Z 2C nH 2nOR 1Or R 2, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the alkyl by hydrogen atom and carbon number 1～4 forms, n is 1～3 integer, (ii) k=2～4 o'clock, Z 2Expression singly-bound or 2～4 valency organic groups.}。
As containing one of phenolic compound of alkoxyalkyl shown in the general formula (8), can list the phenolic compound that contains alkoxyalkyl shown in the following general formula (15),
[chemical formula 30]
Figure BPA00001259067700301
{ in the formula, R is methyl or ethyl independently of one another, Z 3Expression singly-bound or be selected from substituting group in the group shown in the following general formula (16).}。
[chemical formula 31]
In the middle of these, consider from the viewpoint of the light sensitivity of resin combination, the phenol that contains alkoxyalkyl shown in the preferred following general formula of use (17), further, in the middle of these, from stable on heating viewpoint, most preferably use the phenolic compound that contains alkoxyalkyl shown in the following general formula (18).
[chemical formula 32]
Figure BPA00001259067700311
{ in the formula, R can be the same or different each other, expression methyl or ethyl.}
[chemical formula 33]
Figure BPA00001259067700312
{ in the formula, R can be the same or different each other, expression methyl or ethyl.}
As with the compound of the phenol reaction that contains alkoxyalkyl, can list the compound shown in the following general formula (19):
[chemical formula 34]
Figure BPA00001259067700313
In the formula, R 3～R 5The organic group of carbon number 1～9 independently of one another, R 6The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, and R 7～R 10The organic group of carbon number 1～12 independently of one another.}
Example as the compound shown in the general formula (19), can list acetyl chloride, cyclopropanecarbonyl chloride, ethy succinyl chloride, tert-butyl group acetyl chloride, 3-cyclohexene-1-carboxyl acyl chloride, 2-furans carboxyl acyl chloride, crotonyl chloride, cinnamoyl chloride, methacrylic chloride, acryloyl chloride, the propine acyl chlorides, the butine acyl chlorides, thiophene-2-acetyl chloride, the 2-ethoxy benzoyl chloride, the 2-methoxy benzoyl chloride, the 4-methoxy benzoyl chloride, the trimellitic acid chloride, 3,5,5-trimethyl acetyl chlorine, 2,4, the 6-tri-methyl chloride, chloro-carbonic acid-4-nitrobenzophenone ester, chloro-carbonic acid 9-fluorenyl methyl esters, di-tert-butyl dicarbonate, two dimethyl benzyls, 4-ethylbenzene sulfonic acid chloride, paratoluensulfonyl chloride, benzene sulfonyl chloride, p-dimethylbenzene-2-sulfonic acid chloride, 2-sym-trimethyl benzene base sulfonic acid chloride, 4-propylbenzene sulfonic acid chloride, 4-methoxybenzene sulfonic acid chloride, 4-tert-butyl benzene sulfonic acid chloride, 4-xenyl sulfonic acid chloride, 2,4, the 6-triisopropylphenylsulfonyl chloride, methane sulfonyl chloride, phenyl isocyanate, the methacrylic acid isocyanato ethyl, isocyanic acid 3-isopropenyl-α, the α-dimethylbenzyl ester, isocyanic acid-2-trifluoromethyl phenyl ester, n-butyl isocyanate, isocyanic acid n-octadecane base ester, the isocyanic acid o-toluene ester, Chlorodimethyl silane, trimethyl chlorosilane, the chlorine triethyl silicane, chlorine diisopropyl silane, diethyl isopropyl chloride silane, tert-butyl chloro-silicane, the dimethyl ethyl chlorosilane, dimethyl isopropyl chloride silane, tri isopropyl chlorosilane, the Chlorodimethyl propyl silane, the allyl chloride dimethylsilane, the normal-butyl dimethylchlorosilane, the Chlorodimethyl vinyl silanes, dimethyl-n-octyl chloride silane, chlorine (decyl) dimethylsilane, chlorine (dodecyl) dimethylsilane, (3-cyanopropyl) dimethylchlorosilane, (chloromethyl) dimethylchlorosilane, (bromomethyl) Chlorodimethyl silane etc., wherein, as preferred example, can list trimethyl chlorosilane, paratoluensulfonyl chloride, methacrylic chloride, crotonyl chloride etc.Wherein, from the deliquescent viewpoint organic solvent, methacrylic chloride is most preferred.
The solvent that uses during as the compound shown in the synthetic general formula (7), can list acetone, tetrahydrofuran (THF), gamma-butyrolacton (GBL), METHYLPYRROLIDONE (NMP), DMA (DMAc), dimethyl sulfoxide (DMSO) etc.
In addition, for accelerated reaction when synthesizing this compound, preferably make the alkali compounds coexistences such as pyridine, picoline, trimethylpyridine, lutidines, triethylamine, 4-dimethylaminopyridine.Base catalyst can use separately or with two or more combinations.The consumption of base catalyst is adjusted according to the kind of base catalyst, with respect to 1 mole of phenolic compound that contains alkoxyalkyl as raw material, can in the scope of 0.01～10 equivalent (molar equivalent), select, be generally 0.1～5 equivalent, more preferably about 1～3 equivalent.
Temperature of reaction preferably is controlled between 10 ℃～50 ℃.For carboxyl acyl chloride, compound that the sulfonic acid chloride isoreactivity is high, 10 ℃～30 ℃ is preferred.Reaction time according to the addition of the compound that reacts, catalyzer with kind and different, 1 hour～48 hours is preferred, for carboxyl acyl chloride, compound that the sulfonic acid chloride isoreactivity is high, is preferred about 1 hour～5 hours.
For one of method of removing the alkali compounds that contains in the synthetic like this compound that contains alkoxyalkyl, can list: after precipitating in the poor solvents such as water, again dissolving in the THF equal solvent is with the method for Zeo-karb processing again.During synthetic this compound, using in the halid situation such as carboxyl acyl chloride, the selection according to the solvent of catalyzer makes to salt out outside the reaction system, can reclaim salt by filtering, preferred compositions is processed filtrate with Zeo-karb and anion exchange resins.Concentrated by the solution that evaporation will be processed, be dissolved in the good solvent such as ethyl acetate, recrystallization in the poor solvents such as hexane carries out vacuum drying, can isolate object thus.
The compound that contains alkoxyalkyl that obtains by said method is the compound that contains alkoxyalkyl shown in the following general formula (9),
[chemical formula 35]
Figure BPA00001259067700341
(in the formula, R is methyl or ethyl independently of one another, Z 1To be selected from following general formula (10) independently of one another
[chemical formula 36]
Figure BPA00001259067700342
(in the formula, R 3～R 5The organic group of carbon number 1～9 independently of one another, R 6The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, and R 7～R 10The organic group of carbon number 1～12 independently of one another.) shown in group in substituting group, Z 3Be singly-bound or be selected from following general formula (11)
[chemical formula 37]
Figure BPA00001259067700343
Substituting group in the shown group }.
Wherein, in general formula (9), Z 3Be singly-bound, Z 1Preferred for the compound substituent, that contain alkoxyalkyl in the group that is selected from following general formula (12) expression independently of one another.
[chemical formula 38]
Figure BPA00001259067700351
In the formula, R 3And R 5The organic group of carbon number 1～9 independently of one another, and R 7It is the organic group of carbon number 1～12.}
In addition, from stable on heating viewpoint, in general formula (9), Z 3Be singly-bound, Z 1Preferred for the compound substituent, that contain alkoxyalkyl that is selected from the group shown in the following general formula (13) independently of one another.
[chemical formula 39]
Figure BPA00001259067700352
(B) compound that contains alkoxyalkyl can use separately, also can be use mixing two or more.
With respect to 100 mass parts (A) hydroxypolyamide, the use level that (B) contains the compound of alkoxyalkyl is 0.01～30 mass parts, is preferably 1～20 mass parts.If (B) contain the use level of compound of alkoxyalkyl more than 1 mass parts, residual film ratio ((thickness of the embossing pattern after the curing)/(thickness of the embossing pattern after the development) * 100) after then solidifying is higher, and when 30 mass parts were following, light sensitivity was good.
(C) diazonium naphtoquinone compounds
The diazonium naphtoquinone compounds that uses in the photosensitive polymer combination is the compound with 1,2-benzoquinones, two nitrine structures or 1,2-naphthoquinones, two nitrine structures, according to US Patent specification 2,772, No. 972, the 2nd, 797, No. 213, the 3rd, 669, No. 658 etc. is known material.As preferred example, for example can list following compound,
[chemical formula 40]
Figure BPA00001259067700361
{ in the formula, Q is hydrogen atom or following structural formula
[chemical formula 41]
Figure BPA00001259067700371
Shown naphthoquinones two nitrine sulfonate groups, and whole Q is not hydrogen atom simultaneously.}。
Particularly preferably be following compound in the middle of these,
[chemical formula 42]
Figure BPA00001259067700372
(Q be hydrogen atom or
Figure BPA00001259067700373
Be not hydrogen atom simultaneously).
With respect to 100 mass parts (A) hydroxypolyamide, (C) use level of diazonium naphtoquinone compounds is 1～100 mass parts, is preferably 10～30 mass parts.(C) use level of diazonium naphtoquinone compounds is 1 mass parts when above, and the pattern voltinism of resin is good, on the other hand, is 100 mass parts when following, and the tensile elongation of the film after the curing is good, and the development residue (dregs) of exposure section is few.
In photosensitive polymer combination, can add thermic free-radical generating agent (thermal radical generator).As free-radical generating agent used herein, the compound that produces free radical under heat-treat condition is preferred, as preferred example, can list organic peroxide, for example dicumyl peroxide, organic non-superoxide, for example dimethyl diphenyl butane.
With respect to 100 mass parts (A) hydroxypolyamide, the addition when adding the thermic free-radical generating agent is preferably 0～20 mass parts, more preferably 0.1～10 mass parts.Addition is in 20 mass parts the time, and storage stability is good.
Can add as required in the past phenolic compound, dyestuff, surfactant that the adjuvant as photosensitive polymer combination uses in the photosensitive polymer combination, be used for improving and the bonding agent of the adhesion of substrate, stabilizing agent etc.
About above-mentioned adjuvant, more particularly, phenolic compound can list ballast agent (ballast agent), to cumyl phenol, two amino-phenol, resorcinol etc.In addition, the ballast agent refers in aforementioned diazonium naphtoquinone compounds the phenolic compound that uses as raw material, is the phenolic compound that the part of phenol hydrogen atom is carried out the naphthalene quinone di-azide sulfonic acid ester.As dyestuff, such as listing methyl violet, crystal violet, peacock green etc.
With respect to 100 mass parts (A) hydroxypolyamide, the addition when adding phenolic compound is preferably 0～50 mass parts, more preferably 1～30 mass parts.If addition is in 50 mass parts, then the tensile elongation of the film after the heat curing is good.
In addition, as surfactant, the nonionic that can list polyethylene glycols such as comprising polypropylene glycol or polyoxyethylene lauryl ether or its derivant is surfactant, Fluorad (registered trademark, trade name for example, the production of Sumitomo 3M company), Megafac (registered trademark, trade name, large Japanese ink chemical industrial company produces) or the fluorine such as LUMIFLON (registered trademark, trade name, Asahi Glass company produces) be surfactant; Organosiloxane surfactants such as KP341 (trade name, chemical industrial company of SHIN-ETSU HANTOTAI produce), DBE (trade name, Chisso Corporation produces), GLANOL (trade name, chemical company of common prosperity society produces) for example.
With respect to 100 mass parts (A) hydroxypolyamide, the addition when adding surfactant is preferably 0～10 mass parts, more preferably 0.01～1 mass parts.If addition is in 10 mass parts, then the film after the heat curing has good tensile elongation.By adding this surfactant, the filming of Waffer edge in the time of can making coating more is difficult to cave in.
In addition, as bonding agent, such as listing alkyl imidazoline, butyric acid, alkyl acid, polycarboxylated styrene, polyvinyl methyl ether, tert-butyl group phenolic novolac, epoxy silane, epoxy polymer etc. and various silane coupling agent.
As the concrete preferred embodiment of silane coupling agent, for example can list N-phenyl-3-aminopropyl trialkoxy silane, 3-sulfydryl propyl trialkoxy silane, 2-(trialkoxysilyl ethyl) pyridine, 3-methacryloxypropyl trialkoxy silane, 3-methacryloxypropyl dialkoxy alkyl silane, 3-glycidoxy propyl trialkoxy silane, 3-glycidoxy propyl group dialkoxy alkyl silane, the reactant of 3-aminopropyl trialkoxy silane or 3-aminopropyl dialkoxy alkyl silane and acid anhydrides or acid dianhydride, the amino of 3-aminopropyl trialkoxy silane or 3-aminopropyl dialkoxy alkyl silane is transformed to material that carbamate groups or urea groups form etc.In addition, as alkyl herein, can list methyl, ethyl, butyl etc.; As acid anhydrides, can list maleic anhydride, phthalic anhydride etc.; As acid dianhydride, for example can list pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4, the two O-phthalic acid dianhydrides of 4 '-oxygen etc.; As carbamate groups, can list tert-butoxycarbonyl amino etc.; As urea groups, can list phenyl amino carbonylamino etc.
With respect to 100 mass parts (A) hydroxypolyamide, the addition when adding bonding agent is preferably 0～30 mass parts, more preferably 0.1～10 mass parts.If addition is in 30 mass parts, then the film after the heat curing has good tensile elongation.
Above-mentioned photosensitive polymer combination is dissolved in solvent, form the varnish shape, can be used as photosensitive polymer combination solution and use.
As this solvent, can be used alone or as a mixture METHYLPYRROLIDONE, gamma-butyrolacton (hereinafter referred to as " GBL "), isophorone, N, N-dimethyl acetamide (below be also referred to as " DMAc "), dimethyl-imidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (below be also referred to as " DMDG "), diethylene glycol diethyl ether, the diethylene glycol dibutyl ethers, propylene glycol monomethyl ether, propylene glycol list ethylether, DPGME, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, butyl lactate, methyl isophthalic acid, 3-butylene glycol acetic acid esters, 1,3-BDO-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propyl acid esters etc.In the middle of these solvents, from the little viewpoint of impact on photoresist etc., non-acid amides series solvent is preferred.Instantiation comprises gamma-butyrolacton, ethyl lactate, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol monomethyl ether etc.
With respect to 100 mass parts hydroxypolyamides, the addition of solvent is preferably 50～1000 mass parts.The addition of solvent can be set the viscosity that is suitable for apparatus for coating and coating thickness, and can easily make cured relief pattern, thereby be preferred in above-mentioned scope the time.
The manufacture method of＜cured relief pattern and semiconductor device 〉
Below be described more specifically the method for making cured relief pattern at substrate coating photosensitive polymer combination of the present invention.
(1) forms the operation (the first operation) of the photo-sensitive resin that is consisted of by photosensitive polymer combination at substrate
Rotary coating by using spin coater or the coating machines such as die coater or roll coater with the photosensitive polymer combination solution coat on substrates such as silicon chip, ceramic substrate, aluminium base.Perhaps, use inkjet nozzle or divider, can be coated on the position of regulation.Dry under 50～140 ℃ temperature with baking oven or hot plate, desolventizing (" prebake ").
(2) across the operation (second operation) of mask with active ray exposure or direct irradiation light, electron beam or ion line.
Then, photo-sensitive resin is exposed with active ray across mask, that is, use contact aligner (contact aligner) or ledex (stepper), expose with chemical ray.Perhaps, expose by direct irradiation light, electron beam or ion line.As active ray, can use g ray, h ray, i ray, KrF laser.
(3) developing procedure (the 3rd operation)
As the 3rd operation, with the developer solution stripping or remove exposure section or irradiation section.Then, preferably, by washing with washing fluid, obtain the embossing pattern of expectation.Developing method can be the modes such as spraying, stirring (puddle), dipping, ultrasound wave.Washing fluid can use distilled water, deionized water etc.
The developer solution that is used for the development of the photo-sensitive resin that is made of photosensitive polymer combination is dissolving and the material of removing the alkali-soluble polymkeric substance, must be the alkaline aqueous solution of dissolving alkali cpd.The alkali cpd that dissolves in the alkaline aqueous solution can be any of inorganic alkali compound or organo-alkali compound.
As this inorganic alkali compound, for example can list lithium hydroxide, NaOH, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen phosphate, lithium metasilicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, sal tartari, lithium borate, sodium borate, potassium borate, ammonia.
In addition, as this organo-alkali compound, for example can list tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide trimethyl hydroxyethyl ammonium, methylamine, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyl diethylamide, dimethylethanolamine, monoethanolamine, triethanolamine.
In addition, as required, in above-mentioned alkaline aqueous solution, can add in right amount the water-miscible organic solvents such as methyl alcohol, ethanol, propyl alcohol, ethylene glycol, surfactant, preserving stabilizer, the dissolution inhibitor of resin etc.
(4) operation (the 4th operation) of heating gained embossing pattern
At last, the gained embossing pattern is carried out heat treated, form the thermotolerance cured relief pattern that is consisted of by the resin with polybenzoxazole structure.As heating arrangement, can use baker, hot plate, vertical heater, conveying belt stove, pressure baking oven etc., as heating means, recommendation hot blast, infrared ray, electromagnetic induction heating etc.Temperature is preferably 200～450 ℃, more preferably 250～400 ℃.
Be preferably 15 minutes heat time heating time～8 hours, more preferably 1 hour～4 hours.
Atmosphere is preferably in the inert gases such as nitrogen, argon gas.Semiconductor device can by with cured relief pattern as surface protection film, interlayer dielectric, wiring, makes up to make with the manufacture method of known semiconductor device with diaphragm or have the diaphragm of the device of projection (bump) structure with dielectric film, flip chip device again.
In addition, photosensitive polymer combination of the present invention also can be used for the interlayer dielectric of multilayer circuit, the purposes such as seal coat, soldering-resistance layer or liquid crystal orientation film of flexible copper-clad plate.
Embodiment
Followingly according to reference example, embodiment the present invention is described.The evaluate root of the photosensitive polymer combination among the embodiment is carried out according to following methods.
The evaluation of＜photosensitive polymer combination 〉
(1) patterning evaluating characteristics
With spin coater (LTD. makes for DspinSW-636, DAINIPPON SCREEN MFG.CO.) with the photosensitive polymer combination rotary coating on 5 inches silicon chips, on hot plate, 125 ℃ of 180 seconds of lower prebake, form filming of thickness 9.0 μ m.Use intensification program control type curing oven (Ltd. makes for VF-2000 type, Koyo Thermo Systems Co.), in nitrogen atmosphere, under 320 ℃, this is filmed and carry out thermal treatment (curing) in 1 hour, obtain cured film at silicon chip.The detecting refractive index of thickness optical profile type determining film thickness device (LTD. makes for LAMBDA-ACE VM-1200, DAINIPPON SCREEN MFG.CO.) with 1.65.Thickness before and after solidifying is calculated cure shrinkage (%).
Then, with said method rotary coating photosensitive polymer combination on 5 inches silicon chips, formation is filmed.By the photomask (reticle) with test pattern, use NIKON ledex processed (NSR2005i8A) of the exposure wavelength with i ray (365nm) to change stage by stage exposure, this is filmed expose.Alkaline developer (the AZ300MIF developer that uses AZ Electronic Materials company to make, 2.38 quality % tetramethyl ammonium hydroxide (TMAH) aqueous solution), regulate development time so that the development residual film ratio of unexposed section is 85%, carrying out the oar formula under 23 ℃ condition develops, use pure water rinsing, form positive relief pattern.After this, implement 320 ℃ of curing of 1 hour.The final thickness of the embossing pattern that the coating film thickness of filming of this moment obtains according to implementing 320 ℃ of curing in 1 hour is 7.0 μ m, is set by the cure shrinkage inverse operation.
In addition, the ageing stability of the light sensitivity after the light sensitivity of photosensitive polymer combination, resolution, the exposure and storage stability evaluation as described below.
[light sensitivity (mJ/cm 2)]
Under above-mentioned time of developing, dissolve and remove the minimum exposure amount of the exposure section of filming fully.
[resolution (μ m)]
Minimum under above-mentioned exposure is differentiated pattern dimension.
[ageing stability of the light sensitivity after the exposure]
With said method rotary coating photosensitive polymer combination on 5 inches silicon chips, formation is filmed, and with after the said method exposure, places 24 hours in the toilet on this is filmed.After this, develop with said method, form embossing pattern.The rheological parameters' change with time of the light sensitivity after the exposure of this moment is less than ± 50 (mJ/cm 2) be good, ± 50 (mJ/cm 2) above be bad.
[storage stability evaluation]
Use E type viscosity meter (RE-80E, eastern machine industry (strain) is made) 23 ℃ of lower viscosity of measuring above-mentioned photosensitive polymer combination, then at room temperature placed for 2 weeks, and then measure viscosity, calculate its rate of change (tackify rate).Viscosity changes less than ± 5% be well, for then being bad more than ± 5%.
Synthesizing of＜hydroxypolyamide 〉
[reference example 1]
In the releasable flask of capacity 2L, with 197.8g (0.54mol) 2, two (3-amino-4-the hydroxyphenyl)-HFC-236fa of 2-, 75.9g (0.96mol) pyridine and 692g DMAc at room temperature (25 ℃) mix and dissolve.In addition, with 19.7g (0.12mol) 5-norborene-2, the 3-dicarboxylic anhydride be dissolved among the 88g DMDG and solution be added drop-wise in the above-mentioned flask by tap funnel.Dripping the required time is 40 minutes, and reacting liquid temperature is up to 28 ℃.
After dripping end, be heated to 50 ℃ by hot bath, stirred 18 hours, then, the IR spectrum of assaying reaction liquid confirms to have occurred 1385cm -1And 1772cm -1The characteristic absorption of the imino group at place.
Then, by water-bath reactant liquor is cooled to 8 ℃, drips 142.3g (0.48mol) 4 in addition by tap funnel, 4 '-diphenyl ether dicarboxylic acid dichloride be dissolved among the 398g DMDG and solution.Dripping the required time is 80 minutes, and reacting liquid temperature is 12 ℃ to the maximum.Drip to finish under high-speed stirred, above-mentioned reactant liquor to be added drop-wise in the water of 12L after 3 hours, disperse and separate out polymkeric substance, reclaim, suitably washing, the dehydration final vacuum is dry, obtains hydroxypolyamide (P-1).According to GPC, the weight-average molecular weight of synthetic hydroxypolyamide is 14000 by polystyrene conversion like this.The analysis condition of GPC is as follows.
Post: clear and electrician company makes, trade name Shodex 805/804/803 series connection
Eluant, eluent: 40 ℃ of tetrahydrofurans
Flow velocity: 1.0ml/ minute
Detecting device: clear and electrician makes trade name Shodex RI SE-61
(reference example 2)
In reference example 1, use 125.35g (0.48mol) octahydro-1H-4,7-benzofulvene dicarboxylic acid dichloride replaces 142.3g (0.48mol) 4,4 '-diphenyl ether dicarboxylic acid dichloride, and use 139.45g (0.54mol) 2, two (3-amino-4-the hydroxyphenyl)-propane of 2-replace 197.8g (0.54mol) 2, two (3-amino-4-the hydroxyphenyl)-HFC-236fa of 2-, in addition, fully similarly obtain polybenzoxazole resin precursor (P-2) with reference example 1.The polystyrene conversion weight-average molecular weight of this resin is 22000 (Mw).
(reference example 3)
In the releasable flask of capacity 1L, add 109.9g (0.3mol) 2, two (3-amino-4-the hydroxyphenyl)-HFC-236fa of 2-, 330g tetrahydrofuran (THF), 47.5g (0.6mol) pyridine, at room temperature in this flask, add again pulverous 98.5g (0.6mol) 5-norborene-2, the 3-dicarboxylic anhydride.Under this state, at room temperature stirring reaction is 3 days, then confirms reaction with HPLC, does not detect raw material fully, and product is detected as simple spike, and purity is 99%.This reactant liquor under agitation directly is added drop-wise in the ion exchange water of 1L, leaches after the precipitate, add therein 500mL THF, stirring and dissolving makes this homogeneous solution by having filled the glass column of Zeo-karb, removes residual pyridine.Then, under high-speed stirred, this solution is added drop-wise in the ion exchange water of 3L, product is separated out, after filtering, carry out vacuum drying.
The imidizate of product is confirmed by following method: 1394cm occurs in IR spectrum -1And 1774cm -1Imide characteristic absorption and do not have 1540cm -1And 1650cm -1Near the characteristic absorption of amide group, and in the NMR spectrum, do not have the peak of the proton of acid amides and carboxylic acid.
Then, add 53.7g (0.2mol) 1 in this product of 65.9g (0.1mol), 2-naphthoquinones diazido-4-sulfonic acid chloride, 560g acetone are 20 ℃ of lower stirring and dissolving.In gained solution, the dilution that by the certain speed dropping 21.2g (0.21mol) triethylamine was obtained with the 106.2g acetone diluted through 30 minutes.At this moment, reactant liquor with temperature controls such as ice-water baths in 20～30 ℃ scope.
Drip after the end, further after 20 ℃ of lower stirrings are placed 30 minutes, drop into the aqueous hydrochloric acid solution of 5.6g 36 % by weight concentration quickly, then, cool off reactant liquor with ice-water bath, the solid constituent that suction strainer is separated out.Under agitation dripped the filtrate that obtain this moment through 1 hour in the aqueous hydrochloric acid solution of 5L 0.5 % by weight concentration, object is separated out, suction strainer reclaims again.Gained pie regenerant is disperseed in the 5L ion exchange water again, stirring, washing, filtered and recycled, triplicate should the washing operation.The pie that obtains at last 40 ℃ of lower vacuum drying 24 hours, is obtained diazonium naphtoquinone compounds (Q-1).
(reference example 4)
In the releasable flask of capacity 1L, add 30.6g (0.1mol) 4,4 '-[1-[4-[1-(4-hydroxyphenyl)-1-Methylethyl] phenyl] ethidine] bis-phenol (trade name Tris-P-PA-MF, Honshu chemical industry (strain) production), 67.1g (0.25mol) 1,2-naphthoquinones diazido-4-sulfonic acid chloride, 560g acetone are 20 ℃ of lower stirring and dissolving.In gained solution, the dilution that by the certain speed dropping 26.2g (0.26mol) triethylamine was obtained with the 131.1g acetone diluted through 30 minutes.At this moment, use ice-water bath etc. with the reactant liquor temperature control in 20～30 ℃ scope.
Drip after the end, further placed 30 minutes 20 ℃ of lower stirrings, then drop into the aqueous hydrochloric acid solution of 5.6g 36 % by weight concentration quickly, then, cool off reactant liquor with ice-water bath, the solid constituent that suction strainer is separated out, in the aqueous hydrochloric acid solution of 5L 0.5 % by weight concentration, under agitation dripped the filtrate that obtain this moment through 1 hour, object is separated out, and suction strainer reclaims again.Gained pie regenerant is dispersed in the 5L ion exchange water again, stirring, washing, filtered and recycled, triplicate should the washing operation.The pie that obtains at last obtains diazonium naphtoquinone compounds (Q-2) 40 ℃ of lower vacuum drying 24 hours.
(reference example 5)
Add 235g (1.4mol) 1,3 in being provided with the 5L releasable flask of stirring rod, drying tube, thermometer, 5-trimethoxy-benzene, 156g (5.19mol) acetaldehyde, 532g glacial acetic acid 20 ℃～25 ℃ lower stirrings 2 hours, form pulp-like.In this slurry, drip 2000g be equivalent to 7.41 moles the mixed solution of 30% aqueous solution of hydrogen bromide and acetic acid the time, generate heat to 56 ℃.Along with the carrying out that drips, the color of the solution is changed to yellow, purple by white.Drip after the end,, dissolve fully in the time of 50 minutes 70 ℃ of lower stirrings, when further stirring 3 hours, reactant liquor is changed to brown.After this, be cooled to 20 ℃, in 7860g water, drop into reactant liquor.It is added 9000g chloroform, abstraction reaction thing.In reactant, add 4080g 5% sodium bicarbonate aqueous solution, 600g sodium bicarbonate, wash.After this add 4080g 20% saline solution, further add 600g magnesium sulphate, dewater, filter and the washing chloroform layer, then on one side with solvent heating to 50 ℃, vacuum drying under 8mmHg on one side distills solvent, obtains 1 of 456g brown liquid shape, 3,5-trimethoxy-2,4, the 6-trisbromomethyl benzene.
Then, in the 1L four neck flasks that are provided with stirring rod, nitrogen ingress pipe, thermometer, with 108.28g (0.2435mol) 1,3,5-three (bromomethyl)-2,4,6-trimethoxy methylbenzene is dissolved in the 435g toluene.In gained solution, about 23 ℃, dripped 235.05g (1.217mol) 28% sodium methoxide solution through 8 minutes.After 35 ℃ of lower stirrings 27 hours, further add 46.97g (1.0mol) 28% sodium methoxide solution, stirred 25 hours.This reactant liquor is put in 5 ℃ of cold water of 2176g, further added 1741g toluene, separatory is organic solvent layer and water layer.Add 1306g 20% saline solution, discarded water layer is with this triplicate.In toluene layer, add 200g magnesium sulphate, add 300ml toluene, then filter and wash magnesium sulphate, on one side solvent is heated to 50 ℃, under 10mmHg, carry out vacuum drying on one side, distill toluene solvant, obtain the crude product of the object of 81.9g.Use, is carried out chromatographic column with 3kg silica gel with this crude product and is purified the developing solvent that hexane and ethanol mix with 4: 1 ratio, reclaims main chromatogram product, by 50 ℃ of lower vacuum drying 40 hours, obtain 56g 1,3,5-three (methoxy)-2,4, the 6-trimethoxy-benzene.When confirming reaction by HPLC, do not detect raw material fully, product is detected as simple spike, and purity is 99%.
(reference example 6)
In the capacity 2.0L four neck flasks that are provided with thermometer, drying tube and stirring machine, add 101.7g (0.226 mole) 1,2,4,5-four (bromomethyl) benzene (production of Aldrich company) and 1.5L methyl alcohol at room temperature stir.When further adding 80.9g (1.49 moles) sodium methoxide, temperature rises about 20 ℃.Be immersed in 65 ℃ the oil bath, 65 ℃ of lower stirrings 4 hours, stir finish after, use Rotary Evaporators, distill 500ml methyl alcohol, carry out concentration operation.This concentration of reaction solution is put in the 2L frozen water.In the gained material, add after the 2L toluene, transfer in the separating funnel, extract operation, object is extracted in the toluene layer.In toluene layer, add 50g magnesium sulphate, carry out dehydrating operations, filter out after the magnesium sulphate, use Rotary Evaporators, distill toluene, obtain the crude product of object.Use toluene and ethyl acetate as developing solvent, this crude product is carried out the chromatographic column of 600g silica gel amount and purify.Reclaim major part, again use Rotary Evaporators, distill solvent, obtain 20g 1,2,4, the refined product of 5-four (trimethoxy methyl) benzene.When confirming object with HPLC, raw material does not detect fully, and product is detected as simple spike, and purity is 99%.
(reference example 7)
In the releasable flask of capacity 500ml, drop into 36.2g (0.1mol) 3,3 ', 5,5 '-four (methoxy)-4, and 4 '-dihydroxybiphenyl (trade name TMOM-BP, Honshu chemical industry (strain) is produced, structural formula is as follows), 110g GBL, 19.0g (0.24mol) pyridine, drip 28.1g (0.2mol) chlorobenzoyl chloride.At this moment, reactant liquor in 10～30 ℃ scope, after stirring and reacting 2 hours, is confirmed reaction by HPLC with the ice-water bath temperature control, and the result does not detect raw material fully, and product is detected as simple spike, and purity is 99%.Under stirring this reactant liquor directly is added drop-wise in the 1L ion exchange water, filter out after the precipitate, add again 500ml GBL, stirring and dissolving, allow this homogeneous solution by being filled with the glass column of Zeo-karb and anion exchange resins, remove residual chlorion and pyridine.Then, by this solution is added drop-wise in the ion exchange water of 3L under high-speed stirred, product is separated out, filter, vacuum drying, acquisition contains the compound (C-1, structural formula illustrates following) of alkoxyalkyl.
(reference example 8)
In reference example 7, except using 21.0g (0.2mol) methacrylic chloride replacement 28.1g (0.2mol) chlorobenzoyl chloride, all similarly obtain to contain the compound (C-2, structural formula illustrates following) of alkoxyalkyl with reference example 7.When confirming reaction by HPLC, raw material does not detect fully, and product is detected as simple spike, and purity is 99%.
(reference example 9)
In reference example 7, except using 38.2g (0.2mol) paratoluensulfonyl chloride replacement 28.1g (0.2mol) chlorobenzoyl chloride, all similarly obtain to contain the compound (C-3, structural formula illustrates following) of alkoxyalkyl with reference example 7.When confirming reaction by HPLC, raw material does not detect fully, and product is detected as simple spike, and purity is 97.7%.
(reference example 10)
In reference example 7, except using 30.6g (0.1mol) 3,3 ', 5,5 '-four (methylol)-4,4 '-dihydroxybiphenyl (trade name TML-BP, Honshu chemical industry (strain) is produced, structural formula illustrates following) replacement 36.2g (0.1mol) 3,3 ', 5,5 '-four (methoxy)-4, beyond 4 '-dihydroxybiphenyl, all similarly obtain to contain the compound (C-4, structural formula illustrates following) of methylol with reference example 7.When confirming reaction by HPLC, raw material does not detect fully, and product is detected as simple spike, and purity is 99%.
[chemical formula 43]
Figure BPA00001259067700501
(embodiment 1)
The diazonium naphtoquinone compounds (Q-1) that obtains in the above-mentioned reference example 3 with the hydroxypolyamide (P-1) that obtains in the above-mentioned reference example 1 of 100 mass parts, 20 mass parts, 2 mass parts are as 4 of the compound that contains alkoxyalkyl, 4 '-two (methoxy) biphenyl is dissolved in the 170 mass parts gamma-butyrolactons, then filter preparation photosensitive polymer combination A with 0.2 μ m filtrator.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 2)
The diazonium naphtoquinone compounds (Q-1) that obtains in the above-mentioned reference example 3 with the hydroxypolyamide (P-1) that obtains in the above-mentioned reference example 1 of 100 mass parts, 20 mass parts, 8 mass parts are as 4 of the compound that contains alkoxyalkyl, 4 '-two (methoxy) biphenyl is dissolved in the 170 mass parts gamma-butyrolactons, then filter preparation photosensitive polymer combination B with 0.2 μ m filtrator.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 3)
The diazonium naphtoquinone compounds (Q-1) that obtains in the above-mentioned reference example 3 with the hydroxypolyamide (P-1) that obtains in the above-mentioned reference example 1 of 100 mass parts, 20 mass parts, 20 mass parts are as 4 of the compound that contains alkoxyalkyl, 4 '-two (methoxy) biphenyl is dissolved in the 170 mass parts gamma-butyrolactons, then filter preparation photosensitive polymer combination C with 0.2 μ m filtrator.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 4)
Except use Isosorbide-5-Nitrae-two (methoxy) benzene conduct contains the compound of alkoxyalkyl, similarly to Example 2, preparation photosensitive polymer combination D.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 5)
Except using 4,4 '-two (methoxy) diphenyl ether as containing beyond the compound of alkoxyalkyl, similarly to Example 2, preparation photosensitive polymer combination E.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 6)
Except using 4,4 '-two (methoxy) diphenyl methane as containing beyond the compound of alkoxyalkyl, similarly to Example 2, preparation photosensitive polymer combination F.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 7)
Except the conduct of use 4-methoxy biphenyl contains the compound of alkoxyalkyl, similarly to Example 2, preparation photosensitive polymer combination G.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 8)
The compound that contains alkoxyalkyl (C-1) that obtains in using above-mentioned reference example 7 similarly to Example 2, prepares photosensitive polymer combination H as containing the compound of alkoxyalkyl.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 9)
Use the hydroxypolyamide (P-2) that obtains in the reference example 2 to replace hydroxypolyamide (P-1), use the diazonium naphtoquinone compounds (Q-2) that obtains in the 14 mass parts reference examples 4 to replace 20 mass parts diazonium naphtoquinone compounds (Q-1), in addition, similarly to Example 2, preparation photosensitive polymer combination I.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 10)
Use the hydroxypolyamide (P-2) that obtains in the reference example 2 to replace hydroxypolyamide (P-1), use the diazonium naphtoquinone compounds (Q-2) that obtains in the 14 mass parts reference examples 4 to replace 20 mass parts diazonium naphtoquinone compounds (Q-1), in addition, similarly to Example 4, preparation photosensitive polymer combination J.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 11)
Use the hydroxypolyamide (P-2) that obtains in the reference example 2 to replace hydroxypolyamide (P-1), and with 1,3,5-three (methoxy)-2,4,6-trimethoxy-benzene is the compound that contains alkoxyalkyl, in addition, similarly to Example 2, preparation photosensitive polymer combination K.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 12)
Except using 1,2,4,5-four (methoxy) benzene as containing beyond the compound of alkoxyalkyl, similarly to Example 11, preparation photosensitive polymer combination L.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 13)
The compound that contains alkoxyalkyl (C-2) that obtains in using above-mentioned reference example 8 similarly to Example 11, prepares photosensitive polymer combination M as containing the compound of alkoxyalkyl.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(embodiment 14)
The compound that contains alkoxyalkyl (C-3) that obtains in using above-mentioned reference example 9 similarly to Example 11, prepares photosensitive polymer combination N as containing the compound of alkoxyalkyl.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 1)
Except the Compound D ML-PTBP (Honshu chemical industry (strain) production) (structural formula illustrates following) that uses 8 mass parts to contain methylol replaces containing the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination O.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 2)
Except using 8 mass parts DMOM-PTBP (Honshu chemical industry (strain) production) (structural formula illustrates following) as containing the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination P.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 3)
Except using 8 mass parts 2,6-dihydroxymethyl-paracresol replaces containing beyond the compound of alkoxyalkyl, similarly to Example 1, and preparation photosensitive polymer combination Q.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 4)
Except using 8 mass parts Isosorbide-5-Nitrae-dibenzyl alcohol to replace containing the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination R.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
[chemical formula 44]
Figure BPA00001259067700561
(comparative example 5)
Except the compound TML-BP (Honshu chemical industry (strain) production) (structural formula is as implied above) that uses 8 mass parts to contain methylol replaces containing the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination S.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 6)
Except using 8 mass parts TMOM-BP (Honshu chemical industry (strain) production) (structural formula is as implied above) as containing the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination T.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 7)
The compound that contains methylol (C-4) that obtains in using 8 mass parts reference examples 10 replaces containing the compound of alkoxyalkyl, similarly to Example 1, and preparation photosensitive polymer combination U.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 8)
Except using 8 mass parts dimethoxy-methyl ureas (trade name MX-290, Mitsui Cytec Ltd. produces) as containing beyond the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination V.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 9)
(trade name EPOLIGHT 4000 except the hydrogenated bisphenol A diglycidyl ether that uses 8 mass parts to belong to contain epoxy compounds, common prosperity society chemistry (strain) is produced) replace containing beyond the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination W.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
(comparative example 10)
Except using 8 mass parts benzoxazine compounds (trade name B-a type benzoxazine, four countries change into industry (strain) and produce) to replace containing beyond the compound of alkoxyalkyl, similarly to Example 1, preparation photosensitive polymer combination X.Use the gained photosensitive polymer combination, make embossing pattern by said method at silicon chip, the light sensitivity of evaluate cure shrinkage factor, composition, resolution.Further, the ageing stability by the light sensitivity after the said method evaluation exposure.In addition, by said method, measure the viscosity of composition, estimate storage stability.
The guide look of composition of the photosensitive polymer combination of embodiment 1～14, comparative example 1～10 has been shown in the following table 1, and following table 2 shows evaluation result.
As can be seen from Table 2, photosensitive polymer combination of the present invention has good storage stability, can form ISO, high-resolution embossing pattern, and in addition, the ageing stability of the light sensitivity after the exposure also is excellent.In contrast, can find out that the composition that does not contain the comparative example 1～10 of the compound that contains alkoxyalkyl that satisfies necessary condition of the present invention has can not obtain good light sensitivity, resolution, perhaps stable inferior and so on the rough sledding of composition.
Figure BPA00001259067700591
Utilizability on the industry
Photosensitive polymer combination of the present invention can be aptly as the surface protection film of semiconductor device, interlayer dielectric, again wiring with dielectric film, flip chip device with the interlayer dielectric of diaphragm, the diaphragm with device of projection cube structure, multilayer circuit, the utilizations such as seal coat, soldering-resistance layer and liquid crystal orientation film of flexible copper-clad plate.

Claims (6)

1. a photosensitive polymer combination is characterized in that, comprises:
100 mass parts (A) contain the hydroxypolyamide of structure shown in the following general formula (1),
Figure FSB00000899981400011
In the formula (1), X 14 valency organic groups with carbon atom, X 2, Y 1And Y 2Be the divalent organic group with 2 above carbon atoms independently of one another, l is 2～1000 integer, and m is 0～500 integer, l/ (l+m)＞0.5, and contain X 1And Y 1L dihydroxy diamides unit and contain X 2And Y 2Putting in order of m diamides unit be arbitrarily, wherein, X 1From being selected from 3,3 '-dihydroxybiphenyl amine, 3,3 '-diamido-4,4 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxybiphenyl, 3,3 '-diamido-4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-diamido-3,3 '-dihydroxy-diphenyl sulfone, two-(3-amino-4-hydroxyphenyl) methane, 2,2-pair-(3-amino-4-hydroxyphenyl) propane, 2,2-pair-(3-amino-4-hydroxyphenyl) HFC-236fa, 2,2-pair-(4-amino-3-hydroxyphenyl) HFC-236fa, two (4-amino-3-hydroxyphenyl) methane, 2,2-pair-(4-amino-3-hydroxyphenyl) propane, 4,4 '-diamido-3,3 '-dihydroxy benaophenonel, 3,3 '-diamido-4,4 '-dihydroxy benaophenonel, 4,4 '-diamido-3,3 '-dihydroxydiphenyl ether, 3,3 '-diamido-4,4 '-dihydroxydiphenyl ether, Isosorbide-5-Nitrae-diamido-2, the 5-dihydroxy benzenes, 1,3-diamido-2, the 4-dihydroxy benzenes, remove 4 valency residues of amino and hydroxyl at least a compound in the group that 1,3-diamido-4,6-dihydroxy benzenes form;
0.01 the compound that contains alkoxyalkyl shown in the following general formulas of～30 mass parts (B) (2),
Figure FSB00000899981400021
In the formula (2), k is 1 or 2, and (i) during k=1, X is C nH 2nOR 1Or R 2, R 1It is the 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R2 is the 1 valency organic group that is selected from the group that the alkoxy by the carbamate groups of the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10, carbon number 2～10 and carbon number 1～10 forms, n is 1～3 integer, p is 1～5 integer, q is 0～4 integer, and (p+q)=5, (ii) during k=2, X is the group shown in singly-bound or the following general formula (4), R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2It is the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, p is 1～5 integer, q is 0～4 integer, and (p+q)=5, wherein, at C nH 2nOR 1And R 2There are in a plurality of situations n, p, q, R 1And R 2Can be the same or different each other; And
1～100 mass parts (C) diazonium naphtoquinone compounds,
Figure FSB00000899981400022
2. photosensitive polymer combination according to claim 1, wherein, the compound that (B) contains alkoxyalkyl is with following general formula (3) expression,
In the formula (3), k is 1 or 2, and (i) during k=1, X is C nH 2nOR 1Or R 2, R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2It is the 1 valency organic group that is selected from the group that the alkoxy by the carbamate groups of the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10, carbon number 2～10 and carbon number 1～10 forms, n is 1～3 integer, (ii) during k=2, X is singly-bound or is selected from divalent organic group in the group shown in the following general formula (4), R 1The 1 valency organic group that is selected from the group that is formed by methyl, ethyl, n-pro-pyl and isopropyl, R 2Be the 1 valency organic group that is selected from the group that the carbamate groups by the ester group of the alkyl of hydrogen atom, carbon number 1～4, carbon number 2～10 and carbon number 2～10 forms, n is 1～3 integer, and p is 1～5 integer, q is 0～4 integer, and (p+q)=5, wherein, at C nH 2nOR 1And R 2There are in a plurality of situations n, p, q, R 1And R 2Can be the same or different each other,
Figure FSB00000899981400032
3. photosensitive polymer combination according to claim 1, wherein, the compound that (B) contains alkoxyalkyl is with following general formula (5) expression,
Figure FSB00000899981400041
In the formula (5), R 1Be the 1 valency organic group that is selected from the group that is comprised of methyl, ethyl, n-pro-pyl and isopropyl, n is 1～3 integer, and p is 1～5 integer, and k is 1 or 2, and (i) during k=1, X is hydrogen atom or C nH 2nOR 1, (ii) during k=2, X is singly-bound or is selected from divalent organic group in the group shown in the following general formula (6), wherein, and at C nH 2nOR 1There are in a plurality of situations n and R 1Can be the same or different each other,
4. photosensitive polymer combination according to claim 1, wherein, the compound that (B) contains alkoxyalkyl is selected from the group that is comprised of two (methoxy) benzene, three (methoxy) benzene, four (methoxy) benzene, five (methoxy) benzene, six (methoxy) benzene, three (methoxy) trimethoxy-benzene, methoxy biphenyl, two (methoxy) biphenyl, two (methoxy) diphenyl ether and two (methoxy) diphenyl methanes.
5. the manufacture method of a cured relief pattern, this manufacture method comprises following operation: the operation that forms the photo-sensitive resin that each the described photosensitive polymer combination by claim 1～4 consists of at substrate; Expose with active ray or the operation of direct irradiation light, electron beam or ion line across mask; Developing procedure; And the operation of heating gained embossing pattern.
6. semiconductor device, it has the cured relief pattern layer that obtains by method claimed in claim 5.
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