CN101713913A - A photomask board and photomask - Google Patents

A photomask board and photomask Download PDF

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Publication number
CN101713913A
CN101713913A CN200910164560A CN200910164560A CN101713913A CN 101713913 A CN101713913 A CN 101713913A CN 200910164560 A CN200910164560 A CN 200910164560A CN 200910164560 A CN200910164560 A CN 200910164560A CN 101713913 A CN101713913 A CN 101713913A
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photomask
compound
photomask board
composite layer
photosensitive composite
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松本洋介
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Fujifilm Corp
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Fujifilm Corp
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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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
    • G03F1/24—Reflection masks; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/36—Masks having proximity correction features; Preparation thereof, e.g. optical proximity correction [OPC] design processes
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/56—Organic absorbers, e.g. of photo-resists
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention provides a photomask board and photomask, wherein the photomask board is provided with a photosensitive composition layer on a cardinal plate; the photosensitive composition layer comprises (A) at least one optical whitener as shown in the following (I-1) to (I-3) formula, (B) initiator of polymerization, (C) compound with ethylene unsaturated linkage, (D) adhesive polymer and (E) lightproof material. The compound shown in the following (I-1) to (I-3) formula can be replaced by alkyl, aromatic radical and alkoxyl group.

Description

Photomask board and photomask thereof
Technical field
The present invention relates to a kind of photomask board (photomask blanks) and photomask.More particularly relate to a kind ofly can make the photomask board of photomask and the photomask that obtains thus thereof, this photomask can be used for flat pannel display such as PDP, FED, LCD, the CRT lithoprinting operation with fields such as shadow mask, printed circuit board (PCB), semiconductors.
Background technology
As can be used for flat pannel display, CRT photomask, the well-known Em mask (emulsion mask) that the Cr mask that is provided with metallic chromium layer (Cr layer) is arranged, be provided with silver halide emulsion layer with the lithoprinting operation in fields such as shadow mask, printed circuit board (PCB), semiconductor (as can compile with reference to the education literal arts, " Off オ ト Off ア Block リ ケ one シ ヨ Application (photo-fabrication) ", the distribution of Japanese photo-fabrication association, 67～80 pages, in June, 1992.)。
The chromium mask is to form the chromium layer with sputtering method on transparency carriers such as quartz or glass, be coated with resist layer then thereon, by HeCd laser (442nm) etc. expose, alkaline aqueous solution etc. develop carry out that the resist layer pattern forms, peeling off of the etch of chromium and resist layer make.Owing to can revise defectives such as pinprick, so the chromium mask has high resolving power, high-durability (mar resistance), the good advantage of high detergency.On the other hand, chromium mask fabrication complex procedures, thereby price height exist in the manufacturing process in addition because of carrying out the environmental problems such as liquid waste processing that the chromium etch causes.
The Em mask is that silver halide emulsion layer (photosensitive layer) is arranged on the transparency carriers such as quartz or glass, makes by exposures such as YAG laser, development, fixing processing.The used silver emulsion of Em mask fabrication is to the light sensitivity height of light, so exposure energy can very little (～0.1mJ/cm 2), be to environment gentleness, inexpensive photomask board in addition.On the other hand, because the Em mask uses silver halide as photosensitive material, so resolution not too high (about 3 μ m), be not suitable for making the pattern of very fine, in addition, because photosensitive layer is a gelatin film, thereby poor durability.In addition, the Em mask defectiveness shortcoming that is difficult to revise also.
Photomask as other type, known also have the photomask that uses photomask board with following photosensitive layer to make, above-mentioned photographic layer contain black material such as black pigment, can by near ultraviolet ray or visible light formation image (with reference to the spy open the 2005-283914 communique, the spy opens the 2001-343734 communique).The photosensitive layer that this photomask board has, because the near ultraviolet of being shone during to the making photomask or the absorbance of visible region are little, thereby light sensitivity height, the absorption characteristic of the light of the ultraviolet region that is shone when using owing to photomask on the other hand is good, so, can obtain the good photomask of resolution by the exposure imaging of photosensitive layer.In addition, the characteristics of this photomask are metal film needn't be set, owing to be the relief painting picture, thereby can carry out defect correction easily, and the equilibrium of light sensitivity or resolution etc. is good, and low price is little to the load of environment.
Yet the photomask board that uses photosensitive layer to contain black material is made under the situation of photomask, because black material has absorbed exposure light fully, has near the problem that is difficult to solidify the substrate when forming image by exposure.For the ISOization of photomask board,,, therefore taked on photosensitive layer, to be provided with the method for oxygen barrier layers because the resistance of airborne oxygen party reduces light sensitivity greatly though the optical free radical polymerization system can have high light sensitivity.But if the oxygen block is too high, the mist (fog) that the dark polyreaction when then being easy to generate by preservation causes makes the long preservation variation.In addition clearly when contained black material dense, exposure light can only arrive the photosensitive layer near surface, if the oxygen block is too high, then have only the photosensitive layer surface portion to be cured, almost does not solidify in darker thus zone, become eaves shape, the problem of the rectilinearity variation of resolution, image border part so exist the deep layer of photosensitive layer when developing to be cut out.In addition, the spy opens the 2004-117669 communique and has delivered in the cloudy type original edition of lithographic printing plate of photo-polymerization type field, and the oxygen permeability by the control oxygen barrier layers improves operability such as safe light appropriateness etc.
In addition, as the problem that has for the photomask board of laser scanning exposure, be for laser radiation part and illuminated portion not, how can enlarge the on-off of the image that forms, i.e. the problem of the opposition of ISO and storage stability.
About laser, use InGaN class material in recent years, semiconductor laser that can continuous shaking in 350nm to 450nm scope enters the practical stage.Use the scan exposure system of such short wavelength light source,, therefore have sufficient output, and have the strong point that to construct economic system because semiconductor laser structurally can cheaply be made.Use the scan laser system of short wavelength light source, compare with the FD-YAG laser (532nm) or Ar laser (488nm) system that use in the past, can use under brighter safe light can operation, have photosensitive photosensitive material in short wavelength range.
For Photocurable composition,, use the sensitizing coloring matter that has the absorption region in this wavelength coverage in order all to have corresponding photonasty in various Wavelength of Laser scopes.
The for example special 2003-295426 communique of opening has been delivered to use and has been contained the laser diode lithographic plate photopolymer version of the composition of optical whitening agent as sensitizing coloring matter.
So far, also do not provide a kind of photomask board that satisfies ISO, storage stability, the linear photosensitive composite of resolution and image border simultaneously that comprises, present situation is to seek a kind of new technology that did not in the past have.
Summary of the invention
The present invention will reach following purpose in view of above-mentioned technical matters in the past.
Promptly, even the object of the present invention is to provide a kind of light screening material that contains in a large number also can solidify with ISO by exposure, and the photomask board that storage stability is good, and make of this photomask board, can form high-definition picture, the photomask that the rectilinearity of image border part is high.
Solution to the problems described above is as described below.
＜1〉have the photomask board of photosensitive composite layer on a kind of substrate, this photosensitive composite layer contains compound that at least a optical whitening agent shown in (A) following formula (I-1)～(I-15), (B) polymerization initiator, (C) have the ethene unsaturated link, (D) binder polymer and (E) light screening material.
[changing 1]
Figure G200910164560XD0000031
[changing 2]
X represents the divalent concatenating group selected in the formula from structure shown below.* in the following radicals represent with formula (I-6) and formula (I-13) in the binding site of heterocycle.
[changing 4]
Figure G200910164560XD0000042
Compound shown in the formula (I-1)～(I-15) can have substituting group, also can not have substituting group.At this; as the substituting group that can import, can enumerate from alkyl, aryl, alkoxy, alkyl-carbonyl, alkoxy carbonyl, acyloxy, carboxyl, itrile group, amino, hydroxyl, alkyl sulphonyl, amino-sulfonyl and halogen atom, select at least a.This substituting group can also be substituted again.
＜2〉above-mentioned＜1〉described photomask board; wherein, the substituting group of above-mentioned (A) optical whitening agent is at least a for what select from alkyl, aryl, alkoxy, alkyl-carbonyl, alkoxy carbonyl, acyloxy, carboxyl, itrile group, amino, hydroxyl, alkyl sulphonyl, amino-sulfonyl and halogen atom.
＜3〉above-mentioned＜1〉described photomask board, wherein, the molar absorptivity (ε) of above-mentioned (A) optical whitening agent is more than 1000.
＜4〉above-mentioned＜1〉described photomask board, wherein, the molecular weight of above-mentioned (A) optical whitening agent is more than 200 below 2000.
＜5〉above-mentioned＜1〉described photomask board, wherein, the content of above-mentioned (A) optical whitening agent is 0.1～10 quality % in all solids composition of photosensitive composite layer.
＜6〉above-mentioned＜1〉described photomask board, wherein, the oxygen permeability that also has on the above-mentioned photosensitive composite layer under 25 ℃ is 50ml/m 2The above 500ml/m of dayatm 2The oxygen barrier layers that dayatm is following.
＜7〉above-mentioned＜6〉described photomask board, wherein, above-mentioned oxygen barrier layers contains water-soluble high-molecular compound.
＜8〉above-mentioned＜6〉described photomask board, wherein, the thickness of above-mentioned oxygen barrier layers is below the above 1.5 μ m of 0.05 μ m.
＜9〉above-mentioned＜1 〉～＜8 any one described photomask board, wherein, aforesaid substrate is the following clear glass of the above 20mm of thick 0.1mm.
＜10〉above-mentioned＜1 〉～＜9 any one described photomask board, wherein, at least a polymerization initiator of above-mentioned (B) polymerization initiator for from hexa-aryl bi-imidazole compound, metallocene compound, triaizine compounds, oxime ester compound and organic borate, selecting.
＜11〉above-mentioned＜1 〉～＜10 any one described photomask board, wherein, the content of above-mentioned (B) polymerization initiator in the photosensitive composite layer is 0.1～20 mass parts with respect to all solids composition 100 mass parts that constitute the photosensitive composite layer.
＜12〉above-mentioned＜1 〉～＜11 any one described photomask board, wherein, the molecular weight of above-mentioned (D) binder polymer counts 5,000～300 with weight-average molecular weight, 000.
＜13〉above-mentioned＜1 〉～＜12 any one described photomask board, wherein, the content of above-mentioned (E) light screening material is 10 quality %～50 quality % in all solids composition of photosensitive composite layer.
＜14〉a kind of photomask, it has above-mentioned＜1 〉～＜13 the photosensitive composite tomographic image that any one described photomask board the had exposure back light shield layer that develops and form.
＜15〉above-mentioned＜14〉described photomask, wherein, utilize the following light of the above 450nm of 350nm to carry out above-mentioned exposure.
＜16〉above-mentioned＜14〉or＜15〉described photomask, wherein, the live width of line in the above-mentioned light shield layer and gap (L/S) is below the above 20 μ m of 0.1 μ m.
ISO that photomask board of the present invention is brought into play and good storage stability are to come from the photosensitive composite layer to contain the optical whitening agent (sensitizing coloring matter) shown in the general formula (I-1)～(I-15) as neccessary composition.Its mechanism of action is still indeterminate, now is presumed as follows.
At first, give the essential factor of ISOization, be speculated as the optical whitening agent shown in the general formula (I-1)～(I-15) that uses as this sensitizing coloring matter and the reaction efficiency height of polymerization initiator, make the photopolymerization of high speed become possibility as this sensitizing coloring matter.As other possibility, the molecular structure that is considered to this optical whitening agent of using as sensitizing coloring matter has improved the efficient of the reaction of proceeding after sensitizing initial reaction stage (electron transfer etc.) or polymerization initiator decompose.
Secondly, improve the essential factor of storage stability as this sensitizing coloring matter, be speculated as since this sensitizing coloring matter nature through the time pigment cohesion, association etc. under the condition lack, thereby suppressed the decline of sensitizing efficient.Sensitizing coloring matter plays an important role to Photoinitiated reactions, because cohesion of the pigment in the photosensitive composite or association are to the minimizing (light sensitivity reduction) of the free base unit weight of exposure generation, i.e. reduction to storage stability has very big influence, so think that few these optical whitening agents (sensitizing coloring matter) such as pigment cohesion, association make the photosensitive composite layer, promptly the storage stability of photomask board improves greatly.
According to the present invention, even can provide under the situation that contains light screening material in a large number, also can carry out the curing of ISO by exposure, and the good photomask board of storage stability, and provide use that this photomask board is made, can form high-definition picture, the photomask that the rectilinearity of image border part is high.
Embodiment
Photomask to photomask board of the present invention and making thus is described in detail below.
[photomask board]
Photomask board of the present invention is characterised in that: have the photosensitive composite layer on substrate, and the photosensitive composite layer contains compound that at least a optical whitening agent shown in (A) following formula (I-1)～(I-15), (B) polymerization initiator, (C) have the ethene unsaturated link, (D) binder polymer and (E) light screening material.In addition, as required, other layers such as oxygen barrier layers can be set on this photosensitive composite layer.
[changing 5]
Figure G200910164560XD0000071
[changing 6]
Figure G200910164560XD0000072
[changing 7]
Figure G200910164560XD0000081
X represents the divalent concatenating group selected in the formula from structure shown below.* in the following radicals represent with formula (I-6) and formula (I-13) in the binding site of heterocycle.
[changing 8]
The compound shown in (I-1)～(I-15) can have substituting group in the formula, also can not have substituting group.At this; as the substituting group that can import, can enumerate from alkyl, aryl, alkoxy, alkyl-carbonyl, alkoxy carbonyl, acyloxy, carboxyl, itrile group, amino, hydroxyl, alkyl sulphonyl, amino-sulfonyl and halogen atom, select at least a.This substituting group can also be substituted again.
(photosensitive composite layer)
The photosensitive composite layer that photomask board of the present invention had contains light shield layer at least, and is the layer that can form image under ultraviolet light or visible light.That is, the photosensitive composite layer is the image exposure with near ultraviolet ray or visible light formation, then by using developer solution to carry out the layer that development treatment can form image.
Consider that from environmental problem the photosensitive composite layer is preferably alkali-developable.The present invention uses exposed portion to solidify, and is insoluble to the cloudy type layer of alkaline-based developer.
Cloudy type photosensitive composite layer is to solidify by exposure, form the layer of light shield layer, be by contain at least compound that (A) optical whitening agent, (B) polymerization initiator, (C) have the ethene unsaturated link, (D) binder polymer and (E) photosensitive composite of light screening material form layer.
Each inscape to the photosensitive composite layer is illustrated below.At first set forth characteristic component optical whitening agent of the present invention.
＜(A) optical whitening agent shown in the formula (I-1)～(I-15) 〉
The photosensitive composite layer that photomask board of the present invention had contains at least a optical whitening agent shown in the following formula (I-1)～(I-15).
[changing 9]
Figure G200910164560XD0000091
[changing 10]
Figure G200910164560XD0000092
[changing 11]
Figure G200910164560XD0000101
X represents the divalent concatenating group selected in the formula from structure shown below.* in the following radicals represent with formula (I-6) and formula (I-13) in heteroatomic binding site.
[changing 12]
Figure G200910164560XD0000102
The compound shown in (I-1)～(I-15) can have substituting group in the formula, also can not have substituting group.At this; as the substituting group that can import, can enumerate from alkyl, aryl, alkoxy, alkyl-carbonyl, alkoxy carbonyl, acyloxy, carboxyl, itrile group, amino, hydroxyl, alkyl sulphonyl, amino-sulfonyl and halogen atom, select at least a.This substituting group can also be substituted again.
In the optical whitening agent shown in above-mentioned formula (I-1)～formula (I-15), the optical whitening agent shown in more preferably following formula (I-1-1)～following formula (I-15-1).
[changing 13]
Figure G200910164560XD0000103
Formula (I-1-1) can be R 1Be methyl, and R 2, R 3, R 4And R 5Be the compound (I-1-1-1) of hydrogen atom, or R 2, R 3, and R 4Be methoxyl, and R 1And R 5Be the compound (I-1-1-2) of hydrogen atom, or R 1Be cyano group, and R 2, R 3, R 4And R 5Be the compound (I-1-1-3) of hydrogen atom, or R 3Be cyano group, and R 1, R 2, R 4And R 5Compound (I-1-1-4) for hydrogen atom.
[changing 14]
Figure G200910164560XD0000111
Formula (I-2-1) can be R 1, R 2, R 3And R 4Be hydrogen atom, and R 5Compound (I-2-1-1) for methoxyl.
[changing 15]
Figure G200910164560XD0000112
Formula (I-3-1) is R 1～R 10Be the compound (I-3-1-1) of hydrogen atom, or R 1, R 2And R 4～R 10Be hydrogen atom, and R 3Be the compound (I-3-1-2) of methoxyl, or R 1, R 2, R 4～R 7, R 9And R 10Be hydrogen atom, and R 3And R 8Compound (I-3-1-3) for methoxyl.
[changing 16]
Formula (I-4-1) can be R 1And R 3Be hydrogen atom and R 2For-SO 3The compound of Ph (I-4-1-1), or R 1Be hydrogen atom, and R 2Be cyano group, R 3Compound (I-4-1-2) for the chlorine atom.
[changing 17]
Figure G200910164560XD0000121
Formula (I-5-1) can be R 1Be the t-butyl, and R2 is hydrogen atom, R 3Be the compound (I-5-1-1) of phenyl, or R 1Be methyl, and R 2Be hydrogen atom, R 3Be the compound (I-5-1-2) of methoxycarbonyl, or R 1And R 2Be hydrogen atom, and R 3Compound (I-5-1-3) for 2-(4-methyl-oxa--3,3-diazole).
[changing 18]
Figure G200910164560XD0000122
Formula (I-6-1) can be X be 4,4 '-talan two bases, and R 1And R 2Be the compound (I-6-1-1) of hydrogen atom, or X is 2,5-thiophene two bases, and R 1And R 2Be the compound (I-6-1-2) of t-butyl, or X is 1,4-naphthalene two bases, and R 1And R 2Be the compound (I-6-1-3) of hydrogen atom, or X is 1,1-ethylene base, and R 1And R 2Compound (I-6-1-4) for methyl.
[changing 19]
Figure G200910164560XD0000123
Formula (I-7-1) can be R 1And R 2Compound (I-7-1-1) for diethylamino.
[changing 20]
Figure G200910164560XD0000124
Formula (I-8-1) can be R 1And R 2Be hydrogen atom, and R 3For-SO 2NH 2Compound (I-8-1-1), or R 1And R 2Be hydrogen atom, and R 3For-SO 2CH 2CH 2OCH 2CH 2NMe 2Compound (I-8-1-2), or R 1And R 2Be hydrogen atom, and R 3For-SO 2CH 2CH 2OCH (CH 3) CH 2NMe 2Compound (I-8-1-3), or R 1And R 2Be hydrogen atom, and R 3For-SO 2CH 3Compound (I-8-1-4), or R 1And R 2Be hydrogen atom, and R 3For-SO 2CH 2CH 2The compound of OH (I-8-1-5).
[changing 21]
Formula (I-9-1) can be R 1Be hydrogen atom, and R 2Be methyl, R 3Be the compound (I-9-1-1) of diethylamino, or R 1Be phenyl, and R 2Be hydrogen atom, R 3Be the compound (I-9-1-2) of 2-N-naphthalene triazolyl, or R 1Be hydrogen atom, and R 2Be methyl, R 3Be the compound (I-9-1-3) of hydroxyl, or R 1Be phenyl, and R 2Be hydrogen atom, R 3Be the compound (I-9-1-4) of NH-(4, the 6-dichloro)-(1,3,5)-triazine, or R 1Be phenyl, and R 2Be hydrogen atom, R 3Compound (I-9-1-5) for 1-(3-methylpyrazole quinoline base).
[changing 22]
Formula (I-10-1) can be R 1Be hydrogen atom, and R 2Be methoxyl, R 3Be the compound (I-10-1-1) of methyl, or R 1And R 2Be ethoxy, and R 3Compound (I-10-1-2) for methyl.
[changing 23]
Formula (I-11-1) can be R 1Be methyl, and X is the compound (I-11-1-1) of hydrogen atom, or R 1Be hydrogen atom, and X is the compound (I-11-1-2) of nitro, or R 1Be hydrogen atom, and X is the compound (I-11-1-3) of dimethylamino, or R 1Be hydrogen atom, and X is the compound (I-11-1-4) of methoxyl, or R 1Be hydrogen atom, and X is the compound (I-11-1-5) of halogen atom.
[changing 24]
Figure G200910164560XD0000141
Formula (I-12-1) can be R 1And R 2Be methyl, and R 3Be the compound (I-12-1-1) of hydrogen atom, or R 1And R 2Be methyl, and R 3Compound (I-12-1-2) for-OCOMe.
[changing 25]
Figure G200910164560XD0000142
Formula (I-13-1) can be that X is 1,2-ethylene base, and R 1Be the compound (I-13-1-1) of methyl, or X be 4,4 '-talan two bases, and R 1Compound (I-13-1-2) for methyl.
[changing 26]
Formula (I-14-1) can be R 1Be phenyl, and R 2Be diethylamino, R 3Compound (I-14-1-1) for ethyl.
[changing 27]
Figure G200910164560XD0000144
Formula (I-15-1) can be R 1And R 2Compound (I-15-1-1) for methoxyl.
In the above-mentioned concrete example, especially preferred compound is I-9-1-1, I-6-1-1, I-4-1-1, I-2-1-1, and preferred compound is I-2-1-1.
Optical whitening agent is a kind of optical absorption pigment, it is preferably the light that absorbs 320～450n m wavelength, molar absorptivity under wavelength 405nm (ε) is more than 100 100, below 000, the light of energy efficient absorption bluish violet zone wavelength, have simultaneously by with the interaction of (B) described later polymerization initiator, produce at least a function free radical, the bronsted lowry acids and bases bronsted lowry base from this polymerization initiator.The molar absorptivity (ε) that optical whitening agent shows is preferably more than 1,000 10,000, below 000, more preferably more than 10,000 10,000, below 000.
That is, optical whitening agent can cause that contained various polymerization initiators decompose efficiently in the photosensitive composite layer as composition (B), demonstrates very high photonasty.
The sensitizing mechanism of the general known light initiation system of being made up of sensitizing coloring matter/polymerization initiator is as follows: (a) based on from the electron excitation state of the sensitizing coloring matter reduction decomposition to the initiator compounds of the electron transfer reaction of initiator compounds, (b) based on from the oxygenolysis of initiator compounds to the initiator compounds of the electron transfer of the electron excitation state of sensitizing coloring matter, (c) shift to the energy of initiator compounds based on electron excitation state from sensitizing coloring matter, arise from the decomposition of the electron excitation state of initiator compounds, the optical whitening agent shown in the used general formula (I-1)～(I-15) of the present invention can cause outstanding efficient in the sensitizing reaction of (c) type.
As the molecular weight of optical whitening agent, be preferably below 2,000, more preferably below 1,000, be generally more than 200.
Optical whitening agent can a kind uses separately, also can be used in combination more than 2 kinds.
Particularly preferred optical whitening agent is for being dissolved in the compound of organic solvent.
Because the rerum natura of the photonasty of photosensitive composite layer, resolution, exposed film is subjected to the influence of the absorbance optical source wavelength under very big, so to consider that these factors suitably select sensitizing coloring matter.For example, if absorbance is 0.1 below and low wavelength coverage, the then light sensitivity of photosensitive composite layer decline.In addition, the photosensitive composite layer is owing to be subjected to the influence of halation that resolution is reduced.But if the above thick film of 5 μ m is solidified, low like this absorbance can improve degree of cure sometimes on the contrary.
The content of these (A) optical whitening agents accounts for 0.1～10 quality % of all solids composition in the photosensitive composite layer, is preferably the scope of 0.5～8 quality %.
In addition, (A) optical whitening agent can also be used with known sensitizing coloring matter.At this moment, guaranteeing under the situation of effect of the present invention that (A) content of optical whitening agent preferably accounts for more than the 1 quality % of contained sensitizing coloring matter in the photosensitive composite [(A) optical whitening agent+other sensitizing coloring matter] total amount, is preferably especially more than the 10 quality %.
＜(B) polymerization initiator 〉
As (B) polymerization initiator among the present invention, can suitably select to use known various Photoepolymerizationinitiater initiaters in special permission, the document etc., or the paralled system of the Photoepolymerizationinitiater initiater more than 2 kinds (photopolymerization initiator system).Among the present invention, the Photoepolymerizationinitiater initiater of use separately and the system of Photoepolymerizationinitiater initiater more than 2 kinds and usefulness are called Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater among the present invention has no particular limits, and can suitably select according to exposure wavelength.For example use under near the situation of light the 400nm, can from known Photoepolymerizationinitiater initiater such as benzyl (ベ Application ジ Le), benzoyl ether, Michler's keton (Micher ' s ketone), anthraquinone, thioxanthones, acridine, azophenlyene, benzophenone, hexa-aryl bi-imidazole compound, extensively select to use as light source.
Wherein, as (B) polymerization initiator, be that the optical excitation energy of accepting sensitizing coloring matter when coexisting down by rayed with (A) optical whitening agent produces living radical, make the free radical generating agent of (C) ethene unsaturated polymerizable compound, can preferably enumerate Hexaarylbisimidazolecompounds compounds, two luxuriant titaniums, metallocene compound, triaizine compounds, oxime ester compound, halogenated hydrocarbons derivant, diaryl group iodized salt, organic borate and organic peroxide etc.From exposure light sensitivity, photosensitive composite layer viewpoints such as the adhesiveness of substrate and storage stability are considered, be preferably Hexaarylbisimidazolecompounds compounds, metallocene compound, triaizine compounds, oxime ester compound and organic borate, be preferably Hexaarylbisimidazolecompounds compounds especially.
Be that the hexa-aryl bi-imidazole compound is illustrated to preferred Photoepolymerizationinitiater initiater among the present invention below.
As the hexa-aryl bi-imidazole compound, can use Europe special permission No. 24629, No. the 107792nd, Europe special permission, the U.S. speciallyyed permit No. 4410621, No. the 215453rd, Europe special permission and Germany's special permission and the described all cpds of each instructions such as disclosed No. 3211312.As preferred compound, can enumerate as 2,45,2 ', 4 ', 5 '-the hexaphenyl diimidazole, 2,2 '-two (2-chlorphenyls)-4,5,4 ', 5 '-the tetraphenyl diimidazole, 2,2 '-two (2-bromophenyls)-4,5,4 ', 5 '-the tetraphenyl diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,5,4 ', 5 '-the tetraphenyl diimidazole, 2,2 '-two (2-chlorphenyl)-4,5,4 ', 5 '-four (3-methoxyphenyl)-diimidazoles, 2,5,2 ', 5 '-four (2-chlorphenyls)-4,4 '-two (3, the 4-Dimethoxyphenyl) diimidazole, 2,2 '-two (2, the 6-dichlorophenyl)-4,5,4 ', 5 '-the tetraphenyl diimidazole, 2,2 '-two (2-nitrobenzophenones)-4,5,4 ', 5 '-the tetraphenyl diimidazole, 2,2 '-two-o-tolyl-4,5,4 ', 5 '-the tetraphenyl diimidazole, 2,2 '-two (2-ethoxyl phenenyl)-4,5,4 ', 5 '-tetraphenyl diimidazole and 2,2 '-two (2, the 6-difluorophenyl)-4,5,4 ', 5 '-the tetraphenyl diimidazole etc.
The hexa-aryl bi-imidazole compound can more than 2 kinds and be used.
When using the hexa-aryl bi-imidazole compound as Photoepolymerizationinitiater initiater, the use amount of this hexa-aryl bi-imidazole compound preferably accounts for 0.05～50 mass parts of (C) described later ethene unsaturated compound total amount 100 mass parts, more preferably accounts for 0.2～30 mass parts.Other Photoepolymerizationinitiater initiater can and be used with the hexa-aryl bi-imidazole compound.
As required, by with the hydrogen supply compound be thio-compounds, N-phenylglycine, N such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, amines such as N-dialkyl amido aromatic series Arrcostab etc. are usefulness also, more can improve the light-initiated ability of Photoepolymerizationinitiater initiater.
As being suitable for the hydrogen supply compound that can improve light-initiated ability of the present invention, can enumerate the compound that contains sulfydryl especially.
As the example that is more suitable for of compounds containing thiol groups, can enumerate following general formula (A) or (B) shown in compound (hereinafter referred to as " heterogeneous ring compound that contains sulfydryl ").Following general formula (A) and (B) expression dynamic isomer structure.
[changing 28]
Figure G200910164560XD0000171
General formula (A) and (B) in, R 2, R 3And R 4Represent hydrogen atom independently of one another, replace or do not have the carbon number 1 to 18 of replacement the straight or branched alkyl, replace or do not have the ester ring type alkyl or the aromatic radical of the carbon number 5 to 20 of replacement.As substituting group, can enumerate halogen atom, hydroxyl, amino, thio group, acetyl group, carboxyl etc.
General formula (A) and (B) shown in the preferred object lesson (SH1) to (SH20) of compound be expressed as follows, but the present invention is not only limited to these object lessons.Following structure is represented with the structure of containing in the above-mentioned dynamic isomer-SH base.
The object lesson of compound shown in the general formula (A)
[changing 29]
Figure G200910164560XD0000181
The object lesson of compound shown in the general formula (B)
[changing 30]
Figure G200910164560XD0000191
Contain the sulfhydryl heterocycle compound and be preferably 0.2～10.0mol with respect to the ratio of Photoepolymerizationinitiater initiater 1mol such as hexa-aryl bi-imidazole compound, the ratio of 0.5～6.0mol more preferably is preferably the ratio of 0.5～4.0mol especially.
The content of the polymerization initiator in the photosensitive composite layer preferably accounts for 0.1～20 mass parts of all solids composition 100 mass parts that constitute the photosensitive composite layer, more preferably accounts for 0.5～15 mass parts, especially preferably accounts for the scope of 1～10 mass parts.
＜(C) have a compound (ethene unsaturated compound) of ethene unsaturated link 〉
The photosensitive composite layer contains the compound (ethene unsaturated compound) with ethene unsaturated link.
The ethene unsaturated compound is meant the compound that has at least one ethene unsaturated link in the molecule, during photosensitive composite layer receptor 1 activity irradiate light, carries out addition polymerization, crosslinked, curing by the effect of Photoepolymerizationinitiater initiater.
The ethene unsaturated compound can have at least one from end, select arbitrarily the compound preferred more than 2, more preferably 2～6 ethene unsaturated links.Has the i.e. compound of 2 aggressiveness, 3 aggressiveness and oligomer or their potpourri and their chemical forms such as multipolymer of monomer, prepolymer.
As the example of ethene unsaturated compound, can enumerate the ester of unsaturated carboxylic acid (as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) and polyol compound, the acid amides of unsaturated carboxylic acid and polyamine compound etc.
Object lesson as the monomer of the ester of polyol compound and unsaturated carboxylic acid; acrylate has glycol diacrylate; triethylene glycol diacrylate; 1; the 3-butanediol diacrylate; the tetramethyl omega-diol diacrylate; propylene glycol diacrylate; neopentylglycol diacrylate; trimethylolpropane triacrylate; trimethylolpropane tris (acryloyl group oxygen propyl group) ether; the trimethylolethane trimethacrylate acrylate; hexanediyl ester; 1,4-cyclohexanediol diacrylate; tetraethylene glycol diacrylate; pentaerythritol diacrylate; pentaerythritol triacrylate; tetramethylol methane tetraacrylate; the dipentaerythritol diacrylate; dipentaerythritol five acrylate; dipentaerythritol acrylate; the D-sorbite triacrylate; the D-sorbite tetraacrylate; D-sorbite five acrylate; D-sorbite six acrylate; three (acryloyl group oxygen ethyl) triisocyanate; polyester acrylic ester oligomer etc.
Methacrylate has tetramethyl glycol dimethylacrylate, the triethylene glycol dimethylacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, dipentaerythritol pentamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two [p-(3-methacryloxypropyl-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two-[p-(methacryloxypropyl ethoxy) phenyl] dimethylmethane etc.
Itaconate has ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,5-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, TEG diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.Butenoate has ethylene glycol bisthioglycolate butenoate, TEG dibutene acid esters, pentaerythrite dibutene acid esters, D-sorbite four dibutene acid esters etc.Methacrylate has glycol ester diisobutylene, pentaerythrite diisobutylene acid esters, D-sorbite tetra methylacrylate etc.
Maleate has ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc.Can also enumerate the potpourri of above-mentioned ester monomer.
In addition, object lesson as the amide monomer of polyamine compound and unsaturated carboxylic acid, methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1 are arranged, 6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, dimethylene triamine three acrylamides, xylylene diacrylamine, xylylene DMAA etc.
As other example, can enumerate the described vinyl urethane compound of special public clear 48-41708 communique, it is that vinyl monomer with the hydroxyl shown in the following general formula (m) adds to be formed in and has the polyisocyanate compounds of 2 above isocyanate group in 1 molecule and make the compound that contains 2 above polymerism vinyl in 1 molecule.
CH 2＝C(R)COOCH 2CH(R′)OH????????(m)
(R and R ' represent H or CH independently of one another 3)
Can enumerate Ru Te in addition opens clear 51-37193 number, the described urethane acrylate class of special fair 2-32293 number each communique, spy and opens polyfunctional acrylic ester or methacrylates such as clear 48-64183 number, special public clear 49-43191 number, the described polyester acrylate class of special public clear 52-30490 communique, epoxy resin and (methyl) acrylic acid reaction gained epoxy acrylate class.Can also use the Japanese bonding will Vol.20 of association, No.7, photo-curable monomer and oligomer that 300～308 pages (1984) are introduced.
The ethene unsaturated compound that preferably uses as the present invention, preferred use has the compound of a plurality of isocyanate group and has the acrylate of hydroxyl or the polymerizable compound with a plurality of urethane bonds of methacrylate addition reaction gained, as the described compound of the public clear 56-17654 communique of spy.
The content of these ethene unsaturated compounds preferably accounts for 5～80 quality % of all-mass in the photosensitive composite layer, especially preferably accounts for the scope of 30～70 quality %.
＜(D) binder polymer 〉
The photosensitive composite layer contains binder polymer.
Binder polymer among the present invention has no particular limits, and considers preferably have the organic polymer of acidic group from the viewpoint to the dissolubility development of alkaline aqueous solution, especially preferably has the organic polymer of carboxyl.
Skeleton as binder polymer, the preferred macromolecular scaffold of from acryl resin, polyvinyl acetal resin, polyvinyl alcohol resin, urethane resin, polyamide, epoxy resin, methacrylic resin, styrene resin, vibrin, selecting, wherein, ethylenic copolymer, urethane resins such as special preferred acrylic resins, methacrylic resin, styrene resin.
As binder polymer, preferably use acryl resin, methacrylic resin, urethane resin.
One of binder polymer suitable examples is to have (a) to contain the multipolymer that carboxylic acid group or sulfonic repetitive, (b) give the repetitive of radical crosslinking.
Contain the object lesson of carboxylic acid group or sulfonic repetitive (below weigh multiple unit (a)) as (a), the structure shown in (a-1) to (a-13) below can enumerating, but the present invention is not only limited to these structures.
[changing 31]
Figure G200910164560XD0000231
Be made as 100 if will always repeat unit number, then the content of repeating unit of copolymer (a) is 5～50, is preferably 5～25, more preferably 5～15.As repetitive (a), especially preferably contain carboxylic acid group's repetitive.
Give the object lesson of the repetitive (below weigh multiple unit (b)) of radical crosslinking as (b), the structure shown in (b-1) to (b-11) below can enumerating, but the present invention is not only limited to these structures.
[changing 32]
Figure G200910164560XD0000241
Be made as 100 if will always repeat unit number, then the content of repeating unit of copolymer (b) is 5～90, is preferably 20～85, more preferably 40～80.
Binder polymer among the present invention also can have the repetitive shown in the following general formula (1) (below weigh multiple unit (1)).
[changing 33]
Figure G200910164560XD0000242
In the general formula (1), X represent oxygen atom, sulphur atom or-the NH-base, Y represent alkyl, the carbon number 5～12 of hydrogen atom, carbon number 1～12 the ester ring type alkyl, have the group of the aromatic rings of carbon number 6～20.Z represent oxygen atom, sulphur atom or-the NH-base, R 1The alkyl of expression carbon number 1～18, have carbon number 5～20 alicyclic structure alkyl or have the group of the aromatic rings of carbon number 6～20.
As the object lesson of repetitive (1), the structure shown in (1-1)～(1-9) below can enumerating, but the present invention is not only limited to these structures.
[changing 34]
Figure G200910164560XD0000251
Be made as 100 if will always repeat unit number, then the content of repetitive (1) is 1～40, is preferably 3～25, more preferably 5～15.
Object lesson as repetitive (a) and (b), (1) appropriate combination can enumerate (PP-1)～(PP-11) shown in the following table 1, but the present invention is not only limited to these combinations.
[table 1]
Concrete example No. Repetitive (1) Repetitive (a) Repetitive (b)
??PP-1 ??1-3 ??a-1 ??b-1
??PP-2 ??1-3 ??a-1 ??b-8
??PP-3 ??1-2 ??a-1 ??b-1
??PP-4 ??1-2 ??a-1 ??b-8
??PP-5 ??1-2 ??a-1 ??b-11
??PP-6 ??1-9 ??a-5 ??b-1
??PP-7 ??1-5 ??a-3 ??b-1
Concrete example No. Repetitive (1) Repetitive (a) Repetitive (b)
??PP-8 ??1-5 ??a-3 ??b-8
??PP-9 ??1-1 ??a-3 ??b-1
??PP-10 ??1-1 ??a-5 ??b-8
??PP-11 ??1-9 ??a-3 ??b-1
The urethane resin that uses as binder polymer among the present invention preferably has crosslinkable groups.When this crosslinkable groups is meant the photomask board exposure, in the photosensitive composite layer, take place to make the crosslinked group of binder polymer in the process of Raolical polymerizable.So long as have the group of such function, then have no particular limits, for example,, can enumerate ethene unsaturated group, amino, epoxy radicals etc. as the functional group that can carry out addition polymerization.Also can be the functional group that becomes free radical by rayed,, can enumerate thio group, halogen radical, salt structure etc. as such crosslinkable groups.Wherein optimal ethylene is unsaturated in conjunction with base, the functional group shown in the preferred especially following general formula (1A)～(3A).
[changing 35]
Figure G200910164560XD0000261
R in the general formula (1A) 1～R 3Represent hydrogen atom or 1 valency organic group independently of one another.As R 1, preferably enumerate hydrogen atom and maybe can have substituent alkyl etc.Wherein, because the free radical reaction height of hydrogen atom, methyl, thereby be preferred.
As R 2And R 3, can enumerate hydrogen atom, halogen atom, amino, carboxyl, alkoxy carbonyl, sulfo group, nitro, cyano group independently of one another, can have substituent alkyl, can have substituent aryl, can have substituent alkoxy, can have substituent aryloxy group, can have substituent alkyl amino, can have substituent arylamino, can have substituent alkyl sulphonyl, can have substituent aryl sulfonyl etc.Wherein hydrogen atom, carboxyl, alkoxy carbonyl, can have substituent alkyl, can have substituent aryl because the free radical reaction height, thereby be preferred.
X in the general formula (1A) represent oxygen atom, sulphur atom or-N (R 12)-, R 12Expression hydrogen atom or 1 valency organic group.As R 121 valency organic group, can enumerate and can have substituent alkyl etc.Wherein as R 12, because the free radical reaction height of hydrogen atom, methyl, ethyl, isopropyl, thereby be preferred.
As the substituting group that can import, can enumerate alkyl, thiazolinyl, alkynyl, aryl, alkoxy, aryloxy group, halogen atom, amino, alkyl amino, arylamino, carboxyl, alkoxy carbonyl, sulfo group, nitro, cyano group, amide group, alkyl sulphonyl, aryl sulfonyl etc.
[changing 36]
Figure G200910164560XD0000271
In the general formula (2A), R 4～R 8Represent hydrogen atom or 1 valency organic group independently of one another.As R 4～R 8, preferably enumerate hydrogen atom, halogen atom, amino, dialkyl amido, carboxyl, alkoxy carbonyl, sulfo group, nitro, cyano group, can have substituent alkyl, can have substituent aryl, can have substituent alkoxy, can have substituent aryloxy group, can have substituent alkyl amino, can have substituent arylamino, can have substituent alkyl sulphonyl, can have substituent aryl sulfonyl etc.Wherein preferred hydrogen atom, carboxyl, alkoxy carbonyl, can have substituent alkyl, can have substituent aryl.
As the substituting group that can import, be exemplified as and the same structure of general formula (1A).
In addition, Y represent oxygen atom, sulphur atom or-N (R 12)-.R 12R with general formula (1A) 12Identical, preferred example is also identical.
[changing 37]
Figure G200910164560XD0000281
In the general formula (3A), R 9～R 11Represent hydrogen atom or 1 valency organic group independently of one another.As R 9, preferably enumerate hydrogen atom and maybe can have substituent alkyl etc.Wherein because the free radical reaction height of hydrogen atom, methyl, thereby be preferred.As R 10, R 11, can enumerate hydrogen atom, halogen atom, amino, dialkyl amido, carboxyl, alkoxy carbonyl, sulfo group, nitro, cyano group independently of one another, can have substituent alkyl, can have substituent aryl, can have substituent alkoxy, can have substituent aryloxy group, can have substituent alkyl amino, can have substituent arylamino, can have substituent alkyl sulphonyl, can have substituent aryl sulfonyl etc.Wherein, owing to hydrogen atom, carboxyl, alkoxy carbonyl, can have substituent alkyl, can have the free radical reaction height of substituent aryl, thereby be preferred.
As the substituting group that can import, be exemplified as and the identical structure of general formula (1A).
In addition, Z represent oxygen atom, sulphur atom ,-N (R 12)-maybe can have substituent phenylene.R 12R with general formula (1A) 12Identical, preferred example is also identical.
Consider that from the viewpoint of the development of keeping the photosensitive composite layer molecular weight of binder polymer is represented with weight-average molecular weight, is preferably 5,000～300,000 scope.Preferred scope is 20,000～150,000.
Binder polymer can be measured arbitrarily in the photosensitive composite layer and contain, but considers from the viewpoint of image intensity etc., preferably accounts for 10～90 quality % of all solids composition in the photosensitive composite layer, especially preferably accounts for 30～80 quality %.
＜(E) light screening material 〉
The photosensitive composite layer of photomask board of the present invention contains light screening material.
Light screening material of the present invention is meant, absorbs the light of 250nm～400nm, and the optical density (OD) (O.D.) when filming formation is preferably at the light absorber below 7.0 more than 2.5.
Light screening material of the present invention be meant have reflection, the light of active ray wavelength that the absorbing light mask is suitable for, and do not make the material of its function that sees through, specifically, be meant that can cover the wavelength coverage that exposure light source (mercury vapor lamp, metal halide lamp, xenon lamp etc.) sends when using as mask in fact is 200～450nm, light about preferred 250～400nm, the optical density (OD) (O.D.) of filming when forming will be preferably the material below 7.0 more than 3.0 more than 2.5 below 7.0.
Light screening material of the present invention can be according to the suitably selections such as application target of the photomask of being made by photomask board.
As light screening material, particularly, can suitably use other particle, fullerenes etc. such as metallics (containing metal compound particles, composite particle, core shell particles etc.), pigment.
As spendable light screening material among the present invention, be preferably black material, as this black material, be preferably at least a in black pigment and the metal microparticle.
Below light screening material of the present invention is described in detail.
-metallics-
Use under the situation of metallics as light screening material, this metallics can be formed by a kind of metal, also can form by the metallic combination more than 2 kinds, and also can be alloy.In addition, metallics also can be the composite particles of metal and metallic compound.Consider that from screening capacity, photostability, stable on heating viewpoint the particle that preferably uses the containing metal compound is as light screening material.
As the example of the preferred metal that contains in the metallics, can enumerate at least a kind that from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, Liao, Osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead and their alloy, selects.Preferred metal is copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, calcium, iridium and their alloy thereof.Preferred metal is at least a kind that selects from copper, silver, gold, platinum, palladium, tin, calcium and their alloy thereof.Particularly preferred metal is at least a kind that selects from copper, silver, gold, platinum, tin and their alloy kind thereof.Preferred especially silver particles (preferred collargol is as silver), the particle with silver-colored ashbury metal part also is suitable.Set forth particle below with silver-colored ashbury metal part.
Metallic compound is meant the compound of other element beyond above-mentioned metal and the metal.As the compound of metal and other element, can enumerate oxide, sulfide, sulfate, carbonate of metal etc., as the metallic compound particle, these particles are suitable.Wherein, consider, be preferably sulfide particles from the difficulty or ease of tone or particulate formation.
As the example of metallic compound, have cupric oxide (II), iron sulfide, silver sulfide, copper sulfide (II), titanium black etc., but the difficulty or ease that form from tone, particulate or the viewpoint of stability consider, be preferably silver sulfide especially.
Composite particle is meant that metal and metallic compound are combined into 1 particle.Can enumerate as at the inside of the particle particle different particle that 2 kinds of particles unite two into one etc. with surface composition.In addition, metallic compound and metal can use a kind respectively, also can more than 2 kinds and use.
As the object lesson of the composite particles of metallic compound and metal, can suitably enumerate the composite particles etc. of composite particles, silver and the cupric oxide (II) of silver and silver sulfide.
Use under the situation of composite particle as light screening material, this composite particle can be the composite particle (core shell particles) with core shell structure.The composite particle of core-shell-type (core shell particles) is meant that the surface coverage in core material has the particle of shell material.
As the shell material that constitutes the core-shell-type composite particle, can enumerate from Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, Se, Te, CuCl, CuBr, CuI, TlCl, TlBr, TlI or their solid solution, and at least a kind the semiconductor of from contain their solid solution more than 90mol%, selecting, perhaps from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium Osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, plumbous, at least a kind the metal of selecting in calcium and their alloy.
Also can suitably use the adjustment agent of shell material in order to reduce reflectivity as refractive index.
As preferred core material, can enumerate at least a kind that from copper, silver, gold, palladium, nickel, tin, bismuth, antimony, lead and their alloy, selects.
Method for making as the composite particle with core shell structure has no particular limits, and as representational method, can enumerate following (1) and (2).
(1) by oxidation, sulfuration on the surface of the metal particle of making by known method, form the method for the shell of metallic compound, as, metal particle is scattered in the dispersion medium such as water the method for adding sodium sulphide or ammonium sulfide sulfides.According to this method the sulfuration of the surface of particle can be formed the core shell particles.
The metallics that use this moment can use known method such as vapor phase method, liquid phase method to make.About the method for making of metallics, set forth to some extent in " the up-to-date trend II of ultramicronized technology and application " (living in ベ テ Network ノ リ サ one チ (share), distribution in 2002).
(2) in metallics manufacturing process, form the method for metallic compound shell continuously on the surface, as, in metal salt solution, add reductive agent, make the part reduction of metallic ion make metal particle, add sulfide then, around the metal particle of making, form the method for metal sulfide.
Metallics except can use commercially available, modulation such as chemical reduction method that can also be by metallics, plated by electroless plating method, evaporation of metal method.
For example, for bar-shaped silver-colored particulate, with the spherical silver particulate as kind of a particle, add silver salt then, in the presence of CTAB surfactants such as (hexadecyltrimethylammonium bromides),, can obtain the silver of silver-colored rod or wire by more weak reductive agents of reducing power such as use ascorbic acid.These methods are at Advanced Materials 2002,14, and 80-82 is on the books.In addition, same method is at Materials Chemistry and Physics 2004,84,197-204, Advanced Functional Materials 2004,14, and 183-189 is also on the books.
In addition as the method for using electrolytic action, at Materials Letters 2001,49,91-95 or the method that generates the silver rod by irradiating microwaves be at Journal of Materials Research2004, and 19,469-473 is on the books.The example of reversed micelle and ultrasound wave and usefulness can be enumerated Journal of Physical Chemistry B 2003,107, the method for 3679-3683.
About gold particle, equally at Journal of Physical Chemistry B 1999,103,3073-3077 and Langmuir1999,15,701-709, Journal ofAmerican Chemical Society 2002,124,14316-14317 is on the books.
Rod-shaped particle also can be modulated with improvement (addition adjustment, the pH control) method of said method.
As particle, comprise particle and argentiferous ashbury metal part and other alloy particle partly of particle, argentiferous ashbury metal part and other metal part of argentiferous ashbury metal with silver-colored ashbury metal part.
In particle with silver-colored ashbury metal part, carry out the spectroscopic assay of each particle center 15nm * 15nm scope under the accelerating potential 200kV by the HD-2300 of use (share) Hitachi manufacturing and the EDS (energy dispersion type x-ray analysis equipment) of ノ one ラ Application (Noran) company manufacturing, can confirm that at least a portion is made of silver-colored ashbury metal.
Owing to have the black concentration height of the particle of silver-colored ashbury metal part, can find good shading performance with a small amount of or film, have high thermal stability simultaneously, thus do not lose the high temperature (more than 200 degree) of black concentration be heat-treated to be possible, can guarantee the light-proofness of stable height.
-pigment and other particle-
As light screening material, can use pigment and other particle.
When using pigment, can constitute more form and aspect near black.Use under the situation of pigment as light screening material, pigment can use separately, also can be shared with above-mentioned metallics.
As pigment and other particle, can enumerate the particle that black materials such as carbon black, titanium are black, graphite form.
As black pigment, can enumerate fat-soluble black HB (C.I.26150), the bad special fast black B (C.I. pigment black 1) of Monot and carbon black etc.
As the example of carbon black, be preferably Pigment Black (pigment black) 7 (carbon black C.I.No.77266).As commercially available product, can enumerate the carbon black MA100 of Mitsubishi (Mitsubishi Chemical's (share) system), the carbon black #5 of Mitsubishi (Mitsubishi Chemical's (share) system).
As the black example of titanium, be preferably TiO 2, TiO, TiN or their potpourri.As commercially available product, can enumerate the 12S or the 13M (trade name) of Mitsubishi Materials (マ テ リ ア Le ズ) (share) system.
The present invention can use above-mentioned known pigment in addition as light screening material.Pigment generally is divided into organic pigment and inorganic pigment, but preferred organic pigment.As the example of the pigment that is fit to use, can enumerate azo class pigment, phthalocyanine pigment, anthraquinone class pigment, dioxazines pigment, quinoline a word used for translation ketone pigment, isoindoline ketone pigment, nitro class pigment etc.As the form and aspect of such organic pigment, can enumerate yellow uitramarine, orange pigment, red pigment, violet pigment, blue pigment, viridine green, brown pigments, black pigment etc.
The particle of operable other pigment of the present invention etc. is listed below.But the present invention not only is defined in these particles.
As concrete example, can use suitably that the spy opens the described look material in 2005-17716 communique [0038]～[0040], the spy opens 2004-361447 communique [0068]～[0072] described pigment or the spy opens 2005-17521 communique [0080]～[0088] described colorant.
In addition, can be with reference to " pigment handbook, Japanese pigment technology association compile, really Wen Tangxin light society, 1989 ", " COLOUR INDEX, THE SOCIETY OF DYES; COLOURIST, THIRDEDITION, 1987 " described pigment suitably uses.
Under the situation that pigment and metal species particle use simultaneously, wish to use the pigment that is complementary relationship with the form and aspect of metal species particle.In addition, pigment can a kind uses separately, also can be used in combination more than 2 kinds.As preferred pigment combinations, can enumerate the combination that pigment composition that pink group and blue class have complementary color relation mutually and yellow class and purple class have the pigment composition that complementary color concerns mutually, or said mixture adds the combination of black pigment, or the pigment combinations of blue class and purple class, black class.
Light screening material of the present invention is preferably carbon black.
Use under the situation of carbon black as light screening material, the photosensitive composite layer can only contain carbon black, also can and use carbon black and other look material (as other colorant).Carbon black and other look material and time spent, if in the contained all coloring agent of photosensitive composite layer 50 quality % above be carbon black, then the colour saturation of photosensitive composite layer becomes high concentration, thereby is preferred.
When using pigment as light screening material, the pigment that preferably has the following mean grain size of 100nm, the more preferably following pigment of the above 60nm of 1nm.Preferably with spreading agent with pigment dispersing in the formation of photosensitive composite layer in the employed photosensitive composite.
The content of light screening material in all solids composition of photosensitive composite layer, light sensitivity when depending on concentration, thickness, the making photomask of the photomask of making by photomask board, resolution etc., different according to kind, but be preferably 10 quality %～50 quality %, more preferably 15 quality %～35 quality %.
＜(F) other composition 〉
Photosensitive composite layer of the present invention except above-mentioned necessary composition (A)～(E), can and be used all cpds as required.Now other composition that can be used for the photosensitive composite layer is illustrated.
-UV absorbing agent-
In order to improve the absorbance of ultraviolet region, UV absorbing agent etc. can also be added in the photosensitive composite layer simultaneously.As the UV absorbing agent, also can use as the spy open flat 9-25360 communique described, by heating ultraviolet region is had the compound of strong absorption.
-thermal polymerization inhibitor-
As other adjuvant, when forming the photosensitive composite layer or during photomask board preserves,, preferably add a spot of thermal polymerization inhibitor in order to stop the unwanted thermal polymerization of the compound that contains ethene unsaturated link that may polymerization.More preferably add thermal polymerization and prevent agent.As an example, can enumerate quinhydrones, p-metoxyphenol, two-t-butyl-p-cresols, pyrogallol, t-butyl catechol, benzoquinones, 4,4 '-sulphur two (3-methyl-6-t-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, the inferior cerium salt of N-nitroso-phenyl hydramine, N-nitroso-phenyl hydramine aluminium salt etc.
The addition of thermal polymerization inhibitor preferably accounts for about 0.01 quality %～about 5 quality % of all solids composition that constitutes the photosensitive composite layer.In addition, as required, poly-for the resistance that prevents to cause by oxygen, can add the such advanced higher fatty acid derivative of behenic acid or n-docosane acid amides etc., these advanced higher fatty acid derivatives etc. also can be in the surface distributed inequality of photosensitive composite layer in the dry run after coating.The addition of advanced higher fatty acid derivative etc. preferably accounts for about 0.5 quality %～about 10 quality % of all solids composition that constitutes the photosensitive composite layer.
-other adjuvant-
In the photosensitive composite of the present invention, can add known additives such as plastifier, surfactant etc. as required.
The formation of＜photosensitive composite layer 〉
The photosensitive composite layer can use method of spin coating, slit method of spin coating, rolling method, get to know coating process or curtain formula curtain coating etc., will contain above-mentioned each must composition and arbitrarily the coating fluid of composition (the photosensitive composite layer forms and uses coating fluid) be arranged on the suitable substrate by direct coating.
The thickness of photosensitive composite layer is considered from the viewpoint of homogeneity, resolution and the light sensitivity of thickness, is preferably the scope of 0.3 μ m～7 μ m.Particularly preferred thickness is 0.5 μ m～3 μ m.
(substrate)
Above-mentioned photosensitive composite layer is formed on the suitable substrate, becomes photomask board of the present invention.Substrate can suitably be selected as required, and from forming substrate together with photomask, the viewpoint that former state is used repeatedly considers, the preferred light mask not have the substrate of absorption to the wavelength of the exposure light source that uses, when for example being used for visible light, preferably uses transparent substrate.At this, transparent substrate is meant that the wavelength region may at 350～750nm does not have the greatly substrate of absorption.
-transparency carrier-
As the transparency carrier of photomask board of the present invention, can suitably use the transparency carrier that resembles glass plate (as quartz glass, soda-lime glass, alkali-free glass etc.), the transparent plastic film (as ethylene glycol terephthalate etc.).The thickness of transparency carrier can suitably be set according to photomask board, is preferably the scope of 0.1mm～20mm, more preferably the scope of 1mm～7mm, the more preferably scope of 1mm～5mm.
(oxygen barrier layers)
Photomask board of the present invention in order suitably to control the permeability of oxygen, preferably has oxygen barrier layers on the photosensitive composite layer.Below oxygen barrier layers is illustrated.
Oxygen barrier layers is preferably oxygen permeability under 25 ℃, 1 atmospheric pressure at 1.0ml/m 2The above 500ml/m of dayatm 2Below the dayatm.
Because the oxygen permeability that oxygen barrier layers has is in above-mentioned scope, thereby when when making photomask board and without use, preserving (unused stock), undesired polymerization can not take place, during the image exposure when making photomask, do not produce unwanted mist, the thick problem of image in addition yet.So, can obtain having the linear photomask of high resolving power and preferable image marginal portion by photomask board of the present invention with related feature.
Even in oxygen barrier layers, consider that from obtaining the linear viewpoint in high resolution and preferable image marginal portion the oxygen permeability of oxygen barrier layers especially is preferably 50ml/m 2The above 500ml/m of dayatm 2Below the dayatm, 80ml/m more preferably 2The above 480ml/m of dayatm 2Below the dayatm, be preferably 100ml/m especially 2The above 470ml/m of dayatm 2Below the dayatm, 150ml/m most preferably 2The above 460ml/m of dayatm 2Below the dayatm.
The oxygen permeability that oxygen barrier layers has in this instructions is that ((モ コ Application) method is agree at the end: the oxygen permeability of Ce Dinging MOCON method) by following assay method.
The assay method of-oxygen permeability-
To coat the high polyethylene film of oxygen permeability (Fuji's film (share) system " エ バ one PVC will be removed in dissolving with same the filming of forming of the oxygen barrier layers that forms on the photosensitive layer ュテ ィOne ペ, one パ one " the polyethylene layer platen made of surperficial gelatin layer) make the sample of measuring usefulness.According to the gas permeation degree test method of JIS-K7126B and ASTM-D3985 record, use the end to agree corporate system OX-TRAN2/21, under 25 ℃, 60%RH environment, measure oxygen permeability (ml/m 2Dayatm).
The control of the oxygen permeability that oxygen barrier layers had, adopts each method such as the resin that demonstrates preferred oxygen permeability or these methods of appropriate combination to be implemented at adjustment that can be by the kind of contained each composition of oxygen barrier layers and the adjustment of content (particularly as the adjustment of polyvinyl alcohol (PVA) saponification degree, the interpolation of plastifier etc.), oxygen barrier layers thickness.
In addition, as the desirable characteristic of oxygen barrier layers, except above-mentioned oxygen permeability, do not hinder the seeing through of the light that is used to expose in addition, good and developing procedure after exposure is removed easily with the adhesion of photosensitive layer.
In order to realize above-mentioned oxygen permeability, elaborate the formation of preferred oxygen barrier layers below.
＜water-soluble high-molecular compound 〉
Consider that from the viewpoint of oxygen block and development oxygen barrier layers preferably contains water-soluble high-molecular compound.
As water soluble polymer, preferably use the better compound of crystallinity.Can enumerate the water-soluble polymers as polyvinyl alcohol (PVA), vinyl alcohol/phthalic acid vinyl ester copolymers, vinyl acetate/vinyl alcohol/phthalic acid vinyl ester copolymers, vinyl acetate/butenoic acid multipolymer, polyvinyl pyrrolidone, poly alkylene glycol (polyglycol, polypropylene glycol etc.), acid cellulose class, gelatin, Arabic gum, polyacrylic acid, polyacrylamide amine polyester, polyurethane etc. particularly, they can be used alone or as a mixture.Wherein, polyvinyl alcohol (PVA) uses as major component, gives best result to fundamental characteristics such as oxygen block, developments.
As the object lesson of polyvinyl alcohol (PVA), 40～100 moles of % that can enumerate vinyl alcohol units are hydrolyzed, and polymer repeating unit is at the compound of 300 to 2400 scopes.
The polyvinyl alcohol (PVA) that oxygen barrier layers uses, as long as in order to have oxygen block and water-soluble and contain unsubstituted vinyl alcohol units, then its part also can be replaced by ester, ether and acetal.
In addition, the polyvinyl alcohol (PVA) that the present invention uses can contain polyvinyl alcohol derivatives such as sour modified polyvinylalcohol, or has the multipolymer of the polymerized unit beyond the vinyl alcohol units.
As water-soluble high-molecular compound, the preferred polyvinyl alcohol (PVA) commercially available product of using can be enumerated the PVA-105 that (Network ラ レ) system is come in (share) storehouse, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-505, PVA-613, L-8, KL-504, KL-506, KL-318, KL-118, KM-618, KM-118, C-506, R-2105, R-1130, R-2130, M-205, MP-203, LM15, LM20, LM25 etc., they can also can mix use separately.
As multipolymer, can enumerate vinyl alcohol/vinylpyrrolidone copolymer etc. with the vinyl alcohol units polymerized unit in addition that is applicable to the used polyvinyl alcohol (PVA) of oxygen barrier layers.
As polyvinyl alcohol derivative, preferably use sour modified polyvinylalcohol.At this, sour modified polyvinylalcohol is meant the polyvinyl alcohol derivative with acidic group groups such as carboxyls.
The acid modified polyvinylalcohol, as long as contain structural unit in the macromolecule with acidic group, this acidic group can use the copolymerization composition with acidic group to import in the macromolecule, and the hydroxyl etc. that also can make vinyl alcohol units after the polyvinyl alcohol (PVA) polymerization is with the compound reaction with acidic group and import.
As preferred sour modified polyvinylalcohol, can enumerate vinyl alcohol/phthalic acid vinyl ester copolymers, vinyl alcohol/itaconic acid copolymer etc., wherein optimal ethylene alcohol/itaconic acid copolymer etc.
The acid modified polyvinylalcohol, optimal ethylene alcohol copolymerization ratio is at the compound more than 85%.For example, as sour modified polyvinylalcohol, if use vinyl alcohol/itaconic acid copolymer, then this multipolymer optimal ethylene alcohol copolymerization ratio is more than 90%, preferred especially 95～99.5% compound.As the commercially available product of vinyl alcohol/itaconic acid copolymer, can enumerate the KL-504, the KL-506 that produce as (share) storehouse.
Consider that from the viewpoint of adjusting the oxygen block saponification degree of polyvinyl alcohol (PVA) is preferably below the above 88mol% of 40mol%.The following polyvinyl alcohol (PVA) of the preferred especially above 88mol% of saponification degree 60mol%, the most preferably following polyvinyl alcohol (PVA) of the above 88mol% of 70mol%.
As the commercially available product of saponification degree, can enumerate PVA-205, the PVA-405, PVA-420, PVA-505, KL-504, the KL-506 that produce as (share) storehouse at the polyvinyl alcohol (PVA) of above-mentioned scope.Such polyvinyl alcohol (PVA) is applicable to oxygen permeability 50ml/m 2The above 500ml/m of dayatm 2The formation of the oxygen barrier layers that dayatm is following.
The present invention is used for polyvinyl pyrrolidone, poly alkylene glycol, acrylic resin, cellulose of oxygen barrier layers etc. and also contains its derivant.
As polyvinyl pyrrolidone, can enumerate the polyvinyl pyrrolidone single polymers.In addition, as polyvinyl pyrrolidone, preferred viscosity average molecular weigh is 5,000～50,000 compound.As polyvinyl pyrrolidone, can use commercially available product, be preferably PVPK15, PVPK30 that BASF AG produces particularly.
As poly alkylene glycol, can enumerate as polyglycol, ethylene glycol/propylene glycol copolymers etc.
As polyglycol, preferable weight-average molecular weight 5,000～100,000 polyglycol.
As polyglycol, can use commercially available product, be preferably PEG#10000, PEG#5000 that (share) WAKO produces particularly.
As ethylene glycol/propylene glycol copolymers, preferred copolymerization ratio is that 90: 10～70: 30, molecular weight are 2,000～20,000 ethylene glycol/propylene glycol copolymers.
As ethylene glycol/propylene glycol copolymers, can use commercially available product, particularly, can enumerate Pu Luluonike (the プ Le ロ ニ that ADEKA company produces ッNetwork) L144, Pu Luluonike L62, PLURONIC L64, Pu Luluonike F68, Pu Luluonike P84, Pu Luluonike F9.
As acrylic resin, can enumerate as polyacrylic acid and derivant thereof.
As polyacrylic acid derivative, can enumerate as with acrylic acid slaine as the compound that constitutes the unit.As such polyacrylic acid derivative, can use commercially available product, can enumerate synthetic A Lun (ア ロ Application) A-93, A Lun A-1015, the A Lun A-1017 that produces in (share) East Asia particularly.
Can only contain a kind of water-soluble high-molecular compound in the oxygen barrier layers, also can more than 2 kinds and use.
As the content of the macromolecular compound in the oxygen barrier layers, preferably account for the 80 quality %～99.5 quality % of all solids composition of oxygen barrier layers, more preferably account for 85 quality %～99.5 quality %, more preferably account for 90 quality %～99.0 quality %.
＜surfactant 〉
Can add surfactant in the oxygen barrier layers.
As surfactant, can use as polyoxyethylene castor oil ether, the polyoxyethylene lauryl ether, the polyoxyethylene cetyl ether, polyethylene oxide alkyl ethers classes such as polyoxyethylene stearyl ether, polyoxyethylene octyl group phenylate, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonyl phenylate, polyoxyethylene alkyl esters such as polyoxyethylene stearate, Span-20, sorbitan monostearate, the sorbitan distearate, sorbitan monooleate, Span-83, sorbitan alkyl esters such as sorbitan trioleate, glyceryl monostearate, non-ionic surfactants such as monoglyceride alkyl esters such as glycerin mono-fatty acid ester; Alkyl naphthalene sulfonic acid salts such as alkyl benzene sulfonates such as neopelex, sodium butylnaphthalenesulfonate, amyl naphthalene sodium sulfonate, hexyl sodium naphthalene sulfonate, octyl group sodium naphthalene sulfonate, alkylsurfuric acid salts such as lauryl sodium sulfate, alkyl sulfonates such as sodium dodecylsulphonate, anionic surfactants such as sulfosuccinate ester salt class such as two dodecyl sodium sulfosuccinates; Alkyl betaine such as empgen BB, stearyl betaine class, amphoteric surfactantes such as amino acids.
As the particularly preferred surfactant that is used for oxygen barrier layers, can enumerate polyoxyethylene castor oil ethers surfactant.The major component castor oil of polyoxyethylene castor oil ethers surfactant is the vegetalitas non-drying oil that the seed by castor-oil plant obtains by milling process.This seed contains 35～57% oil.Contain 85% unsaturated carboxylic acid 12 hydroxyoleic acids in the composition approximately.12 hydroxyoleic acids are that end has carboxyl, 12 and has hydroxyl, 9 stearic acic derivatives with unsaturated double-bond.Polyoxyethylene castor oil ethers surfactant is that oxirane is added to major component 12 hydroxyoleic acids of this castor oil and the general name of synthetic nonionic class surfactant.In the addition process, according to condition, the hydroxyl of 12 hydroxyoleic acids and carboxyl reaction become polyester, and molecular weight also can reach 10,000 to 20,000, thereby form the surfactant of pbz polymer.
In addition, the surfactant that oxirane is added the glycerol type that is formed in 12 hydroxyoleic acids is also contained in the polyoxyethylene castor oil ethers surfactant.
The HLB of polyoxyethylene castor oil ethers surfactant is preferably 10.0～16.0, and more preferably 11.0～15.0.If HLB is then water-soluble low less than 10.0, when adding in the polyvinyl alcohol water solution, can produce muddiness.If HLB is greater than 16, water wettability is too high, and the hydroscopicity of oxygen barrier layers can increase.The weight-average molecular weight of polyoxyethylene castor oil ethers surfactant is thought of as 800～5 from friction factor and deliquescent viewpoint in addition, and 000, be preferably 1,000～3,000.
As the object lesson of such polyoxyethylene castor oil ethers surfactant, can enumerate that this grease of bamboo joint-stock company produces send Europe such (パ イ オ ニ Application) D-225, send Europe such D-240-W, send Europe such D-230, send Europe such D-236, send Europe such the Chinese mugwort horse that produces of D-225-K, flower king joint-stock company such (エ マ ノ one Application) CH-25, that CH-40 of horse that ends, that CH-60 of horse etc. ends.
When using polyoxyethylene castor oil ethers surfactant, its addition preferably accounts for 1.0～10 quality % of oxygen barrier layers all solids composition, more preferably accounts for 2.0～6.0 quality %.If addition is few, then the effect of friction factor reduction is sometimes little, and on the other hand, if addition is too much, then the coating variation of oxygen barrier layers produces the coating spot sometimes.
As the content of the surfactant in the oxygen barrier layers, preferably account for 0.1～2 quality % of oxygen barrier layers all solids composition.
The formation of＜oxygen barrier layers 〉
Oxygen barrier layers can be used to form the coating fluid of oxygen barrier layers by modulation, this coating fluid is coated on the above-mentioned photosensitive composite layer and is formed.The coating process of oxygen barrier layers can suitably use one by one coating process and any in the multi-layer coating method simultaneously, and any all it doesn't matter.
The thickness of oxygen barrier layers is preferably below the above 1.5 μ m of 0.05 μ m, more preferably below the above 1.0 μ m of 0.1 μ m.
(adhesiveness undercoat)
In photomask board, preferably on substrate (as transparency carriers such as glass baseplates), be coated with the adhesiveness undercoat.When being coated with the adhesiveness undercoat, the photosensitive composite layer is arranged on the adhesiveness undercoat.When making photomask, for exposed portion, the adhesiveness undercoat can be strengthened the adhesion between substrate and the photosensitive composite layer, and for unexposed portion, the photosensitive composite layer is peeled off easily from transparency carrier, and improves development.
As the adhesiveness undercoat, for improve and the photosensitive composite layer between adhesion, preferably have polymerizable compound.As polymerizable compound, especially preferably have the compound of ethene unsaturated link, particularly, preferably use above-mentioned " compound (ethene unsaturated compound) " described compound with ethene unsaturated link.As the ethene unsaturated group, preferred (methyl) acryloyl group, styryl, the allyl ether of using.
In addition, in order to improve the adhesion with substrate, the adhesiveness undercoat preferably contains the compound with silicyl.The preferred especially compound that uses above-mentioned ethene unsaturated compound and have silicyl.
As the contained compound of adhesiveness undercoat, particularly, be preferably the 3-TSL 8330, the octyl group trimethoxy silane, 3-cyano group propyl-triethoxysilicane, [2-(3,4-epoxy radicals cyclohexyl) ethyl] trimethoxy silane, phenyltrimethoxysila,e, the 3-glycidoxypropyltrime,hoxysilane, allyltrimethoxysilanis, the vinyl methoxy silane, 3-(N, the N-diethylamino) propyl trimethoxy silicane, ethyl trimethoxy silane, the hexyl trimethoxy silane, p-styryl trimethoxy silane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane wherein is preferably the 3-methacryloxypropyl trimethoxy silane especially, 3-methacryloxypropyl methyldiethoxysilane.
The amount of being coated with of adhesiveness undercoat in dry mass, is preferably 2mg/m 2～200mg/m 2, 5mg/m more preferably 2～100mg/m 2
So, on substrate, form the photosensitive composite layer that contains (A)～(E) each composition, preferably form oxygen barrier layers, thereby obtain photomask board of the present invention on this surface.Be preferably formed the adhesiveness undercoat this moment between substrate and photosensitive composite layer.
[manufacture method of photomask and photomask]
Photomask of the present invention is characterised in that it uses the photomask board of having stated of the present invention, has the light shield layer that the photosensitive composite that photomask board is had develops behind image exposure and forms.
Particularly, with near ultraviolet ray or visible light the photomask board of having stated is carried out image exposure (exposure process), use the photomask board development after developer solution makes exposure then, remove the unexposed portion (developing procedure) of photosensitive composite layer, can obtain having the photomask of the decent light shield layer of figure (exposed portion).
As the photomask (photomask of the present invention) that uses photomask board of the present invention to make, suitable form is to use the laser (more preferably radiating the following laser of the above 450nm of 390nm) of the following light of the radiation above 450nm of 350nm that this photomask board is carried out image exposure, then the photomask that develops and make.
[exposure process]
Exposure process is preferably as follows: make photomask board carry out the decent exposure of figure by the transparent original painting with line image, halftone dot image etc., or make photomask board carry out the decent exposure of figure by digital data laser scanning etc.Image to photomask board of the present invention forms, and is fit to use laser explosure.
As exposure light source, preferably radiate the laser of the following scope light of the above 450nm of 350nm, concrete, the InGaN based semiconductor laser is suitable.
Laser as the following scope light of the radiation above 450nm of 350nm is listed below.
＜gas laser 〉
Can enumerate Ar ion laser (364nm, 351nm), Kr ion laser (356nm, 351nm), He-Cd laser instrument (441nm, 325nm) etc.
＜solid state laser 〉
Can enumerate Nd:YAG (YVO 4) and the combination (430nm) of combination (355nm), Cr:LiSAF and the SHG crystallization of THG crystallization etc.
＜semiconductor laser class 〉
Can enumerate KNbO 3Ring type resonant device (430nm), waveguide type wavelength inverting element and the semi-conductive combination of AlGaAs, InGaAs (380nm～450nm), waveguide type wavelength inverting element and the semi-conductive combination of AlGaInP, AlGaAs (300nm～350nm), AlGaInN (350nm～450nm) etc.
＜other laser instrument 〉
As pulsed laser, can enumerate N 2Laser instrument (337nm), XeF (351nm) etc.
Wherein, consider that (InGaN based semiconductor laser device 400nm～410nm) is specially suitable to the AlGaIn semiconductor laser from wavelength characteristic, cost face.
[developing procedure]
As developer solution, can enumerate the described developer solution of special public clear 57-7427 communique, inorganic alkaline agents such as sodium silicate, potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, sodium phosphate, dibastic sodium phosphate, ammonium phosphate, ammonium hydrogen phosphate, sodium metasilicate, sodium bicarbonate, ammoniacal liquor, perhaps the aqueous solution of organic basic such as monoethanolamine or diethanolamine reagent is suitable.Such alkaline reagent is 0.1～10 quality % with the concentration of the alkaline aqueous solution that contains them, and the mode of preferred 0.5～5 quality % is added.
In the alkaline aqueous solution as the developer solution use, can add a spot of surfactant or benzyl alcohol, 2-phenoxetol, the such organic solvent of butoxy ethanol as required.Can enumerate compound as No. the 3375171st, United States Patent (USP) and same No. 3615480 record.Also have special open clear 50-26601 number, with 58-54341 number, spy open clear 56-39464 number, also be good with the developer solution of 56-42860 number each communique record.
As particularly preferred developer solution, can enumerate and contain the nonionic compound that the spy opens 2002-202616 communique record, pH is 11.5～12.8 and developer solution with 3～30mS/cm conductivity.
In the developing procedure,, can enumerate manual process, dip treating and mechanical treatment etc. as the form of the photomask board after the developer solution contact exposure.
As manual process, can enumerate as: make sponge or absorbent cotton fully contain developer solution, wiping photomask board integral body is handled, and the fully form of washing of back handle to end.
As dip treating, can enumerate to impregnated in enamel tray that developer solution is housed or the dark container and stir, then the method for fully washing with absorbent cotton or wiping limit, sponge limit as: the photomask board after will exposing.Dip time is preferably about 60 seconds.
Mechanical treatment can use automatic processing machine.As the situation of using automatic processing machine, for example the developer solution of packing in the developing trough is drunk up with pump, be sprayed onto the processing mode of the photomask board after the exposure by nozzle, in filling the groove of developer solution, by deflector roll in the liquid etc., dipping is carried the processing mode of the photomask board after the exposure, and untapped developer solution is supplied with by the required amount of the photomask board after each piece exposure, be disposable processing mode, more than any mode all be suitable for.For any mode, be equipped with more preferably that high pressure is cleaned, mechanisms such as brush or glue suede.In addition, also can utilize the device of laser instrument exposed portion and automatic processing machine part one assembling.
In addition, the temperature of developer solution is preferably 20 ℃～35 ℃ scope, more preferably 25 ℃～30 ℃ scope during as development.
[other operation]
For photomask board, as required, before exposure, the exposure in, in the process from exposing to developing, can implement comprehensive heat treated.By implementing heat treated, can promote that the image in the photographic layer forms reaction, improve the stability of light sensitivity and light sensitivity etc.In addition, in order to improve image intensity, the image after developing is carried out back heating comprehensively or blanket exposure also is effective.
Usually the heating before developing is preferably carried out under the condition of the gentleness below 150 ℃.On the other hand, the heating after the development can utilize very strong condition, carries out under 150～500 ℃ scope usually.
In addition, photomask board is being carried out after image forms, the diaphragm of the epoxy resin etc. of thermohardening type can be set on image.By diaphragm is set, can more improve film strength on image.
As above use photomask board of the present invention, can obtain photomask (photomask of the present invention).
The thickness of the light shield layer of photomask of the present invention is preferably below the above 2.0 μ m of 0.8 μ m, more preferably below the above 1.8 μ m of 0.8 μ m.
Optical density (OD) under the 360nm of the light shield layer of photomask of the present invention (O.D.) is preferably more than 3.5 below 7.0, more preferably more than 4.0 below 7.0.
The only form of the light shield layer of photomask of the present invention is the thickness of light shield layer and the form that the O.D. both sides under the 365nm satisfy above-mentioned scope.
Because photomask board of the present invention can form high-resolution image, therefore can under the edge line good state, form the image of fine live width.One of suitable form of using the photomask that such photomask board forms is the preferred form below 30 μ m more than the 0.1 μ m of live width of line in the light shield layer and gap (L/S).The live width of formed L/S preferably below 25 μ m more than the 0.1 μ m, more preferably below 20 μ m more than the 0.1 μ m, by the photomask board of the invention described above, can form the light shield layer of the L/S with above-mentioned fine live width.
The gained photomask has under the situation of defective, can carry out defect correction with following method.
At this, for the defective of photomask, mainly be meant the dawn part of black part under the situation of black part, the defective of the light transmission such like an elephant pin hole.And be meant under the situation of white portion, for example, should become on the transparency carrier of white portion the defective that light transmission rate is reduced with impurity or photosensitive layer.Black part is divided under the situation that dawn takes place, and by photosensitive layer coating fluid (photosensitive composite) is coated the defective periphery, removes photosensitive layer not with the development of HeCd laser explosure, can corrective pitting.In addition, need not develop, will not want part with YAG laser and ablate that remove also can corrective pitting.Under the situation of white portion defective, can remove with the YAG laser ablation.In this case, different with the Em mask, do not have organic principles such as photosensitive layer on the white portion, so can not produce new defective during laser ablation.
Use photomask board of the present invention, can obtain the good photomask of rectilinearity of resolution height, image border part.In addition, can obtain photomask by simple operation high productivity.The defect correction of photomask is also easier, can make cheap photomask.
Use the photomask of photomask board gained of the present invention, go for the lithoprinting operation in fields such as flat pannel display such as PDP, FED, LCD, CRT shadow mask, printed circuit board (PCB), semiconductor.
When the photomask that the present invention is used is used for the pattern formation of ultraviolet photonasty diaphragm, bandpass filter is assembled into ultraviolet exposure machines such as extra-high-pressure mercury vapour lamp, can selects exposure wavelength.
[embodiment]
The present invention is described by the following examples in further detail, but the present invention not only is defined in these embodiment.
[embodiment 1～3, comparative example 1～2]
1. the making of photomask board
(formation of photosensitive composite layer)
The photosensitive composite layer of following composition is coated glass substrate with coating fluid composition (P-1), and (on the 10cm * 10cm), making drying coated quality is 1.4g/m 2,, form the photosensitive composite layer in 100 ℃ of dryings 1 minute.
＜photosensitive composite layer coating fluid composition (P-1) 〉
Carbon black dispersion liquid (dispersion liquid of following composition) 16.0 mass parts
Ethene unsaturated compound (C-1) (compound of following structure) 4.2 mass parts
Binder polymer (D-1) (polymer binder 3.6 mass parts of following structure
(MW：50000)
Optical whitening agent or comparison sensitizing coloring matter (compound shown in the table 2 and amount) 0.21 mass parts
Polymerization initiator (compound shown in the table 2) 0.81 mass parts
Chain-transferring agent (F-1) (compound of following structure) 0.3 mass parts
Fluorine class non-ionic surfactant 0.05 mass parts
(the wheat loud, high-pitched sound is sent out storehouse (メ ガ Off ァ ッNetwork) F780, big Japanese ink chemical industry (share) are produced)
Methyl ethyl ketone 58 mass parts
Propylene glycol methyl ether acetate 53 mass parts
[table 2]
(A) optical whitening agent or comparison sensitizing coloring matter The addition of optical whitening agent or comparison sensitizing coloring matter (B) polymerization initiator
Embodiment 1 ??A-1 0.21 mass parts ??B-1
Embodiment 2 ??A-2 0.21 mass parts ??B-1
Embodiment 3 ??A-3 0.21 mass parts ??B-1
Comparative example 1 3,3 '-carbonyl two (7-dimethylamino cumarin) 0.21 mass parts ??CGI7460
(A) optical whitening agent or comparison sensitizing coloring matter The addition of optical whitening agent or comparison sensitizing coloring matter (B) polymerization initiator
Comparative example 2 3,3 '-carbonyl two (7-dimethylamino cumarin) 0.21 mass parts ??B-1
Be used to modulate photosensitive composite layer composed as follows with the carbon black dispersion liquid of coating fluid composition (P-1).
The composition of＜carbon black dispersion liquid 〉
Carbon black 13.1 mass parts
(the assorted Japan of trade name: Nipex35, Ai Bainikedaigu (エ ボ ニ ッNetwork デ グ サ ジ ャThe パ Application)
(share) produced)
Spreading agent (compound of following structure) 0.65 mass parts
[changing 38]
Figure G200910164560XD0000451
Polymkeric substance 6.72 mass parts
(random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand)
Propylene glycol methyl ether acetate 79.53 mass parts
The photosensitive composite layer of embodiment and comparative example is as follows with the details and the structure of the employed optical whitening agent of the modulation of coating fluid composition (A-1)～(A-3), polymerization initiator (B-1), the compound (C-1) that contains the ethene unsaturated link, binder polymer (D-1) and chain-transferring agent (F-1).In addition, polymerization initiator: CGI7640 is the commercially available initiating agent (organic boronic salt Photoepolymerizationinitiater initiater) that vapour crust beggar one (チ バ ガ イ ギ one) company produces.
Optical whitening agent (A-1): I-1-1-2 compound (addition 0.21 mass parts)
Optical whitening agent (A-2): I-6-1-1 compound (addition 0.21 mass parts)
Optical whitening agent (A-3): I-7-1-1 compound (addition 0.21 mass parts)
[changing 39]
Figure G200910164560XD0000461
(formation of oxygen barrier layers)
The oxygen barrier layers coating fluid of following composition is coated on each photosensitive composite layer,, formed oxygen barrier layers 100 ℃ of dryings 2 minutes.The thickness of oxygen barrier layers (μ m) is directly measured with " SURFCOM130A, Tokyo precision (share) system ", is 0.2 μ m.In addition, measure the oxygen permeability of this oxygen barrier layers, be 170ml/m with said method 2Dayatm.
＜oxygen barrier layers coating fluid 〉
Water 87g
PVA-405 (storehouse produces) 6g
PVA-K30 (BASF AG's production) 6g
EMALEX710 (Japanese emulsion (エ マ Le ジ ョApplication) (share) production, surfactant) 1g
As above operation obtains having possessed on the transparency carrier photomask board of embodiment 1～3 of photosensitive composite layer and oxygen barrier layers and the photomask board of comparative example 1～2.
2. the evaluation of photomask board
(1) light sensitivity evaluation
With each photomask board of above embodiment that obtains and comparative example (10cm * 10cm), expose as laser plotter with VIOLD (big Japanese Si Kulin (ス Network リ one Application) makes (share) and produces) (laser instrument output 350mW, light source is the 405nm violet laser).Each photomask board after then will exposing developed in 30 ℃ of alkaline-based developer 1L that impregnated in following composition in 15 seconds, and the washing back is dry.180 ℃ of heat treated 30 minutes, obtain desirable photomask again.The exposure light sensitivity is to find the exposure of the line/gap 20 μ m/20 μ m that reproduce this photomask to estimate as the suitableeest exposure by continuous variation exposure.This numerical value is more little to form image with ISO more.The results are shown in following table 3.
Photomask after development, the heat treated is about 4.0 in the absorbance of 365nm.
In addition, to detain the thickness of the light shield layer that mother (サ one Off コ) 480A measures recklessly be 1.5 μ m to the Sa made from Tokyo precision (share) company.
＜alkaline-based developer is formed 〉
The aqueous solution that comprises the pH11.95 of following composition
Potassium hydroxide 0.2g
1K potassium silicate 2.4g
(SiO 2/K 2O＝1.9)
Following compound 5.0g
Ethylenediamine tetraacetic acid 4Na salt 0.1g
Water 91.3g
[changing 40]
Figure G200910164560XD0000471
(2) resolving power determination, image border part rectilinearity are estimated
Each photomask board (10cm * 10cm), expose as laser plotter with embodiment and comparative example with VIOLD (big Japanese Si Kulin makes (share) and produces) (laser instrument output 350mW, light source is the 405nm violet laser).Each photomask board after then will exposing developed in 30 ℃ of alkaline-based developer 1L that impregnated in following composition in 15 seconds, and the washing back is dry.180 ℃ of heat treated 30 minutes, obtain desirable photomask again.Constantly change exposure and form image, exposure during with line/gap 20 μ m/20 μ m of playback light mask is decided to be the suitableeest exposure, describe the line/gap with 4,6,8,15,20,25,30 μ m under the condition simultaneously, the thinnest live width is decided to be resolution in the line/gap that can reproduce.
Use the marginal portion photography of microscope that (share) Kai Ansi (キ one エ Application ス) company makes again, the linear deviation chart of marginal portion is shown standard deviation 20 μ m lines.The more little expression rectilinearity of σ value is good more.
(3) storage stability evaluation
The variation of exposure rate is estimated
Each photomask board (60 ℃) under hot conditions of embodiment and comparative example was preserved 3 days, same with above-mentioned (1) light sensitivity evaluation then, change exposure light amount, the exposure when seeking line/gap 20 μ m/20 μ m reproduction.The suitableeest exposure (X of initial stage shown in the result that above-mentioned (1) light sensitivity is estimated 0) and the exposure (X of preservation after 3 days 3) poor (X 0-X 3) very little, the variation of exposure rate (%) shown in the following formula is decided to be the value of storage stability, if this value in 10%, it is good then to be evaluated as storage stability.
Variation of exposure rate (%)=(X 0-X 3)/X 0* 100
[table 3]
Optimum light quantity (mJ/cm 2) Resolution (μ m) Rectilinearity σ Storage stability
Embodiment 1 ??80 ??15 ??2.9 ??5.5
Optimum light quantity (mJ/cm 2) Resolution (μ m) Rectilinearity σ Storage stability
Embodiment 2 ??150 ??10 ??3.8 ??6.6
Embodiment 3 ??180 ??15 ??5.5 ??8.7
Comparative example 1 ??1000↑ Can not measure Can not measure Can not measure
Comparative example 2 ??1000↑ Can not measure Can not measure Can not measure
(1000 ↑ be illustrated in 1000mJ/cm 2Under the following exposure, line/gap 20 μ m/20 μ m can not reproduce.)
The photomask board light sensitivity height of each embodiment as shown in Table 3, and storage stability is good, the resolution height of the photomask that obtains thus, the rectilinearity of image border part is outstanding.

Claims (16)

1. photomask board, it has on substrate: comprise compound that at least a optical whitening agent shown in (A) following formula (I-1)～following formula (I-15), (B) polymerization initiator, (C) have the ethene unsaturated link, (D) binder polymer and (E) the photosensitive composite layer of light screening material
Figure F200910164560XC0000011
Figure F200910164560XC0000021
Wherein, compound shown in formula (I-1)～formula (I-15) can have substituting group, also can not have substituting group, and X represents to be selected from the divalent concatenating group in the structure shown below in the formula, * in the following structure represent with formula (I-6) and formula (I-13) in the binding site of heterocycle
Figure F200910164560XC0000022
2. photomask board according to claim 1, wherein,
The substituting group of described (A) optical whitening agent is to be selected from least a in alkyl, aryl, alkoxy, alkyl-carbonyl, alkoxy carbonyl, acyloxy, carboxyl, itrile group, amino, hydroxyl, alkyl sulphonyl, amino-sulfonyl and the halogen atom.
3. photomask board according to claim 1, wherein,
The molar absorptivity (ε) of described (A) optical whitening agent is more than 1000.
4. photomask board according to claim 1, wherein,
The molecular weight of described (A) optical whitening agent is more than 200 and below 2000.
5. photomask board according to claim 1, wherein,
The content of described (A) optical whitening agent is 0.1～10 quality % in all solids composition of photosensitive composite layer.
6. photomask board according to claim 1, wherein,
The oxygen permeability that also has on the described photosensitive composite layer under 25 ℃ is 50ml/m 2Above and the 500ml/m of dayatm 2The oxygen barrier layers that dayatm is following.
7. photomask board according to claim 6, wherein,
Contain water-soluble high-molecular compound in the described oxygen barrier layers.
8. photomask board according to claim 6, wherein,
The thickness of described oxygen barrier layers is more than the 0.05 μ m and below the 1.5 μ m.
9. photomask board according to claim 1, wherein,
Described substrate is the clear glass that thick 0.1mm is above and 20mm is following.
10. photomask board according to claim 1, wherein,
Described (B) polymerization initiator is at least a polymerization initiator that is selected from hexa-aryl bi-imidazole compound, metallocene compound, triaizine compounds, oxime ester compound and the organic borate.
11. photomask board according to claim 1, wherein,
The content of described (B) polymerization initiator in the photosensitive composite layer is 0.1～20 mass parts with respect to all solids composition 100 mass parts that constitute the photosensitive composite layer.
12. photomask board according to claim 1, wherein,
The molecular weight of described (D) binder polymer counts 5,000～300 with weight-average molecular weight, 000.
13. photomask board according to claim 1, wherein,
The content of described (E) light screening material is 10 quality %～50 quality % in all solids composition of photosensitive composite layer.
14. a photomask, it has: by the light shield layer that any photosensitive composite layer that described photomask board had in the claim 1～13 is carried out develop and form behind the image exposure.
15. photomask according to claim 14, wherein,
Utilize 350nm light above and that 450nm is following to carry out described exposure.
16. photomask according to claim 14, wherein,
The live width in line in the described light shield layer and gap (L/S) is more than the 0.1 μ m and below the 20 μ m.
CN200910164560A 2008-09-30 2009-07-20 A photomask board and photomask Pending CN101713913A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105404092A (en) * 2015-12-01 2016-03-16 冠橙科技股份有限公司 Photomask substrate and photomask
CN109369612A (en) * 2018-12-17 2019-02-22 桂林理工大学 A kind of aryl radical precursor molecule of symmetrical configuration and preparation method thereof
CN110225665A (en) * 2015-07-30 2019-09-10 日立化成株式会社 Photosensitive element, barrier layer form the manufacturing method for using resin combination, the forming method of resist pattern and printing distributing board
CN110945428A (en) * 2017-07-20 2020-03-31 旭化成株式会社 Photosensitive resin structure for printing plate and method for producing same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110225665A (en) * 2015-07-30 2019-09-10 日立化成株式会社 Photosensitive element, barrier layer form the manufacturing method for using resin combination, the forming method of resist pattern and printing distributing board
CN110225665B (en) * 2015-07-30 2021-04-06 昭和电工材料株式会社 Photosensitive element
CN105404092A (en) * 2015-12-01 2016-03-16 冠橙科技股份有限公司 Photomask substrate and photomask
CN110945428A (en) * 2017-07-20 2020-03-31 旭化成株式会社 Photosensitive resin structure for printing plate and method for producing same
US11796914B2 (en) 2017-07-20 2023-10-24 Asahi Kasei Kabushiki Kaisha Photosensitive resin structure for printing plate, and method for producing same
CN109369612A (en) * 2018-12-17 2019-02-22 桂林理工大学 A kind of aryl radical precursor molecule of symmetrical configuration and preparation method thereof

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