CN102650830B - Eurymeric anti-corrosion agent composition, corrosion-resisting pattern forming method - Google Patents
Eurymeric anti-corrosion agent composition, corrosion-resisting pattern forming method Download PDFInfo
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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
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Abstract
A kind of eurymeric anti-corrosion agent composition, it applies the discharge nozzle-type coating process of the operation of anti-corrosion agent composition for having by making discharge nozzle and substrate relative movement in the whole applicator surface of substrate, and it is alkali-soluble novolac resin (A) and the compound (C) containing naphthoquinone diazido to be dissolved in the organic solvent (S) of the glycol (S1) containing carbon number more than 6 and is formed.
Description
Technical field
The present invention relates to a kind of eurymeric anti-corrosion agent composition being suitable to discharge nozzle-type coating process and employ the corrosion-resisting pattern forming method of this eurymeric anti-corrosion agent composition.
The application at the Japanese Patent Application 2011-040168 CLAIM OF PRIORITY of Japanese publication, is hereby incorporated its content based on February 25th, 2011.
Background technology
At present, in the liquid crystal display cells manufacture field employing small-size glass substrate, as resist coating method, after using central authorities' dropping, carry out the method (following non-patent literature 1) rotated.
For carrying out, after central authorities' dropping, the coating process rotated, although available good coating uniformity, but, the situation of the large substrate of the square rank of such as 1m, the dosage against corrosion thrown away when rotated and discard is quite a lot of, it addition, produce the problem rupturing or guaranteeing interval time of the substrate caused because of high speed rotating.There is a problem in that: after central authorities' dropping, carry out the rotary speed when coating property in the method rotated depends on rotation and the coating amount of resist, therefore, during the 5th generation substrate (1000mm × 1200mm～about 1280mm × 1400mm) etc. of maximization to be further applied, there is no to obtain the general-purpose motor of the acceleration of needs, as ordered such motor, then component costs increases.
Additionally, even if substrate size or plant bulk maximize, such as apply uniformity ± 3%, interval time 60～70 seconds/etc. requirement performance in working procedure of coating almost unchanged, therefore, the method rotated after central authorities' dropping is difficult to adapt with the requirement applied beyond uniformity.
So carry out the maximization of substrate, also begin to the manufacture of the 10th generation substrate (2880mm × 3130mm) recently, wherein, as the new resist coating method that can apply to the later large substrate of the 4th generation substrate (680mm × 880mm) the most particularly the 5th generation substrate, it is proposed that the resist coating process of discharge nozzle-type.
The resist coating process of discharge nozzle-type be by make discharge nozzle and substrate relatively move and substrate whole applicator surface apply eurymeric anti-corrosion agent composition method, such as, it is proposed that use has multiple nozzle bore and arranges discharge opening or the discharge opening of slit-shaped, the method for the discharge nozzle being banding that can be spued by anti-corrosion agent composition of shape in column.It addition, it is also proposed to spue nozzle-type after the whole applicator surface of substrate applies anti-corrosion agent composition, make this substrate rotate and the method that adjusts thickness.
As the anti-corrosion agent composition for the purpose of being coated on large substrate, disclose containing alkali-soluble novolac resin, containing the compound of naphthoquinone diazido, the organic solvent of propylene glycol monomethyl ether acetate and the eurymeric anti-corrosion agent composition (patent documentation 1) containing surfactant；Containing alkali novolak resin, naphthoquinone two nitrine photosensitive compounds and the anti-corrosion agent composition (patent documentation 2) of the organic solvent comprising benzylalcohol or benzylalcohol derivative.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 2005-107130 publication
[patent documentation 2] Japanese Unexamined Patent Application Publication 2007-531897 publication
[non-patent literature]
[non-patent literature 1] electronic journal (ElectronicJournal) in August, 2002 number, page 121～123.
Summary of the invention
About discharge nozzle-type coating process, developing recently, delivered preferred applying device, result is important topic from now on for the preferably chemical conversion of the anti-corrosion agent composition of described coating process.
It addition, in large substrate, being dried after it applies is used mostly decompression dry device.When using decompression dry device, the face contrary with anti-corrosion agent composition applicator surface of substrate is carried out drying under reduced pressure when by multiple pin multi-point support.Now, there are the following problems: equal, so remaining the vestige of pin on the film after dry behaviour due to the heat conductivity in the part beyond the contact of pin and its.The problem of this pin trace also occurs when the baking of anti-corrosion agent composition.
And, as it has been described above, in large substrate, the requirement of coating property is identical with small-sized substrate, accordingly, it would be desirable to there is no purlin speckle or striated vestige after coating, anti-corrosion agent composition that uniform coating can be formed.
The present invention is the invention completed in view of the foregoing, and its problem is, it is provided that a kind of eurymeric anti-corrosion agent composition that can be preferred for discharge nozzle-type coating process and use have the corrosion-resisting pattern forming method of this eurymeric anti-corrosion agent composition.
In order to solve above-mentioned problem, the present invention uses following composition.
I.e., the 1st aspect of the present invention is a kind of eurymeric anti-corrosion agent composition, it applies the discharge nozzle-type coating process of the operation of anti-corrosion agent composition for having by making discharge nozzle and substrate relatively move in the whole applicator surface of substrate, wherein, alkali-soluble novolac resin (A) and the compound (C) containing naphthoquinone diazido are dissolved in the organic solvent (S) of the glycol (S1) containing carbon number more than 6 and are formed.
The 2nd aspect of the present invention is a kind of corrosion-resisting pattern forming method, and it includes following operation: by making discharge nozzle and supporting mass relatively move and apply the operation of the eurymeric anti-corrosion agent composition of described first method in the whole applicator surface of supporting mass；Described supporting mass is formed the operation of etchant resist；The operation that described etchant resist is exposed；And described etchant resist is carried out alkali development and forms the operation of corrosion-resisting pattern.
In this specification and present claims, as long as no specified otherwise, " alkyl " comprises straight-chain, branched and 1 ring-type valency saturated hydrocarbyl.
As long as no specified otherwise, " alkylidene " comprises straight-chain, branched and the saturated hydrocarbyl of ring-type divalent.Alkyl in alkoxyl is too.
" expose " concept of the full illumination being set as comprising lonizing radiation.
According to the present invention it is possible to provide a kind of eurymeric anti-corrosion agent composition that can be preferred for discharge nozzle-type coating process and use to have the corrosion-resisting pattern forming method of this eurymeric anti-corrosion agent composition.
Detailed description of the invention
" eurymeric anti-corrosion agent composition "
Eurymeric anti-corrosion agent composition as first method of the present invention is (hereinafter referred to as " (A) composition " by alkali-soluble novolac resin (A).) and contain the compound (C) of naphthoquinone diazido (below, it is referred to as " (C) composition ") it is dissolved in the organic solvent (S) of glycol (S1) containing carbon number more than 6 (hereinafter referred to as " (S) composition ".) and formed.
<(A) composition>
In the present invention, (A) composition is alkali-soluble novolac resin, generally can be used alone a kind or is applied in combination two or more alkali-soluble novolac resin used as the base material component of chemically amplified photoresist.
Here, " base material component " refers to the organic compound with film Forming ability, organic compound that molecular weight be more than 500 is preferably used.Being more than 500 by the amount of having divided of this organic compound, film Forming ability improves, it addition, easily form the corrosion-resisting pattern of nanometer level.
As the concrete example of (A) composition, the novolac resin making phenols and aldehydes react under acidic catalyst and to obtain can be enumerated.
As above-mentioned phenols, can enumerate such as: phenol；The cresol classes such as metacresol, paracresol, orthoresol；2,3-xylenols, 2,5-xylenols, 3, the dimethylbenzene phenols such as 5-xylenols, DMP；M-ethylphenol, paraethyl phenol, o-ethyl phenol, 2,3, the induced by alkyl hydroxybenzene such as 5-pseudocuminol, 2,3,5-triethyl group phenol, 4-TBP, 3-tert-butyl phenol, 2-TBP, 2-tert-butyl-4-methyl-Phenol, the 2-tert-butyl group-5-methylphenol；P methoxy phenol, meta-methoxy phenol, to thanatol, m-oxethyl phenol, to alkoxyl phenols such as propoxyl group phenol, propoxyl group phenol；Adjacent isopropenyl phenol, to isopropenyl phenols such as isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2-ethyl-4-isopropenyl phenols；The aryl phenyl classes such as phenylphenol；4, the polyhydroxy phenols etc. such as 4 '-dihydroxybiphenyl, bisphenol-A, resorcinol, hydroquinone, pyrogallol.In these phenols, particularly preferred metacresol, paracresol.
These phenols can be used alone, and maybe can also be applied in combination two or more.Wherein, preferred compositions uses two or more, and most preferred combinations uses metacresol and paracresol.
As above-mentioned aldehydes, such as formaldehyde, paraformaldehyde, three alkane, acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, acrylic aldehyde, crotonaldehyde, hexamethylene aldehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, ethylalbenzene, α-hydrocinnamicaldehyde, beta-phenyl propionic aldehyde, salicylaldhyde, m-hydroxybenzaldehyde, hydroxy benzaldehyde, o-tolualdehyde, a tolyl aldehyde, p-tolyl aldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, cinnamic aldehyde etc. can be enumerated.In these aldehydes, consider from the easy degree obtained, preferably formaldehyde.
These aldehydes can be used alone, or is applied in combination two or more.
As above-mentioned acidic catalyst, such as hydrochloric acid, sulphuric acid, formic acid, oxalic acid, p-methyl benzenesulfonic acid etc., preferably oxalic acid can be enumerated.
(A) composition can be made up of a kind of novolac resin, it is also possible to is made up of two or more novolac resin.Mix especially by by novolac resin of more than two kinds, can suitably adjust the sensitivity of anti-corrosion agent composition.
In the present invention, as (A) composition, the composition of the novolac resin containing (A ') composition the most illustrated below.
[(A ') composition]
In the present invention, (A ') composition be matter average molecular weight (Mw) (utilizing the polystyrene conversion benchmark of gel permeation chromatography) be the novolac resin of 1000～15000, above-mentioned novolac resin be the charge proportion (mol ratio) relative to metacresol and paracresol be metacresol/paracresol=20/80～80/20 mixed phenols formaldehyde is used as the novolac resin that condensing agent synthesizes.Time in (A) composition containing (A ') composition, be suitable to the preparation of highly sensitive anti-corrosion agent composition, improve the residual film in unexposed portion, the most preferably.
In (A ') composition, the charge proportion (mol ratio) of particularly preferred metacresol and paracresol is metacresol/paracresol=20/80～50/50.
In the present invention, for (A) composition, different with the charge proportion of paracresol or Mw for metacresol multiple (A ') composition can be used in mixed way, furthermore it is possible to containing the novolac resin beyond (A ') composition.Wherein, the content ratio of the total of (the A ') composition in (A) composition is preferably more than 50 mass %, more than more preferably 90 mass %, can be 100 mass %.Most preferably 100 mass %.
Additionally, as (A) composition of the present invention, be preferably used by alkali-solubility preferably 25～below 400nm/ second, more preferably above 25nm/ second and 400nm/ second, further preferred 50～the alkali-soluble novolac resin that constitutes of the novolac resin of scope of 400nm/ second.When alkali-solubility is above-mentioned scope, can prepare as the preferred eurymeric anti-corrosion agent composition of discharge nozzle-type coating process.
When particularly alkali-solubility is in the range of 50～400nm/ seconds, available high sensitivity, the residue in exposure portion is few, and contrast is excellent, and the high-resolution under the conditions of low NA and the verticality excellence of Resist profile, the most preferably.
It should be noted that, in the description, " alkali-solubility " refers to: be arranged on supporting mass with the thickness (about 0.5～2.0 μm) of regulation by the resist layer being made up of alkali-soluble novolac resin, this resist layer impregnated in 2.38 mass % Tetramethylammonium hydroxide (hereinafter referred to as TMAH.) aqueous solution (about 23 DEG C), obtain the thickness of this resist layer and become to the time required for 0 μm, utilize the value (nm/ second) that following formula [thickness of alkali-solubility=resist layer/this thickness became to the time required for 0] calculates.The resist layer being made up of alkali-soluble novolac resin is formed by the following method, i.e., such as novolac resin is dissolved in propylene glycol monomethyl ether acetate (PGMEA) and makes the solution of 20 mass % concentration, it is carried out on 3 inch silicon wafer spin coating, the hot plate be set as 110 DEG C carries out 90 seconds heat treated.
Above-mentioned " alkali-solubility " can control by adjusting the kind of Component units constituting (A) composition or the Mw etc. of its ratio, (A) composition.
(A) Mw that composition is overall is preferably more than 1000, more preferably 2000～15000, and more preferably 3000～10000.When this Mw is more than 1000, making this one side of uniform film thickness of etchant resist preferably, the photolithographic characteristics of anti-corrosion agent composition improves.
(A), when composition is made up of novolac resin of more than two kinds, the Mw of respective novolac resin is not particularly limited, overall as (A) composition, preferably prepare in the way of Mw is more than 1000.
<(C) composition>
In the present invention, (C) composition is the compound containing naphthoquinone diazido, for photonasty composition.For (C) composition, the material of photonasty composition as discharge nozzle-type coating process eurymeric anti-corrosion agent composition can be used at present.
Concrete example as (C) composition, can enumerate the most following chemistry formula (II) represent containing phenolic hydroxyl group compound and 1, the esterification reaction product (c1) of 2-naphthoquinone two nitrine sulfoacid compound is (hereinafter referred to as (c1) composition.) as preferred material.
As above-mentioned 1,2-naphthoquinone two nitrine sulfoacid compound, can enumerate 1,2-naphthoquinone two nitrine-5-sulfonyl compound, 1,2-naphthoquinone two nitrine-4-sulfonyl compound etc., preferably 1,2-naphthoquinone two nitrine-5-sulfonyl compound.
The average esterification rate of above-mentioned (c1) composition is preferably 50～70%, more preferably 55～65%.When this average esterification rate is more than 50%, the film after suppression alkali development reduces, residual film ratio raises this most preferably.If this average esterification rate is less than 70%, then storage stability improves.
Although above-mentioned (c1) composition is dirt cheap, but, preparing highly sensitive eurymeric anti-corrosion agent composition, this is the most particularly preferred.
It addition, as (C) composition, in addition to above-mentioned (c1) composition, it is possible to use other naphthoquinone two nitrine carboxylate (c2) is (hereinafter referred to as (c2) composition.).
As (c2) composition; the compound containing phenolic hydroxyl group and 1 that logical formula (III) the most described later represents can be enumerated; 2-naphthoquinone two nitrine sulfoacid compound (preferably 1; 2-naphthoquinone two nitrine-5-sulfonyl compound or 1,2-naphthoquinone two nitrine-4-sulfonyl compound) esterification reaction product.
(C) content ratio of (c2) composition in composition is preferably below 50 mass %, below particularly preferably 25 mass %.
For the content ratio of (C) composition in the eurymeric anti-corrosion agent composition of the present invention, 100 mass parts are measured relative to (A) composition and the total of (B) composition (aftermentioned) coordinated as required, preferably in the range of 15～40 mass parts, more preferably in the range of 18～35 mass parts, further preferably in the range of 18～30 mass parts.(C) when the content ratio of composition is more than 15 mass parts, transferability improves, and easily forms the corrosion-resisting pattern of desired shape.On the other hand, if the content ratio of (C) composition is below 40 mass parts, sensitivity or definition improve, it addition, the generation of the residue after suppression alkali development treatment.
<(S) composition>
The anti-corrosion agent composition of the present invention is dissolved in (S) composition of the glycol (S1) (hereinafter referred to as " (S1) composition ") containing carbon number more than 6 and manufactures.
For (S) composition, in addition to (S1) composition, can be containing the organic solvent (S2) (hereinafter referred to as " (S2) composition ") being not belonging to (S1) composition.
((S1) composition)
In the present invention, (S1) composition is the glycol of carbon number more than 6.
As the glycol of carbon number more than 6, the preferably glycol of carbon number 6～9, specifically enumerate such as hexanediol (2-methyl-2,4-pentanediol), 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,3-hexanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptandiol, 1,7-heptandiol, 1,2-ethohexadiol, 1,8-ethohexadiol, 2,6-dimethyl-3,5-heptandiol etc..
Wherein, as (S1) composition in the present invention, the glycol of further preferred carbon number 6～7, further preferred hexanediol, 1,2-hexanediol or 1,7-heptandiol.
(S1) composition can be used alone or two or more kinds may be used.
For the ratio of (S1) composition in (S) composition, relative to the gross mass of (S) composition, can be 100 mass %, preferably 0.1～40 mass %, more preferably 0.5～20 mass %, more preferably 1～10 mass %.In being set as above-mentioned scope, pin trace remaining when reducing drying under reduced pressure or bakee, also reduces purlin speckle or the striated vestige of film.
((S2) composition)
(S2) composition is not particularly limited, and at present, can suitably select use one kind or two or more for the organic solvent of the eurymeric anti-corrosion agent composition of the nozzle-type coating process that spues.
Wherein, as (S2) composition in the present invention, from screening characteristics excellence, on large-size glass substrate, from the standpoint of the film thickness uniformity excellence of overlay film against corrosion, propylene glycol monomethyl ether acetate (PGMEA) is preferably comprised.
In (S2) composition, PGMEA most preferably uses with separate solvent but it also may and with the solvent beyond PGMEA, such as ethyl lactate, gamma-butyrolacton, glycol monobutyl ether etc. can be enumerated.
When using ethyl lactate, it is being preferably that 0.1～10 times amount, preferably 1～5 coordinate in the range of times amount by quality ratio relative to PGMEA.
During it addition, use gamma-butyrolacton, it is being preferably that 0.01～1 times amount, preferably 0.05～0.5 coordinate in the range of times amount by quality ratio relative to PGMEA.
For the ratio of (S2) composition in (S) composition, relative to the gross mass of (S) composition, preferably 60～99.9 mass %, more preferably 80～99.5 mass %, more preferably 90～99.0 mass %.
In the present invention, (S) composition is preferably used the total ratio of above-mentioned (A) composition in eurymeric anti-corrosion agent composition and (C) composition and aftermentioned (B) composition is set as below 30 mass %, below more preferably 25 mass %, more preferably below 20 mass %.It addition, more than this ratio preferably 5 mass %, more than more preferably 10 mass %.
That is, (S) composition is preferably used the total ratio of above-mentioned (A) composition in eurymeric anti-corrosion agent composition and (C) composition and (B) described later composition is set as below more than 5 mass %, 30 mass %；More than more preferably 5 mass %, below 25 mass %；More preferably more than 10 mass %, below 25 mass %；More than particularly preferably 10 mass %, below 20 mass %.
When this content ratio is above-mentioned scope, in corrosion-resisting pattern is formed, from discharge nozzle, eurymeric anti-corrosion agent composition discharge during coating, be can get good screening characteristics for banding on supporting mass.Even if it addition, rotate after this coating, it is possible to obtain good mobility, therefore, form well this one side of the etchant resist having good uniformity of thickness preferably in yield rate.
<any composition (B) composition>
The eurymeric anti-corrosion agent composition of the present invention preferably with the purposes such as sensitivity raising contain further molecular weight less than 1000 containing phenolic hydroxyl group compound (B) (hereinafter referred to as (B) composition.).
(B) molecular weight of composition is preferably less than 1000,200～1000.
(B), when the molecular weight of composition is less than 1000, it is readily obtained the effect that sensitivity improves.
Particularly use in the field of discharge nozzle-type coating process in liquid crystal cell manufacture etc., handling capacity rise to the biggest problem, it addition, resist consumption easily increases.Therefore, in terms of eurymeric anti-corrosion agent composition, preferably high sensitivity and also cheap, use should (B) composition time, it is possible to achieve less expensive and high-sensitivity.During it addition, use (B) composition, in corrosion-resisting pattern is formed, more securely form surface difficulty deliquescent layer, therefore, when alkali develops, the film decrement of the etchant resist of unexposed portion is few, suppresses by the uneven generation of developing of the difference generation of developing time, thus preferably.
As (B) composition, can suitably use the compound containing phenolic hydroxyl group of the molecular weight less than 1000 utilized in the eurymeric anti-corrosion agent composition of discharge nozzle-type coating process at present.
As the concrete example of (B) composition, such as, from the standpoint of can being effectively improved sensitivity, the compound containing phenolic hydroxyl group that following logical formula (III) represents is enumerated as preferred compound.
(in formula, R1～R8Separately represent hydrogen atom, halogen atom, the alkyl of carbon number 1～6, the alkoxyl of carbon number 1～6 or the cycloalkyl of carbon number 3～6；R9～R11Separately represent hydrogen atom or the alkyl of carbon number 1～6；Q represents hydrogen atom, the alkyl of carbon number 1～6 and R9The residue that the cycloalkyl of the carbon number 3～6 being bonded and formed or following chemistry formula (IV) represent；A, b represent the integer of 1～3；D represents the integer of 0～3, and n represents the integer of 0～3)
(in formula, R12And R13Separately represent hydrogen atom, halogen atom, the alkyl of carbon number 1～6, the alkoxyl of carbon number 1～6 or the cycloalkyl of carbon number 3～6；C represents the integer of 1～3)
These groups can use any one, it is also possible to and use two or more.
In upper formula (III), R1～R8Separately represent hydrogen atom, halogen atom, the alkyl of carbon number 1～6, the alkoxyl of carbon number 1～6 or the cycloalkyl of carbon number 3～6.
R1～R8In, as halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine etc., particularly preferred fluorine atom can be enumerated.
As the alkyl of carbon number 1～6, preferably methyl, ethyl, propyl group, normal-butyl or the tert-butyl group, most preferable.
As the alkoxyl of carbon number 1～6, preferably methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy or tert-butoxy.
As the cycloalkyl of carbon number 3～6, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl can be enumerated.
Wherein, as R1～R8, preferably hydrogen atom or methyl.
R9～R11Separately represent hydrogen atom or the alkyl of carbon number 1～6, preferably hydrogen atom or methyl.
A, b represent the integer of 1～3, most preferably 1.
D represents the integer of 0～3, most preferably 1.
N represents the integer of 0～3, most preferably 0 or 1.
Q represents hydrogen atom, the alkyl of carbon number 1～6 and R9The residue that the cycloalkyl of the carbon number 3～6 being bonded and formed or above-mentioned logical formula (IV) represent, the residue that the most above-mentioned logical formula (IV) represents.
In upper formula (IV), R12And R13Separately represent hydrogen atom, halogen atom, the alkyl of carbon number 1～6, the alkoxyl of carbon number 1～6 or the cycloalkyl of carbon number 3～6, most preferably hydrogen atom.
As R12And R13, can enumerate and R1～R8Same group.
C represents the integer of 1～3, most preferably 1.
In above-mentioned, from the standpoint of sensitivity, residual film ratio especially excellence, the compound containing phenolic hydroxyl group that particularly preferred following chemistry formula (I) or (I ') represent.
In the present invention, (B) composition can be used alone or two or more kinds may be used.
When the eurymeric anti-corrosion agent composition of the present invention contains (B) composition, for the use level of (B) composition, relative to alkali-soluble novolac resin 100 mass parts as (A) composition, preferably 1～25 mass parts, more preferably 5～20 scopes of mass parts.When the content of (B) composition in anti-corrosion agent composition is very few, it is impossible to obtain the raising effect of high-sensitivity, high residual film ratio fully, when it is too much, substrate surface after development easily produces residue, it addition, cost of material also raises, the most preferred.
(any composition (E) composition)
The eurymeric anti-corrosion agent composition of the present invention preferably contains surfactant (E) (hereinafter referred to as " (E) composition ") further with the purpose that is produced as of suppression striated vestige.For the content of (E) composition, in terms of can being effectively prevented the generation of striated vestige, it is generally in the scope of below 900ppm preferably with respect to eurymeric anti-corrosion agent composition.
As (E) composition, it is not particularly limited, such as, can use currently as compound known to resist surfactant one kind or two or more.
As (E) composition, the most fluoro-silicon system surfactant, wherein, the nonionic fluoro-silicon system's surfactant (E-1) that preferably perfluoroalkyl ester group and alkylsiloxane base and ethyleneoxy and propenyloxy group are bonded to.As this surfactant (E-1), such as メ ガ Off ァ Star Network R-08, R-60 (goods name, the ink liquefaction of big Japan is learned) industry society system can be enumerated) etc..
Additionally; further preferably Oil repellent is 10～25 mass % and surfactant component (E-2) that silicone content is 3～10 mass %; such as X-70-090, X-70-091, X-70-092, X-70-093 (goods name can be enumerated; chemical industry society of SHIN-ETSU HANTOTAI system) etc.; particularly X-70-093, even if resist dripping quantity is a small amount of, the effect that suppression striated vestige or uneven drying occur is the highest; therefore, more preferably.
And, it is also preferred that have polyester modification polydialkysiloxane base system surfactant (E-3) of specific siloxy group skeleton, such as BYK-310, BYK-315, (goods can be enumerated, Bi Ke chemistry society system) etc., particularly BYK-310, can preferably suppress purlin speckle or dropping trace and the generation of striped speckle (striated vestige), the most more preferably.
Total metering of the surfactant of these (E-1)～(E-3) preferably comprises more than 50 mass % in (E) composition, and its ratio can be 100 mass %.
Concrete example as the surfactant beyond above-mentioned (E-1)～(E-3), the surfactant for preventing striped can be enumerated, such as Off ロ ラ mono-De FC-430, FC431 (goods name, Sumitomo 3M society system), the fluorine system surfactant such as エ Off ト Star プ EF122A, EF122B, EF122C, EF126 (goods name, ト mono-ケ system プ ロ ダ クツ society system).
(E) as long as composition meets Oil repellent and the silicone content of above-mentioned scope, just it is not particularly limited, as preferred concrete example, nonionic fluorine silicon system surfactant that can enumerate that perfluoroalkyl and alkylsiloxane base and alkylidene epoxide as trade name X-70-090, X-70-091, X-70-092, X-70-093 (being chemical industry society of SHIN-ETSU HANTOTAI system) be bonded to etc..Concrete example is Oil repellent 21 mass %, silicone content 7 mass % listed herein.
Wherein, even if particularly X-70-093 resist dripping quantity is a small amount of, the effect that suppression striated vestige or uneven drying occur is the highest, the most more preferably.
For the use level of (E) composition, in order to effectively and excellent in efficiency prevent the generation of striated vestige in discharge nozzle-type coating process, relative to the removing organic solvent (S) in anti-corrosion agent composition and the solid constituent of (E) composition, it is preferably set to 0.001～1 mass %, more preferably 0.01～0.5 scope of mass %.
<other composition>
In the present compositions, the various additives such as preserving stabilizer can be used in the range of the purpose of the present invention further not damaging.
For example, it is possible to suitably containing the UV absorbent for preventing halation.As UV absorbent, such as 2 can be enumerated, 2 ', 4,4 '-tetrahydroxybenzophenone, 4-dimethylamino-2 ', 4 '-dihydroxy benaophenonel, 5-amino-3-methyl isophthalic acid-phenyl-4-(4-hydroxyphenyl azo) pyrazoles, 4-dimethylamino-4 '-hydroxyazobenzene, 4-diethylamino-4 '-ethyoxyl diphenyl diimide, 4-DEAB, curcumin etc..
Furthermore it is possible to suitably improve agent (G) ((G) composition) containing the adaptation for making the adaptation of layer and its lower floor being made up of anti-corrosion agent composition improve.Agent is improved as adaptation, preferably 2-(2-hydroxyethyl) pyridine, by making it suitably contain in anti-corrosion agent composition, when can form corrosion-resisting pattern on the metal films such as such as Cr film, the adaptation of layer and the metal film being made up of anti-corrosion agent composition is made to be effectively improved.
When improving agent containing adaptation, when its use level is too much, the rheological parameters' change with time of anti-corrosion agent composition tends to deterioration, when it is very few, it is impossible to obtains adaptation fully and improves effect.Therefore, adaptation improves the use level of agent is in the range of 0.1～10 mass % preferably with respect to total solid composition.
As described above, the eurymeric anti-corrosion agent composition of the present invention is suitable to the coating process of discharge nozzle mode, it is possible to prevent the purlin speckle when anti-corrosion agent composition discharge is coated on substrate by discharge nozzle for banding or the generation of striated vestige, and the generation of pin trace when this film is dried or bakees by minimizing.
The reason obtaining the effect above is unclear, but be considered because, (S1) composition is contained by the eurymeric anti-corrosion agent composition of the present invention, can make the volatility reduction of (S) composition of eurymeric anti-corrosion agent composition, and by the drying process of this film or the evaporation rate homogenization that bakees (S) composition in operation.
In LCD manufacture field, compared with the silicon wafer used in semiconductor element manufacture field, generally use large-scale substrate (such as 360mm × more than 460mm), therefore, applicable discharge nozzle-type coating process.It addition, the substrate surface manufactured at LCD exists the most small concavo-convex, it addition, the deformation etc. that there is also substrate self be coated with the state of the substrate surface of anti-corrosion agent composition LCD manufacture with and semiconductor element manufacture in terms of difference.Therefore, LCD manufactures anti-corrosion agent composition and the anti-corrosion agent composition of semiconductor element manufacture are different technically.
According to eurymeric anti-corrosion agent composition of the present invention, excellent to the wetting quality on supporting mass.For described effect, the supporting mass forming etchant resist is large glass side's substrate that LCD manufactures, contain the supporting mass with the layer (surface layer) that molybdenum is main composition for being formed with molybdenum layer or Mo alloy etc. on the surface of substrate, all can effectively obtain.
Therefore, the eurymeric anti-corrosion agent composition of the present invention can be preferably used as using the liquid crystal cell manufacture of discharge nozzle-type coating process to use.
The anti-corrosion agent composition of the present invention is also suitably for final required thickness coating anti-corrosion agent composition and carrying out the method (non-rotating method) rotated in the whole applicator surface of substrate with discharge nozzle-type coating process.It addition, be also suitably in the whole applicator surface of substrate applying after anti-corrosion agent composition, make substrate rotate and carry out the method for adjustment of thickness.The method being particularly suitable for the latter, can suppress resist coating amount, and prevent postrotational striated vestige, therefore, it can contribute to the minimizing of resist consumption, yield rate raising, cost reduction.
" forming method of corrosion-resisting pattern "
The forming method of the corrosion-resisting pattern of the 2nd aspect of the present invention has the operation using discharge nozzle-type coating process to be coated on substrate by the eurymeric anti-corrosion agent composition of the invention described above.
This working procedure of coating can utilize to possess has the device of the facility making discharge nozzle and substrate relatively move to carry out.For discharge nozzle, as long as can be constituted in the mode that the eurymeric anti-corrosion agent composition spued from here applies as banding on substrate, it is not particularly limited, the discharge nozzle such as with the discharge opening that multiple nozzle bore arranges shape in column can be used, or there is the discharge nozzle of the discharge opening of slit-shaped.As the applying device with this working procedure of coating, it is known to TR28000S, TR45000S, TR63000S, TR70000S, TR90000S, TR117000S, TR130000S of non-rotatable manner (are goods name；Tokyo answers chemical industry (strain) to make) etc..
It addition, above-mentioned working procedure of coating can also use after utilizing discharge nozzle-type coating process to apply eurymeric anti-corrosion agent composition on substrate, make the method that substrate rotates and relatively unfertile land adjusts thickness.As the applying device with this working procedure of coating, it is known to SK-1100G (the goods name of slit & rotation mode；Big Japan SCREEN manufactures (strain) system), utilize CL1200 (the goods name of the scanning coating+rotation mode of MMN (many micro-nozzles)；TEL's (strain) make), coating & rotation mode TR63000F (goods name；Tokyo answers chemical industry (strain) to make) etc..
Being used for after so applying eurymeric anti-corrosion agent composition in the whole applicator surface of substrate forms the operation of etchant resist and can suitably use well-known method for forming the operation of corrosion-resisting pattern.
Such as, the substrate being coated with anti-corrosion agent composition is thermally dried (prebake) under about 100～140 DEG C, forms overlay film against corrosion, thereafter, carries out selecting exposure via desired mask pattern to overlay film against corrosion.Wavelength during exposure can be preferably used ghi line (g line, h line and i line) or i line, uses applicable light source respectively.
Thereafter, to select exposure after overlay film against corrosion, use be made up of alkaline aqueous solution developer solution, such as 1～10 mass % Tetramethylammonium hydroxide (TMAH) aqueous solution carry out development treatment.
As the method making developer solution contact with overlay film against corrosion, it is possible to use the method that such as hydraulically full up to another end from substrate end method or the dropping nozzle of the developer solution from the top of the immediate vicinity being arranged on substrate make developer solution spread all on the whole surface of substrate.
Then, stand about 50～60 seconds and after developing, by carrying out the flushing operation that the flushing liquors such as developer solution pure water by remaining in corrosion-resisting pattern surface wash out, available corrosion-resisting pattern.
According to the forming method of this corrosion-resisting pattern, owing to using discharge nozzle-type coating process, therefore, even if substrate size, plant bulk maximize, it is also possible to do not make coating uniformity or interval time deteriorate, and form overlay film against corrosion on substrate.
And, the anti-corrosion agent composition of use is suitable for discharge nozzle mode, can prevent the striated vestige of overlay film against corrosion, the generation of purlin speckle or the generation of pin trace.When particularly rotating after being coated, resist coating amount can be suppressed, and prevent the generation of striated vestige, therefore, it can contribute to the reduction of manufacturing cost.
[embodiment]
Below, utilize embodiment that the present invention is described in further detail, but the present invention is not limited by these examples.
[embodiment 1～7, comparative example 1～5]
Each composition shown in table 1 is mixed and dissolves, the anti-corrosion agent composition of preparation eurymeric.
[table 1]
Each breviary symbol in table 1 has following meaning.It addition, the numerical value in [] is use level (mass parts).
(A)-1: with formaldehyde as condensing agent, use Catalyzed by Oxalic Acid agent, conventional method is utilized to make the mixed phenols of metacresol/paracresol=40/60 (raw materials components mole ratio) carry out condensation reaction, the novolac resin of the Mw=5000 obtained novolac resin Water-Methanol Mixtures enforcement respectively process obtained.
(B)-1: following compound (B)-1.
(C)-1: following compound (C)-1.
(E)-1:BYK-310 (trade name, Bi Ke chemistry society system).
(G)-1:2-(2-hydroxyethyl) pyridine.
(S)-11: hexanediol.
(S)-12:1,2-hexanediol.
(S)-13:1,7-heptandiol.
(S)-14: benzylalcohol.
(S)-15:1,4-butanediol.
(8)-16:1,2-butadiene.
(S)-17:1,5-pentanediol.
(S)-18: propylene glycol.
(S)-2:PGMEA.
Sample is made by being used the membrane filter of aperture 0.2 μm to carry out filtering by eurymeric anti-corrosion agent composition obtained above, use this sample, method shown below is utilized to form etchant resist, the evaluation of pin trace when carrying out the evaluation of striated vestige, the evaluation of purlin speckle, drying under reduced pressure respectively and the evaluation of pin trace when bakeing.
<formation of etchant resist>
Use has the non-rotating application pattern applying device such as decompression dry device and heat treatment apparatus (chemical industry society system, goods name TR45000S are answered in Tokyo), in the glass substrate (680 × 880mm) being formed with Cr film upper coating embodiment 1～7 and the positive light anti-etching agent composition of comparative example 1～5, thereafter, under the reduced pressure of 60Pa, carry out drying under reduced pressure (drying under reduced pressure operation).Then, the temperature of hot plate is set as 110 DEG C, utilizes the proximity at the interval vacating about 2mm to bakee and carry out 60 seconds the 1st time and be dried, on hot plate, directly implement 80 seconds be dried for the 2nd time, form the etchant resist (baking operation) of thickness 1.5 μm.
[purlin speckle, the evaluation of striated vestige]
The surface of the etchant resist formed is observed under sodium vapor lamp, carries out purlin speckle or the evaluation of striated vestige (vertical stripe) according to following benchmark respectively.The results are shown in table 2.
5: do not see purlin speckle or striated vestige.
4: when carefully observing, there are purlin speckle or striated vestige.
3: have purlin speckle or striated vestige.
2: purlin speckle or striated vestige are in the degree can seen at a glance.
1: purlin speckle or striated vestige are the denseest.
[evaluation of pin trace]
The surface of the etchant resist after drying under reduced pressure (VCD) operation or after baking operation is observed under sodium vapor lamp, carries out the evaluation of pin trace according to following benchmark respectively.The results are shown in table 2.
5: do not see pin trace.
4: when examining, there is pin trace.
3: have pin trace.
2: pin trace is in the degree can seen at a glance.
1: pin trace is the denseest.
[table 2]
| Purlin speckle | Striated vestige | VCD pin trace | Bakee pin trace | |
| Embodiment 1 | 5 | 5 | 5 | 5 |
| Embodiment 2 | 5 | 5 | 5 | 5 |
| Embodiment 3 | 5 | 5 | 5 | 5 |
| Embodiment 4 | 5 | 5 | 5 | 5 |
| Embodiment 5 | 5 | 5 | 5 | 5 |
| Embodiment 6 | 5 | 5 | 5 | 5 |
| Embodiment 7 | 5 | 5 | 5 | 5 |
| Comparative example 1 | 3 | 3 | 3 | 3 |
| Comparative example 2 | 3 | 2 | 3 | 3 |
| Comparative example 3 | 2 | 2 | 2 | 3 |
| Comparative example 4 | 3 | 2 | 3 | 3 |
| Comparative example 5 | 2 | 2 | 2 | 3 |
By the above results it has been confirmed that the anti-corrosion agent composition of embodiments of the invention 1～7 is compared with the anti-corrosion agent composition of comparative example 1～5, decrease purlin speckle, striated vestige and the generation of pin trace.
Claims (5)
1. an eurymeric anti-corrosion agent composition, it applies the discharge nozzle-type coating process of the operation of anti-corrosion agent composition for having by making discharge nozzle and substrate relative movement in the whole applicator surface of substrate,
It is by alkali-soluble novolac resin A and to be dissolved in the glycol S1 containing carbon number more than 6 and the organic solvent S of solvent S2 with propylene glycol monomethyl ether acetate containing the compound C of naphthoquinone diazido and formed,
Relative to the gross mass of described organic solvent S, the ratio of the glycol S1 of described carbon number more than 6 is 0.1 mass %～10 mass %.
Eurymeric anti-corrosion agent composition the most according to claim 1, wherein, the glycol S1 of described carbon number more than 6 is the glycol of carbon number 6 or 7.
Eurymeric anti-corrosion agent composition the most according to claim 1, it is possibly together with the compound B containing phenolic hydroxyl group that molecular weight is less than 1000.
Eurymeric anti-corrosion agent composition the most according to claim 1, it is possibly together with surfactant E.
5. a corrosion-resisting pattern forming method, it includes following operation:
The operation of the eurymeric anti-corrosion agent composition according to any one of Claims 1 to 4 is applied in the whole applicator surface of supporting mass by making discharge nozzle and supporting mass relative movement；
Described supporting mass is formed the operation of etchant resist；
The operation that described etchant resist is exposed；And
The development of described etchant resist alkali is formed the operation of corrosion-resisting pattern.
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