WO2009123109A1 - 感光性透明樹脂組成物、カラーフィルタの製造方法及びカラーフィルター - Google Patents
感光性透明樹脂組成物、カラーフィルタの製造方法及びカラーフィルター Download PDFInfo
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- WO2009123109A1 WO2009123109A1 PCT/JP2009/056491 JP2009056491W WO2009123109A1 WO 2009123109 A1 WO2009123109 A1 WO 2009123109A1 JP 2009056491 W JP2009056491 W JP 2009056491W WO 2009123109 A1 WO2009123109 A1 WO 2009123109A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
Definitions
- the present invention relates to a color filter used for a liquid crystal display element (LCD) and an image sensor (CCD, CMOS), a method for producing the color filter, and a photosensitive transparent resin composition used for producing the color filter.
- the present invention relates to a photosensitive transparent resin composition that is excellent in resolution, suppresses development residue, reduces pixel thickness, and forms a desired image pattern, a color filter manufacturing method using the same, and a color filter.
- a transparent resin layer pattern may be formed in accordance with each purpose.
- a photospacer see, for example, FIG. 4 and Patent Documents 1 and 2 used for maintaining a predetermined cell gap between the color filter layer and the TFT layer, and MVA (Multi -domain Vertical Alignment)
- a pattern of a transparent resin layer is formed by a color filter or the like of a liquid crystal display device (for example, see Patent Documents 3 and 4).
- the photo spacer may be formed on the display screen, that is, on RGB.
- a pattern is formed with a photosensitive transparent resin composition, and one color of a plurality of color filters may be white (transparent) for the purpose of increasing sensitivity (for example, FIG. 3).
- Patent Document 5 As a background, for the purpose of improving the resolution, pixel miniaturization has been progressed with the increase in the number of pixels. However, on the other hand, the opening becomes small, leading to a decrease in sensitivity. Therefore, in order to compensate for the decrease in sensitivity, one color of the color filter is made white (transparent) to increase the sensitivity.
- the characteristics, shapes, and the like required for pattern formation of the transparent resin layer are different from each other, they have a common problem. That is, since the transparent resin film easily transmits light of active energy rays (i-line or the like), there is a problem that the pattern line width of the transparent resin layer is easily increased, and the resolution and pattern shape are deteriorated. In particular, in a color filter for an image sensor, in addition to the above problem, pattern formation on a wafer often causes pattern resolution on the transparent resin layer due to exposure halation.
- the problem of exposure illuminance dependency is difficult only by adjusting the type and amount of the initiator, particularly when the i-line transmittance is a coating film.
- a measure to increase the start amount is used in order to improve the exposure illuminance dependency.
- the line width is too thick, the resolution is deteriorated, or a peripheral residue due to exposure halation is generated.
- Patent Document 6 a technique for improving the resolution of a pattern and reducing the illuminance of an exposure machine by using an antioxidant is disclosed (for example, see Patent Document 6).
- Patent Documents 7 and 8 a technique for improving the resolution of a pattern by adding a pigment or a dye and reducing the transmittance at an exposure wavelength is disclosed (for example, Patent Documents 7 and 8).
- the transmittance of visible light falls to the transparent pattern.
- the present invention has been made in view of the above, and exposure illuminance dependency (particularly, shape variation such as line width at low illuminance of 95% or less of high illuminance) is suppressed to be small, and the remaining film ratio is high.
- a photosensitive transparent resin composition capable of stably forming a pattern with little development residue and excellent resolution, and a color filter capable of displaying a fine and high-quality image with little decrease in visible light transmittance. And it aims at providing the manufacturing method, and makes it a subject to achieve this objective.
- a photosensitive transparent resin composition comprising at least a polymerizable monomer, an alkali-soluble resin, a photopolymerization initiator, and a compound represented by the following general formula (I).
- R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 1 and R 2 may be the same or different from each other, but do not represent a hydrogen atom at the same time, and R 1 and R 2 may form a cyclic amino group together with a nitrogen atom.
- R 3 and R 4 each independently represents an electron withdrawing group.
- R 3 and R 4 may combine with each other to form a cyclic electron withdrawing group.
- the content of the compound represented by the general formula (I) is 0.01 to 30% by mass in the total solid content of the photosensitive transparent resin composition, described in ⁇ 1> above Photosensitive transparent resin composition.
- ⁇ 4> Applying the photosensitive transparent resin composition according to any one of the above items ⁇ 1> to ⁇ 3>, and exposing and developing the coated layer formed with at least ultraviolet rays through a photomask.
- exposure illuminance dependency (particularly, shape variation such as line width at a low illuminance of 95% or less of high illuminance) is suppressed to be small, the residual film ratio is high, the development residue is small, and the resolution is reduced.
- the photosensitive transparent resin composition which can form the pattern excellent in the property stably can be provided.
- ADVANTAGE OF THE INVENTION According to this invention, the fall of the transmittance
- the photosensitive transparent resin composition of the present invention the color filter constituted by using the photosensitive transparent resin composition, and the production method thereof will be described in detail.
- the photosensitive transparent resin composition of the present invention is constituted by containing at least a polymerizable monomer, an alkali-soluble resin, a photopolymerization initiator, and a compound represented by the following general formula (I) (ultraviolet absorber). Generally, a solvent is used.
- the photosensitive transparent resin composition of the present invention contains at least one compound represented by the following general formula (I), which is a conjugated diene compound, as an ultraviolet absorber.
- this conjugated diene compound suppresses subsequent development performance fluctuations particularly when low-illuminance exposure is performed, so it is related to pattern formability such as pattern line width, film thickness, and spectral spectrum. Dependence on exposure illuminance can be suppressed.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 1 and R 2 May be the same or different from each other, but do not represent a hydrogen atom at the same time.
- the alkyl group having 1 to 20 carbon atoms represented by R 1 or R 2 may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, i-propyl group N-butyl group, i-butyl group, n-hexyl group, cyclohexyl group, n-decyl group, n-dodecyl group, n-octadecyl group, and eicosyl group.
- the alkyl group having 1 to 20 carbon atoms represented by R 1 or R 2 may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen atom.
- the number of carbon atoms of the substituent that the alkyl group as R 1 and R 2 may have is preferably 10 or less.
- the number of carbon atoms of 1 to 20 for the alkyl group represented by R 1 or R 2 includes the number of carbon atoms of the substituent.
- the alkyl group having a substituent include methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, phenethyl group, benzyl group, p -T-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- A furylethyl group etc.
- the alkyl group having 1 to 20 carbon atoms represented by R 1 and R 2 is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or an n-hexyl group.
- the aryl group having 6 to 20 carbon atoms represented by R 1 or R 2 may be a monocyclic ring or a condensed ring, and is either a substituted aryl group having a substituent or an unsubstituted aryl group. There may be. Examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like.
- Examples of the substituent of the substituted aryl group include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, a cyano group, and an alkyloxy.
- Examples include a carbonyl group, an aryloxycarbonyl group, a substituted carbamoyl group, a substituted sulfamoyl group, a nitro group, a substituted amino group, an alkylsulfonyl group, and an arylsulfonyl group.
- the number of carbon atoms of the substituent that the aryl group as R 1 and R 2 may have is preferably 10 or less.
- the number of carbon atoms of 6 to 20 for the aryl group represented by R 1 or R 2 includes the number of carbon atoms of the substituent.
- a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are particularly preferable.
- R 1 and R 2 may form a cyclic amino group together with the nitrogen atom.
- the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.
- R 1 and R 2 are each a lower alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl) , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (for example, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, etc.) preferable. It is also preferred that R 1 and R 2 are combined to form a ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring) containing the nitrogen atom represented by N in the formula.
- a ring for example,
- R 3 and R 4 each independently represents an electron withdrawing group.
- the electron-withdrawing group is an electron-withdrawing group having a Hammett's substituent constant ⁇ p value (hereinafter simply referred to as “ ⁇ p value”) of 0.20 or more and 1.0 or less.
- ⁇ p value a Hammett's substituent constant
- ⁇ p value a Hammett's substituent constant
- it is an electron withdrawing group having a ⁇ p value of 0.30 or more and 0.8 or less.
- Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. .
- Substituent constants obtained by Hammett's rule include a ⁇ p value and a ⁇ m value, and these values are described in many general books. For example, the JA Dean edition “Lange's Handbook of Chemistry” “Twelfth edition, 1979 (Mc Graw-Hill)", “Chemical domain special issue", 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, 1991 detailed. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.
- the electron withdrawing group having a ⁇ p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group.
- R 3 is preferably a cyano group, a group selected from —COOR 5 , —CONHR 5 , —COR 5 , —SO 2 R 5 , and R 4 is cyano.
- a group selected from the group, —COOR 6 , —CONHR 6 , —COR 6 , —SO 2 R 6 is preferred.
- R 5 and R 6 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R 5 and R 6 have the same meanings as in R 1 and R 2 , and the preferred embodiments are also the same.
- R 3 and R 4 acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group are preferable.
- an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.
- R 3 and R 4 may be bonded to each other to form a cyclic electron withdrawing group. Examples of the cyclic electron withdrawing group formed by combining R 3 and R 4 with each other include a 6-membered ring containing two carbonyl groups.
- R 1 , R 2 , R 3 , and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.
- other monomers include acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters and amides such as Acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate , Lauryl methacrylate, methylenebisacrylamide, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, methacryloni Tolyl, aromatic vinyl compounds (for example, styrene and its derivatives such as vinyl toluen
- acrylic acid esters methacrylic acid esters, and aromatic vinyl compounds are particularly preferable.
- Two or more of the above comonomer compounds can also be used together.
- n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid, or the like can be used.
- the content of the compound represented by the general formula (I) (conjugated diene compound) in the photosensitive transparent resin composition of the present invention is 0.01% by mass to 30% with respect to the total solid content of the composition. % By mass is preferable, 0.01% by mass to 20% by mass is more preferable, and 0.01% by mass to 15% by mass is particularly preferable.
- the content of the conjugated diene compound (ultraviolet absorber) is 0.01% by mass or more, the light shielding ability at the time of exposure is good and the pattern line width is prevented from being increased due to excessive progress of polymerization. It is easy to obtain the line width and the generation of peripheral residues is further suppressed.
- it is 30% by mass or less the light shielding ability at the time of exposure is not too strong, and the polymerization proceeds better.
- the change in the pattern line width as described above becomes conspicuous in a transparent photocurable composition with little light absorption with respect to ultraviolet rays such as g-line, h-line and i-line as exposure light sources. Therefore, the compound represented by the general formula (I) (conjugated diene compound) is particularly effective when constituting a transparent photosensitive transparent resin composition.
- Photopolymerization initiator examples include halomethyloxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428, and the like. Active halogen compounds such as halomethyl-s-triazine as described, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. US Pat. No. 4,318,871 and European Patent Publication EP-88050A, Aromatic ketone compounds such as benzophenones described in US Pat. No.
- photopolymerization initiator examples include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.
- acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.
- ketal photopolymerization initiator examples include benzyldimethyl ketal and benzyl- ⁇ -methoxyethyl acetal.
- benzophenone photopolymerization initiator examples include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl.
- Preferred examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, and the like.
- benzoin-based or benzoyl-based photopolymerization initiator examples include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.
- Preferred examples of the xanthone photopolymerization initiator include diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chlorothioxanthone, and the like.
- triazine photopolymerization initiator examples include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxysty
- halomethyl oxadiazole photopolymerization initiator examples include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3
- a preferred example is 4-oxodiazole.
- Preferred examples of the acridine series photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.
- Examples of the coumarin photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.
- lophine dimer-based photopolymerization initiator examples include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer.
- 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.
- biimidazole photopolymerization initiator examples include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide, and the like.
- Examples of the oxime ester photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl- Preferable examples include 4 ′-(benzmercapto) benzoyl-hexyl-ketoxime.
- 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt and the like can be mentioned.
- an oxime ester compound is preferable in that it can be highly sensitive by addition in a small amount when used in combination with the conjugated diene compound represented by the general formula (I).
- O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone is most preferred.
- the content of the photopolymerization initiator in the photosensitive transparent resin composition is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0%, based on the total solid content of the composition. % By mass.
- the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.
- thermal polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.
- the photosensitive transparent resin composition of the present invention contains at least one polymerizable monomer.
- a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable.
- the photosensitive transparent resin composition of the present invention can be constituted in a negative type.
- polymerizable monomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxy) (Chill) isocyanurate, polyfunctional alcohols such as
- the content of the polymerizable monomer in the photosensitive transparent resin composition is preferably 10 to 80% by mass and more preferably 10 to 40% by mass with respect to the total solid content of the composition.
- the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the unexposed area, maintain a sufficient degree of cure of the exposed area, and significantly reduce the elution of the unexposed area. Can be prevented.
- Alkali-soluble resin The photosensitive transparent resin composition of the present invention can be constituted using an alkali-soluble resin.
- the alkali-soluble resin is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
- the alkali-soluble resin is preferably a linear organic polymer and is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
- linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957.
- examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer.
- acidic cellulose derivatives having a carboxylic acid in the side chain are useful.
- alkali-soluble resins include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinyl Pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful.
- the linear organic polymer may be a copolymer of hydrophilic monomers.
- examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight
- Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like.
- hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric acid ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and groups derived from salts thereof, morpholinoethyl group, etc. Including monomers are also useful.
- the alkali-soluble resin may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful.
- polymer having a polymerizable group examples include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like.
- KS resist-106 manufactured by Osaka Organic Chemical Industry Co., Ltd.
- cyclomer P series manufactured by Daicel Chemical Industries, Ltd.
- alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
- polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
- acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
- acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
- acrylic resin examples include a copolymer obtained by polymerization of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, and (meth) acrylamide, and a commercially available product.
- KS resist-106 manufactured by Osaka Organic Chemical Industry Co., Ltd.
- cyclomer P series manufactured by Daicel Chemical Industries, Ltd.
- the alkali-soluble resin a polymer having a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 ⁇ 10 5 is preferable from the viewpoint of developability, liquid viscosity, etc., and 2000 to 1 ⁇ 10 5 is preferable.
- a polymer is more preferred, and a polymer of 5000 to 5 ⁇ 10 4 is particularly preferred.
- the content of the alkali-soluble resin in the photosensitive transparent resin composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total solid content of the composition, from the viewpoint of developability and the like. 30 to 70% by mass is particularly preferable.
- the photosensitive transparent resin composition of the present invention can generally be constituted using an organic solvent.
- the organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the photosensitive transparent resin composition, but in particular, considers the solubility, applicability, and safety of the UV absorber and binder. Is preferably selected.
- organic solvent examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate.
- esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate.
- Ethyl lactate methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;
- 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .
- 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropionate Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropi Methyl acetate, ethyl 2-ethoxy-2-methylpropionate, etc .; methyl pyruvate
- Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;
- Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.
- these organic solvents may be used in combination of two or more from the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coating surface state, etc., in particular, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene
- a mixed solution composed of two or more selected from glycol methyl ether acetate is preferably used.
- the content of the organic solvent in the photosensitive transparent resin composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass from the viewpoint of applicability, and is further 5 to 60% by mass. 10 to 50% by mass is preferable.
- additives for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants are added as necessary.
- An agent, an anti-agglomeration agent, etc. can be blended.
- additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimet Adhesion promoters such as silane, 3-chloro
- the photosensitive transparent resin composition of the present invention is an organic carboxylic acid, preferably an organic carboxylic acid, preferably, when promoting alkali solubility in the UV-irradiated part of the photosensitive transparent resin composition and further improving developability.
- a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be contained.
- organic carboxylic acid examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid Aliphatic dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid Acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene
- ⁇ Method of forming transparent pattern with color filter for image sensor ⁇ A method for forming a transparent pattern of a color filter using the photosensitive transparent resin composition of the present invention for the purpose of increasing sensitivity with an image sensor will be described.
- the photosensitive transparent resin composition is applied directly or through another layer on a silicon wafer, and then dried to form a coating film (coating film forming process), and on the coating film,
- a step of exposing a specific pattern exposure step
- a step of developing the exposed coating film with an alkaline developer development step
- post-baking a step of performing a heat treatment on the developed coating film
- a pattern can be formed through these processes.
- the process of hardening the said resist pattern by heating and exposure as needed may be included.
- a method for applying the photosensitive transparent resin composition for example, various methods such as a spray method, a roll coating method, and a spin coating method can be used.
- the coating layer formed in the coating film forming step is exposed by irradiating actinic rays or radiation in an image-like manner with a specific pattern through a mask or the like, for example.
- actinic ray or radiation include infrared rays, visible rays, ultraviolet rays, far-ultraviolet rays, X-rays, electron beams, etc., but at least ultraviolet rays are preferred, and in particular, g rays, h rays, i rays, etc. Ultraviolet rays are preferably used.
- the exposure is preferably exposure using mainly i-line in a stepper exposure machine.
- Exposure illuminance the stepper exposure machine used for manufacturing a color filter for a solid-state imaging device, from the viewpoint of throughput, preferably 300 mW / cm 2 or more, more preferably 500 mW / cm 2 or more, 1000 mW / cm 2 or more and particularly preferable.
- the exposure amount is also from the viewpoint of throughput, generally preferably 1000 mJ / cm 2 or less, more preferably 500 mJ / cm 2 or less, particularly preferably 300 mJ / cm 2 or less.
- the exposed coating layer is developed with a developer to reveal a pattern.
- a developer Any developer can be used as long as it dissolves the unexposed portion of the photosensitive transparent resin composition and hardly dissolves the exposed portion (radiation irradiated portion).
- various organic solvents and combinations thereof, and alkaline aqueous solutions can be used.
- organic solvent examples include the solvents described above that can be used when preparing the photosensitive transparent resin composition.
- alkaline aqueous solution examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, And choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like.
- an alkaline aqueous solution in which the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5.
- the alkali concentration is pH 13 or less, pattern roughness, peeling, and a decrease in the remaining film rate can be avoided more reliably.
- the alkali concentration is pH 11 or more, the development speed is good and the generation of residues can be more reliably prevented.
- development is performed using a developer such as an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, and a paddle method.
- the development temperature is preferably 15 to 40 ° C. Further, after development, washing is generally performed with running water.
- a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, 5 on the hot plate.
- a predetermined transparent pattern can be formed by post-baking for 30 to 90 minutes in an oven for 30 to 90 minutes.
- the transparent pattern thus formed has an array of a plurality of rectangular pixels on the substrate, and one side (maximum side) of the pixel is generally 1.0 to 20 ⁇ m or less. Of these, 5 ⁇ m or less is preferable, 4 ⁇ m or less is more preferable, and 3 ⁇ m or less is particularly preferable from the viewpoint of effective use of a substrate such as a silicon wafer, miniaturization of a device using a solid-state image sensor, and high-speed operation of the solid-state image sensor.
- the thickness of the pixel in the color filter of the present invention is not particularly limited, but it tends to be thin from the viewpoint of effective use of a substrate such as a silicon wafer and shading of a device using a solid-state imaging device, and is 2 ⁇ m or less. Is preferable, 1.5 ⁇ m or less is more preferable, and 1.0 ⁇ m or less is particularly preferable.
- the photosensitive transparent resin composition of the present invention When used for forming an LCD spacer, it can be provided between an array substrate and a color filter substrate. Specifically, (1) When provided on the ITO electrode layer of the array substrate, (2) When provided on the colored layer of the color filter substrate, (3) From both the array substrate side and the color filter substrate side May be provided. It can also be provided on an alignment film such as polyimide (the alignment film is provided on the color filter colored layer).
- the formation of the photospacer is first performed by applying the photosensitive transparent resin composition directly on the glass substrate or through another layer, and then drying to form a coating film (coating film forming step); A process of exposing a specific pattern on the coating film (exposure process), a process of developing the exposed coating film with an alkaline developer (developing process), and a heat treatment of the developed coating film And a step of applying (post-bake step), and a pattern can be formed by passing through these steps. Moreover, the process of hardening the said resist pattern by heating and exposure as needed may be included.
- a substrate made of glass, quartz, silicon, transparent resin or the like can be used as the substrate.
- a method for applying the photosensitive transparent resin composition for example, various methods such as a spray method, a roll coating method, and a spin coating method can be used.
- the coating layer formed in the coating film forming step is exposed by irradiating actinic rays or radiation in an image-like manner with a specific pattern through a mask or the like, for example.
- actinic ray or radiation include infrared rays, visible rays, ultraviolet rays, far-ultraviolet rays, X-rays, electron beams, etc., but at least ultraviolet rays are preferred, and in particular, g rays, h rays, i rays, etc. Ultraviolet rays are preferably used.
- the exposure is preferably exposure using mainly h-line and i-line in proximity exposure machine and mirror projection exposure machine.
- the exposure illuminance is preferably 10 mW / cm 2 or more, more preferably 20 mW / cm 2 or more, and more preferably 30 mW from the viewpoint of throughput in the proximity exposure apparatus and mirror projection exposure apparatus used for the production of color filters for liquid crystal display devices. / Cm 2 or more is particularly preferable.
- the exposure amount is also from the viewpoint of throughput, generally preferably 300 mJ / cm 2 or less, more preferably 200 mJ / cm 2 or less, 100 mJ / cm 2 or less is particularly preferred.
- the exposed coating layer is developed with a developer to reveal a pattern.
- a developer Any developer can be used as long as it dissolves the unexposed portion of the photosensitive transparent resin composition and hardly dissolves the exposed portion (radiation irradiated portion).
- various organic solvents and combinations thereof, and alkaline aqueous solutions can be used.
- organic solvent examples include the solvents described above that can be used when preparing the photosensitive transparent resin composition.
- alkaline aqueous solution examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, And choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like.
- an alkaline aqueous solution in which the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5.
- the alkali concentration is pH 13 or less, pattern roughness, peeling, and reduction in the remaining film ratio can be avoided, and when the alkali concentration is pH 11 or more, the development speed is good and the generation of residues can be prevented.
- development is performed using a developer such as an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, and a paddle method.
- the development temperature is preferably 15 to 40 ° C. Further, after development, washing is generally performed with running water.
- a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, 5 on the hot plate.
- a predetermined transparent pattern can be formed by post-baking for 30 to 90 minutes in an oven for 30 to 90 minutes.
- the dry layer thickness of the layer formed using the photosensitive transparent resin composition is preferably 1 to 50 ⁇ m, more preferably 1.0 to 20 ⁇ m, and still more preferably 1 when a photospacer is formed.
- it is preferably 0.1 to 3 ⁇ m, more preferably 0.2 to 1.5 ⁇ m, and in the case of a contact hole, 0.1 to 3 ⁇ m.
- the thickness is preferably 6.0 ⁇ m, more preferably 0.2 to 3.0 ⁇ m.
- the pattern form of the photo spacer includes a dot shape, a stripe shape, a grid shape, and the like.
- the pitch is reasonable according to the color filter, and this integer multiple is preferable.
- the shape may be a quadrangular prism, a cylinder, an elliptical cylinder, a quadrangular pyramid, a quadrangular trapezoidal cross section, or a polygon thereof.
- Example 1 Formation of transparent pattern of color filter for solid-state imaging device (preparation of flattened film resist solution) The following components were mixed and stirred with a homogenizer stirrer to prepare a flattening film resist solution.
- the halomethyltriazine compound (I) is the following compound.
- This flattening film resist solution was applied onto a 6-inch silicon wafer by spin coating. Subsequently, heat treatment was performed on a hot plate at a surface temperature of 120 ° C. for 120 seconds to obtain a uniform coating film having a thickness of about 2.0 ⁇ m on the silicon wafer. Next, the coating film was cured in an oven at 220 ° C. for 1 hour to obtain a flattened film.
- ⁇ Photosensitive transparent resin composition The following components were stirred and mixed using a magnetic stirrer to prepare the photosensitive transparent resin composition of the present invention.
- Monomer A 7.89 parts (dipentaerythritol pentaacrylate; manufactured by Nippon Kayaku Co., Ltd., product name KAYARAD DPHA) Initiator A 2.63 parts (compound (II) below; manufactured by Ciba Specialty Chemicals, product name IRGACURE OXE01) -The following compound (III) (ultraviolet absorber) 1.26 parts-Solvent A (organic solvent) 57.86 parts (propylene glycol monomethyl ether acetate
- the photosensitive transparent resin composition obtained as described above was applied by spin coating on the flattened film of the silicon wafer, and then dried by heat treatment on a hot plate at a surface temperature of 100 ° C. for 120 seconds. A coating film having a thickness of about 0.8 ⁇ m after drying was formed.
- an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) is passed through a mask pattern in which 1.2 ⁇ m square pixels are arranged in a 4 mm ⁇ 3 mm region on the substrate with respect to the dried coating film. ) At an exposure amount of 200 mJ / cm 2 and exposure at two levels of 1200 mW / cm 2 (high illuminance) and 600 mW / cm 2 (low illuminance).
- the pattern-exposed coating film was subjected to paddle development for 60 seconds at room temperature using a 60% aqueous solution of organic alkaline developer CD-2000 (Fuji Film Electronics Materials Co., Ltd.), and then spin shower for another 20 seconds. And rinsed with pure water. Thereafter, it was further washed with pure water. Thereafter, water droplets were blown with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 220 ° C. for 300 seconds to form a transparent pattern on the silicon wafer. A transparent pattern was produced as described above.
- organic alkaline developer CD-2000 Fluji Film Electronics Materials Co., Ltd.
- ” represents an absolute value.
- cd ⁇ the difference in the remaining film rate
- cd ⁇ the difference in the remaining film rate
- cd ⁇ the difference in the remaining film rate
- Example 1 Formation of transparent pattern of color filter for solid-state imaging device
- Example 1 was the same as Example 1 except that the composition of the photosensitive transparent resin composition was changed as shown in Table 1 below. Similarly, a photosensitive transparent resin composition was prepared, and a color filter was produced. The same evaluation as in Example 1 was performed. The results of evaluation and measurement are shown in Table 2 below.
- Example 1 Formation of transparent pattern of color filter for solid-state imaging device
- Example 1 was the same as Example 1 except that the composition of the photosensitive transparent resin composition was changed as shown in Table 1 below. Similarly, a photosensitive transparent resin composition was prepared, and a color filter was produced. The same evaluation as in Example 1 was performed. The results of evaluation and measurement are shown in Table 2 below.
- the pattern shape was good, the residue was suppressed, and the exposure illuminance dependency was small.
- the line width and the remaining film ratio especially in low illumination exposure The fluctuation of the exposure illuminance was large and the exposure illuminance dependence could not be suppressed.
- the compound XII which is an antioxidant, although the dependency on exposure illuminance was small to some extent, the generation of development residue could not be suppressed.
- Example 8 to 14 and Comparative Examples 4 to 6 Formation of Photospacer for Liquid Crystal Display
- the photosensitive transparent resin compositions used in Examples 1 to 7 and Comparative Examples 1 to 3 were prepared and a glass substrate (Corning 1737).
- the film was spin-coated at 100 ° C. for 120 seconds using an oven, and a coating film having a dried film thickness of 2.0 ⁇ m was formed.
- using a square mask having a mask size of 10 ⁇ m on a side exposure was performed at two levels of illuminance of 20 mW / cm 2 (low illuminance) and 40 mW / cm 2 (high illuminance) at an exposure amount of 100 mJ / cm 2 . .
- a 60% aqueous solution of an organic alkaline developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied on the coating film after exposure, and paddle development was performed at room temperature for 40 seconds. After development, pure water was sprayed in a shower to wash away the developer. Then, the coating film exposed and developed as described above was heat-treated (post-baked) for 30 minutes in an oven at 220 ° C. A photo spacer was produced as described above.
- (2-1) Shape of transparent pattern The shape of the 10 ⁇ m square transparent pattern of the obtained color filter was further measured using a length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.), to the color filter on the glass. Observation was performed at a magnification of 30,000 from above, and the shape of the corner was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3 below. A rounded corner is different from the pattern shape of other colors adjacent to each other at the time of device manufacture, and is measured as a color mixture and noise at the time of image recognition, thereby deteriorating the performance of the device. ⁇ Evaluation criteria> ⁇ : Corners were not round and a good rectangle was obtained. ⁇ : Corners were rounded, but were practically acceptable. X: The corner was rounded like a fan, and a rectangle was not obtained.
- the results are shown in Table 3 below. ⁇ Evaluation criteria> A: The exposure sensitivity was good and the remaining film ratio was 70% or more. X: The exposure sensitivity was insufficient, and the remaining film rate was also less than 70%.
- As described above, for each of the pixel patterns obtained by the exposure at the two levels (high illuminance: 40 mW / cm 2 , low illuminance: 20 mW / cm 2 ), the evaluation of “(2-4) remaining film ratio” is performed. The remaining film rate c (%) at low illuminance obtained in step 1 and the remaining film rate d (%) at high illuminance are compared, and the difference in the remaining film rate (
- the photosensitive transparent resin composition which can form the pattern excellent in the property stably can be provided.
- the photosensitive transparent resin composition of the present invention can be used in a method for producing a color filter that is capable of displaying a fine and high-quality image with little drop in transmittance with visible light.
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Abstract
Description
液晶表示素子用カラーフィルタの場合では、カラーフィルタ層とTFT層の間の決められたセルギャップを保持するために用いられるフォトスペーサー(例えば、図4及び特許文献1、2参照)及びMVA(Multi-domain Vertical Alignment)液晶表示装置(例えば、特許文献3、4参照)のカラーフィルタ等で透明樹脂層のパターンを形成する。フォトスペーサーは、表示画面上すなわちRGB上に形成する場合がある。
一方、イメージセンサ用カラーフィルタの場合では、感光性透明樹脂組成物でパターン形成し、感度を上げる目的で複数色のカラーフィルタの1色を白(透明)にする場合がある(例えば、図3及び特許文献5参照)。背景として、最近解像度向上の目的で画素数の拡大とともに画素の微細化が進展しているが、その反面開口部が小さくなり感度低下に繋がっている。そこで、感度低下を補う目的で、カラーフィルタの1色を白(透明)にし、感度を上げるのである。
特に、イメージセンサ用カラーフィルタでは上記問題に加えて、ウエハー上でパターン形成を行なうため露光のハレーションに因って透明樹脂層のパターン解像度が問題になることが多い。
本発明によれば、可視光での透過率の落ちが少なく、精細で高品質の画像表示が可能なカラーフィルタ及びその製造方法を提供することができる。
2 カラーフィルタ
3 液晶配向膜
4 フォトスペーサー
5 液晶
本発明の感光性透明樹脂組成物は、重合性モノマー、アルカリ可溶性樹脂、光重合開始剤、及び下記一般式(I)で表される化合物(紫外線吸収剤)を少なくとも含有することで構成されたものであり、一般的には溶剤が用いられる。
本発明の感光性透明樹脂組成物は、紫外線吸収剤として、共役ジエン系化合物である下記一般式(I)で表される化合物の少なくとも1種を含有する。本発明においては、この共役ジエン系化合物を用いることで、特に低照度露光を行なった際のその後の現像性能変動を抑えるので、パターンの線幅、膜厚、分光スペクトル等のパターン形成性に関係する露光照度依存性を抑制することができる。
R1またはR2で表される炭素原子数1~20のアルキル基は、置換基を有していてもよく、置換基としては、アリール基、アルコキシ基、アリールオキシ基、アシルオキシ基、ハロゲン原子、アシルアミノ基、アシル基、アルキルチオ基、アリールチオ基、ヒドロキシ基、シアノ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、置換カルバモイル基、置換スルファモイル基、ニトロ基、置換アミノ基、アルキルスルホニル基、アリールスルホニル基等が挙げられ、これら置換基は、更に、これらの置換基で置換されていてもよい。R1、R2としてのアルキル基が有してもよい置換基の炭素数は10以下が好ましい。
R1またはR2で表されるアルキル基についての炭素原子数1~20は、置換基が有する炭素原子数を含めてのものである。
置換基を有するアルキル基としては、メトキシエチル基、エトキシプロピル基、2-エチルへキシル基、ヒドロキシエチル基、クロロプロピル基、N,N-ジエチルアミノプロピル基、シアノエチル基、フェネチル基、ベンジル基、p-t-ブチルフェネチル基、p-t-オクチルフェノキシエチル基、3-(2,4-ジーt-アミルフェノキシ)プロピル基、エトキシカルボニルメチル基、2-(2-ヒドロキシエトキシ)エチル基、2-フリルエチル基などが挙げられる。
R1、R2で表される炭素原子数1~20のアルキル基として、メチル基、エチル基、プロピル基、n-ブチル基、nーへキシル基が好ましい。
R1またはR2で表されるアリール基についての炭素原子数6~20は、置換基が有する炭素原子数を含めてのものである。
R1、R2で表される炭素原子数6~20のアリール基として、中でも、置換又は無置換のフェニル基、1-ナフチル基、2-ナフチル基が好ましい。
ハメット則は、ベンゼン誘導体の反応又は平衡に及ぼす置換基の影響を定量的に論ずるために、1935年にL. P. Hammettにより提唱された経験則であるが、これは今日広く妥当性が認められている。ハメット則により求められた置換基定数には、σp値とσm値とがあり、これらの値は多くの一般的な成書に記載があるが、例えば、J.A. Dean編「Lange’s Handbook of Chemistry」第12版、1979年(Mc Graw-Hill)や「化学の領域増刊」、122号、96~103頁、1979年(南江堂)、Chemical Reviews, 91巻、165頁~195頁、1991年に詳しい。本発明では、これらの成書に記載の文献既知の値がある置換基にのみ限定されるという意味ではなく、その値が文献未知であってもハメット則に基づいて測定した場合にその範囲内に含まれる限り包含されることは勿論である。
これらのうち、R3、R4としては、アシル基、カルバモイル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、ニトロ基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、スルファモイル基が好ましく、特にアシル基、カルバモイル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、スルファモイル基が好ましい。また、R3及びR4は、互いに結合して環状電子求引基を形成してもよい。R3及びR4が互いに結合して形成する環状電子求引基としては、例えば、2個のカルボニル基を含む6員環を挙げることができる。
このうち特にアクリル酸エステル、メタアクリル酸エステル、芳香族ビニル化合物が好ましい。
上記コモノマー化合物の2種以上を一緒に使用することも出来る。例えば、n-ブチルアクリレートとジビニルベンゼン、スチレンとメチルメタアクリレート、メチルアクリレートとメタアクリレート酸等を使用できる。
3-アニリノアクロレインアニル(13.3g)と、エチルフェニルスルホニルアセテート(14.3g)を無水酢酸(40ml)中で85~90℃に2時間加熱する。減圧乾燥下に無水酢酸を除き、エタノール(40ml)とジーn―へキシルアミン(24.1g)を加えて2時間還流する。エタノールを除去し、残渣をカラムクロマトにかけ、精製し、エタノールより再結晶すると目的物が得られる。融点95~96℃。
光重合開始剤としては、例えば、特開平57-6096号公報に記載のハロメチルオキサジアゾール、特公昭59-1281号公報、特開昭53-133428号公報等に記載のハロメチル-s-トリアジン等の活性ハロゲン化合物、米国特許USP-4318791、欧州特許公開EP-88050A等の各明細書に記載のケタール、アセタール、又はベンゾインアルキルエーテル類等の芳香族カルボニル化合物、米国特許USP-4199420明細書に記載のベンゾフェノン類等の芳香族ケトン化合物、FR2456741明細書に記載の(チオ)キサントン類又はアクリジン類化合物、特開平10-62986号公報に記載のクマリン類又はロフィンダイマー類等の化合物、特開平8-015521号公報等のスルホニウム有機硼素錯体等、等を挙げることができる。
上記以外に、2,4,6-トリメチルフェニルカルボニル-ジフェニルフォスフォニルオキサイド、ヘキサフルオロフォスフォロ-トリアルキルフェニルホスホニウム塩等が挙げられる。
また、これらの光重合開始剤を併用することもできる。
光重合開始剤の感光性透明樹脂組成物における含有量としては、該組成物の全固形分に対して、0.1~10.0質量%が好ましく、より好ましくは0.5~5.0質量%である。光重合開始剤の含有量が前記範囲内であると、重合反応を良好に進行させて強度の良好な膜形成が可能である。
本発明の感光性透明樹脂組成物は、重合性モノマーの少なくとも1種を含有する。
重合性モノマーとしては、少なくとも1つの付加重合可能なエチレン性二重結合を有し、かつ常圧下で100℃以上の沸点を持つ化合物が好ましい。重合性モノマーは、前記光重合開始剤等と共に含有することにより、本発明の感光性透明樹脂組成物をネガ型に構成することができる。
更に、日本接着協会誌Vol.20、No.7、300~308頁に光硬化性モノマー及びオリゴマーとして紹介されているものも挙げることができる。中でも、重合性モノマーとしては、多官能(メタ)アクリル化合物が好ましい。
本発明の感光性透明樹脂組成物には、アルカリ可溶性樹脂を用いて構成することができる。アルカリ可溶性樹脂は、アルカリ可溶性であれば特に限定はないが、耐熱性、現像性、入手性等の観点から選ばれることが好ましい。
本発明の感光性透明樹脂組成物は、一般には、有機溶剤を用いて構成することができる。
有機溶剤は、各成分の溶解性や感光性透明樹脂組成物の塗布性を満足すれば基本的には特に制限はないが、特に紫外線吸収剤、バインダーの溶解性、塗布性、安全性を考慮して選ばれることが好ましい。また、本発明の感光性透明樹脂組成物を調製する際には、少なくとも2種類の有機溶剤を含むことが好ましい。
本発明の感光性透明樹脂組成物には、必要に応じて、各種添加物、例えば、充填剤、上記以外の高分子化合物、界面活性剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することかできる。
有機カルボン酸の具体例としては、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸等の脂肪族モノカルボン酸;シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、テトラメチルコハク酸、シトラコン酸等の脂肪族ジカルボン酸;トリカルバリル酸、アコニット酸、カンホロン酸等の脂肪族トリカルボン酸;安息香酸、トルイル酸、クミン酸、ヘメリト酸、メシチレン酸等の芳香族モノカルボン酸;フタル酸、イソフタル酸、テレフタル酸、トリメリト酸、トリメシン酸、メロファン酸、ピロメリト酸等の芳香族ポリカルボン酸;フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸等のその他のカルボン酸が挙げられる。
本発明における感光性透明樹脂組成物を用いて、イメージセンサで感度を上げる目的でカラーフィルタの透明パターンを形成する方法について説明する。
先ず、該光感光性透明樹脂組成物をシリコンウエハー上に直接または他の層を介して塗布し、その後乾燥して塗布膜を形成する工程(塗膜形成工程)と、該塗布膜上に、特定のパターンを露光する工程(露光工程)と、露光された前記塗布膜をアルカリ現像液で現像処理する工程(現像工程)と、現像処理された前記塗布膜に加熱処理を施す工程(ポストベーク工程)と、を含むことを特徴とし、これらの工程を経ることでパターンを形成することができる。また、必要により上記レジストパターンを加熱および露光により硬化する工程を含んでいてもよい。
露光照度は、固体撮像素子用のカラーフィルタの作製に用いられるステッパー露光機では、スループットの観点より、300mW/cm2以上が好ましく、500mW/cm2以上が更に好ましく、1000mW/cm2以上が特に好ましい。また、露光量は、同じくスループットの観点より、一般に1000mJ/cm2以下が好ましく、500mJ/cm2以下が更に好ましく、300mJ/cm2以下が特に好ましい。
現像液としては、感光性透明樹脂組成物の未露光部を溶解し、かつ露光部(放射線照射部)を溶解し難いものであれば、いかなるものも用いることができる。具体的には、種々の有機溶剤及びその組合せ、アルカリ性の水溶液を用いることができる。
現像工程は、アルカリ性の水溶液などの現像液を用いて現像処理するが、現像方法には、例えば、ディップ法、スプレー法、パドル法等がある。現像温度は、15~40℃で行なうことが好ましい。また、現像後は一般に流水にて洗浄が行なわれる。
本発明における感光性透明樹脂組成物を用いて、液晶表示用フォトスペーサーを形成する方法について説明する。
露光照度は、液晶表示装置用のカラーフィルタの作製に用いられるプロキシミテイ露光機及びミラープロジェクション露光機では、スループットの観点より、10mW/cm2以上が好ましく、20mW/cm2以上が更に好ましく、30mW/cm2以上が特に好ましい。また、露光量は、同じくスループットの観点より、一般に300mJ/cm2以下が好ましく、200mJ/cm2以下が更に好ましく、100mJ/cm2以下が特に好ましい。
現像液としては、感光性透明樹脂組成物の未露光部を溶解し、かつ露光部(放射線照射部)を溶解し難いものであれば、いかなるものも用いることができる。具体的には、種々の有機溶剤及びその組合せ、アルカリ性の水溶液を用いることができる。
現像工程は、アルカリ性の水溶液などの現像液を用いて現像処理するが、現像方法には、例えば、ディップ法、スプレー法、パドル法等がある。現像温度は、15~40℃で行なうことが好ましい。また、現像後は一般に流水にて洗浄が行なわれる。
(平坦化膜レジスト液の調製)
下記各成分をホモジナイザー攪拌機で混合・攪拌して、平坦化膜用レジスト液を調製した。
・ベンジルメタアクリレート/メタアクリル酸(=70/30[モル比])共重合体のプロピレングリコールモノメチルエーテルアセテート溶液(45%、質量平均分子量30000、藤倉化成(株)製、製品名アクリベースFF-187)
22部
・ジペンタエリスリトールペンタアクリレート 6.5部
(日本化薬社製、製品名KAYARAD DPHA)
・プロピレングリコールモノメチルエーテルアセテート(ダイセル化学(株)製、製品名MMPGAC) 13.8部
・エチル-3-エトキシプロピオネート(長瀬産業(株)製、製品名エチル-3エトキシプロピオネート) 12.3部
・ハロメチルトリアジン化合物(下記化合物(I))(PANCHIM社製、製品名トリアジンPP) 0.3部
この平坦化膜用レジスト液を6インチシリコンウエハー上にスピンコートで塗布した。次いで、表面温度120℃×120秒、ホットプレート上で加熱処理し、前記シリコンウエハー上に約2.0μmの膜厚の均一な塗布膜を得た。次いで、220℃の条件下で1時間、オーブンにてその塗布膜を硬化処理して、平坦化膜を得た。
次いで、下記組成物を混合し、感光性透明樹脂組成物を調製した。
下記成分をマグネチックスターラーを用いて攪拌、混合し、本発明の感光性透明樹脂組成物を調製した。
・樹脂A(ベンジルメタアクリレート/メタアクリル酸(=70/30[モル比])共重合体のプロピレングリコールモノメチルエーテルアセテート溶液(30%、質量平均分子量30000、藤倉化成(株)製、製品名アクリベースFF-187))
26.3部
・モノマーA 7.89部
(ジペンタエリスリトールペンタアクリレート;日本化薬社製、製品名KAYARAD DPHA)
・開始剤A 2.63部
(下記化合物(II);チバ・スペシャルティケミカルズ(株)製、製品名IRGACURE OXE01)
・下記化合物(III)(紫外線吸収剤) 1.26部
・溶剤A(有機溶剤) 57.86部
(プロピレングリコールモノメチルエーテルアセテート;ダイセル化学(株)製、製品名MMPGAC)
・界面活性剤A 4.21部
(フッ素系界面活性剤;大日本インキ化学工業(株)製、製品名メガファックF-144)
・重合禁止剤A 0.001部
(p-メトキシフェノール;関東化学(株)製、製品名p-メトキシフェノール)
上記より得られた感光性透明樹脂組成物を、前記シリコンウエハーの平坦化膜上にスピンコートにより塗布した後、塗布膜面の表面温度100℃で120秒間、ホットプレートで加熱処理して乾燥させ、乾燥後の膜厚が約0.8μmの塗布膜を形成した。
次に、乾燥後の塗布膜に対して、1.2μmの正方ピクセルがそれぞれ基板上の4mm×3mmの領域に配列されたマスクパターンを介してi線ステッパー(キャノン(株)製のFPA-3000i5+)により、露光量200mJ/cm2にて照度1200mW/cm2(高照度)及び600mW/cm2(低照度)の各2水準で露光した。
以上のようにして、透明パターンを作製した。
上記より得られた透明パターンについて、下記の評価、測定を行なった。評価、測定の結果は、下記表2に示す。
得られたカラーフィルタの1.2μm正方パターンの形状を、測長SEM(S-7800H、(株)日立製作所製)を用いて、シリコンウエハー上のカラーフィルタの更に上方から3万倍で観察し、角(カド)の形状を下記の評価基準にしたがって評価した。評価結果を下記表2に示す。なお、角(カド)の形状が丸まっているものは、デバイス製造時に隣り合った他色のパターン形状と異なってしまい画像認識時に混色、ノイズとして計測されてしまい、デバイスの性能を悪化させる。
<評価基準>
○:角(カド)の丸みが小さく、良好な矩形が得られた。
△:角(カド)に丸みができたが、実用上許容できる程度であった。
×:角(カド)に扇状に丸みがついており、矩形が得られなかった。
得られたカラーフィルタの1.2μmの正方パターンをカラーフィルタ面に直交する面で切断し、その切断面の形状をSEM(S-4800、(株)日立ハイテクノロジ―ズ)を用いて3万倍で観察し、切断面の形状を下記の評価基準にしたがって評価した。なお、断面形状が順テーパーであると、隣接する画素とパターンが重なり合い、隣接する画素パターン形状が求める矩形にならず望ましくない。
<評価基準>
図1に示すように、
形状A:〇 形状が矩形で、良好な形状が得られた。
形状B:△ 形状が逆テーパーだが、実用上許容できる程度であった。
形状C:× 形状が順テーパーで、矩形が得られなかった。
ポストベーク後のカラーフィルタの画素パターンを、測長SEM(S-7800H、(株)日立製作所製)を用いて、シリコンウエハー上のカラーフィルタの更に上方から3万倍で観察し、目測で残渣の発生の有無を下記の評価基準にしたがって評価した。
<評価基準>
○:現像残渣はなかった。
△:現像残渣が僅かにみられたが、実用上許容できる程度であった。
×:残渣の発生が顕著であった。
ポストベーク後カラーフィルタの画素パターンの膜厚D1と、露光後で現像前における膜厚D2とを触針式表面形状測定器(Dektak8、日本ビーコ社製)を用いて測定し、得られた膜厚D1を膜厚D2で除算して残膜率(%;=D1/D2×100)を求め、これを指標として下記の評価基準にしたがって評価した。なお、露光感度の点から残膜率は高い方が望ましい。結果は下記表2に示す。
<評価基準>
○:露光感度は良好で、残膜率は70%以上であった。
×:露光感度は不充分であり、残膜率も70%未満であった。
600mW/cm2(低照度)、1200mW/cm2(高照度)での露光後に現像、ポストベークを行なった後のカラーフィルタの画素パターンの形状を、測長SEM(S-7800H、(株)日立製作所製)を用いて、シリコンウエハー上のカラーフィルタの更に上方から3万倍で観察した。線幅は、マスクパターンの1.2μmの正方ピクセルと対比した適性寸法という観点から、下記の評価基準にしたがって評価した。評価結果は下記表2に示す。
<評価基準>
○:線幅が、1.00μm以上1.40μm未満であった。
×:線幅が、1.00μm未満もしくは1.40μm以上であった。
~A.線幅|a-b|~
上記のように2水準(高照度:1200mW/cm2、低照度:600mW/cm2)での露光により得られた画素パターンの各々について、前記「(1-5)線幅」の評価で得られた低照度での線幅a(μm)と高照度での線幅b(μm)の双方を比較し、線幅差(=|a-b|)求めて指標とし、下記の評価基準にしたがって評価した。固体撮像素子用カラーフィルタでは、得られるパターンの線幅の一定性が重要であるため、0.05μmを閾値に評価した。なお、「| |」の表記は絶対値を表す。
<評価基準>
○:線幅差が0.05μm未満であった。
×:線幅差が0.05μm以上であった。
~B.残膜率|c-d|~
上記のように2水準(高照度:1200mW/cm2、低照度:600mW/cm2)での露光により得られた画素パターンの各々について、上記の「(1-4)残膜率」の評価で得られた低照度での残膜率c(%)と高照度での残膜率d(%)の双方を比較し、残膜率の差(=|c-d|)を求めて指標とし、下記の評価基準にしたがって評価した。固体撮像素子用カラーフィルタでは、得られるパターンの膜厚の一定性が重要であるため、1.0%を閾値に評価した。なお、「| |」の表記は絶対値を表す。
<評価基準>
○:残膜率の差が1.0%未満であった。
×:残膜率の差が1.0%以上であった。
実施例1において、感光性透明樹脂組成物の組成を下記表1に示すように変更したこと以外は、実施例1と同様にして、感光性透明樹脂組成物を調製し、カラーフィルタを作製した。また、実施例1と同様の評価を行なった。評価、測定の結果は下記表2に示す。
実施例1において、感光性透明樹脂組成物の組成を下記表1に示すように変更したこと以外は、実施例1と同様にして、感光性透明樹脂組成物を調製し、カラーフィルタを作製した。また、実施例1と同様の評価を行なった。評価、測定の結果は下記表2に示す。
これに対して、他種類の紫外線吸収剤であるトリアジン系、ベンゾトリアゾ-ル系の紫外線吸収剤(化合物X、化合物XI)を用いた比較例では、特に低照度露光での線幅、残膜率の変動が大きく、露光照度依存性を抑制することはできなかった。また、酸化防止剤である化合物XIIを用いた比較例では、ある程度は露光照度依存性は小さいものの、現像残渣の発生を抑制できなかった。
実施例1~7並びに比較例1~3で用いた感光性透明樹脂組成物を用意し、ガラス基板(Corning 1737)にスピン塗布し、オーブンを用いて100℃で120秒間プリベークした後、乾燥後の膜厚が2.0μmの塗布膜を形成した。その後、一辺が10μmの幅のマスク寸法を持つ正方形マスクを用い、露光量100mJ/cm2で照度20mW/cm2(低照度)及び40mW/cm2(高照度)の各2水準にて露光した。続いて、露光後の塗布膜の上に有機アルカリ性現像液CD-2000(富士フィルムエレクトロニクスマテリアルズ(株)製)の60%水溶液を付与して室温にて40秒間、パドル現像した。現像後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗布膜を220℃のオーブンで30分間加熱処理(ポストベーク)した。
以上のようにして、フォトスペーサーを作製した。
上記より得られたフォトスペーサーについて、下記の評価、測定を行なった。評価、測定の結果は、下記表3に示す。
得られたカラーフィルタの10μm正方の透明パターンの形状を、測長SEM(S-7800H、(株)日立製作所製)を用いて、ガラス上のカラーフィルタの更に上方から3万倍で観察し、角(カド)の形状を下記の評価基準にしたがって評価した。評価結果を下記表3に示す。なお、角(カド)の形状が丸まっているものは、デバイス製造時に隣り合った他色のパターン形状と異なってしまい画像認識時に混色、ノイズとして計測されてしまい、デバイスの性能を悪化させる。
<評価基準>
○:角(カド)の丸みが小さく、良好な矩形が得られた。
△:角(カド)に丸みができたが、実用上許容できる程度であった。
×:角(カド)に扇状に丸みがついており、矩形が得られなかった。
得られたカラーフィルタの10μm四方の透明パターンの形状をカラーフィルタ面に直交する面で切断し、その切断面の形状をSEM(S-4800、(株)日立ハイテクノロジ―ズ)を用いて3万倍で観察し、切断面の形状を下記の評価基準にしたがって評価した。
<評価基準>
図2に示すように、
形状A:〇 形状が順テーパーで、良好な形状が得られた。
形状B:△ 形状が逆テーパーで、実用上許容できない形状であった。
ポストベーク後のカラーフィルタの画素パターンを、測長SEM(S-7800H、(株)日立製作所製)を用いて、ガラス上のカラーフィルタの更に上方から3万倍で観察し、目測で残渣の発生の有無を下記の評価基準にしたがって評価した。
<評価基準>
○:現像残渣はなかった。
△:現像残渣が僅かにみられたが、実用上許容できる程度であった。
×:残渣の発生が顕著であった。
ポストベーク後カラーフィルタの画素パターンの膜厚D1と、露光後で現像前における膜厚D2とを触針式表面形状測定器(Dektak8、日本ビーコ社製)を用いて測定し、得られた膜厚D1を膜厚D2で除算して残膜率(%;=D1/D2×100)を求め、これを指標として下記の評価基準にしたがって評価した。なお、露光感度の点から残膜率は高い方が望ましい。結果は下記表3に示す。
<評価基準>
○:露光感度は良好で、残膜率は70%以上であった。
×:露光感度は不充分であり、残膜率も70%未満であった。
20mW/cm2(低照度)、40mW/cm2(高照度)での露光後に現像、ポストベークを行なった後のカラーフィルタの画素パターンの形状を、測長SEM(S-7800H、(株)日立製作所製)を用いて、ガラス上のカラーフィルタの更に上方から3万倍で観察した。線幅は、マスクパターンの10.0μmの正方ピクセルと対比した適性寸法という観点から、下記の評価基準にしたがって評価した。評価結果は下記表3に示す。
<評価基準>
○:線幅が、9.5μm以上10.5μm未満であった。
×:線幅が、9.5μm未満もしくは10.5μm以上であった。
~A.線幅|a-b|~
上記のように2水準(高照度:40mW/cm2、低照度:20mW/cm2)での露光により得られた画素パターンの各々について、前記「(2-5)線幅」の評価で得られた低照度での線幅a(μm)と高照度での線幅b(μm)の双方を比較し、線幅差(=|a-b|)求めて指標とし、下記の評価基準にしたがって評価した。固体撮像素子用カラーフィルタでは、得られるパターンの線幅の一定性が重要であるため、0.05μmを閾値に評価した。なお、「| |」の表記は絶対値を表す。
<評価基準>
○:線幅差が0.5μm未満であった。
×:線幅差が0.5μm以上であった。
~B.残膜率|c-d|~
上記のように2水準(高照度:40mW/cm2、低照度:20mW/cm2)での露光により得られた画素パターンの各々について、上記の「(2-4)残膜率」の評価で得られた低照度での残膜率c(%)と高照度での残膜率d(%)の双方を比較し、残膜率の差(=|c-d|)を求めて指標とし、下記の評価基準にしたがって評価した。固体撮像素子用カラーフィルタでは、得られるパターンの膜厚の一定性が重要であるため、1.0%を閾値に評価した。なお、「| |」の表記は絶対値を表す。
<評価基準>
○:残膜率の差が1.0%未満であった。
×:残膜率の差が1.0%以上であった。
これに対して、他種類の紫外線吸収剤であるトリアジン系、ベンゾトリアゾ-ル系の紫外線吸収剤(化合物X、化合物XI)を用いた比較例では、特に低照度露光での線幅、残膜率の変動が大きく、露光照度依存性を抑制することはできなかった。また、酸化防止剤である化合物XIIを用いた比較例では、ある程度は露光照度依存性は小さいものの、現像残渣の発生を抑制できなかった。
本発明の感光性透明樹脂組成物は、可視光での透過率の落ちが少なく、精細で高品質の画像表示が可能なカラーフィルタの製造方法に使用することができる。
本出願は、2008年 3月31日出願の日本特許出願(特願2008-094248)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (5)
- 前記一般式(I)で表される化合物の含有量が、感光性透明樹脂組成物の固形分中0.01~30質量%であることを特徴とする請求項1に記載の感光性透明樹脂組成物。
- 前記光重合開始剤の少なくとも1種が、オキシムエステル系化合物であることを特徴とする請求項1又は請求項2に記載の感光性透明樹脂組成物。
- 請求項1~3のいずれか1項に記載の感光性透明樹脂組成物を塗布し、塗布形成された塗布層をフォトマスクを介して露光し、現像することによりパターン形成することを特徴とするカラーフィルタの製造方法。
- 請求項4に記載のカラーフィルタの製造方法により作製されたことを特徴とするカラーフィルタ。
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2009
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WO2013099945A1 (ja) | 2011-12-28 | 2013-07-04 | 富士フイルム株式会社 | 光学部材セット及びこれを用いた固体撮像素子 |
WO2013099948A1 (ja) | 2011-12-28 | 2013-07-04 | 富士フイルム株式会社 | 光学部材セット及びこれを用いた固体撮像素子 |
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WO2014034813A1 (ja) | 2012-08-31 | 2014-03-06 | 富士フイルム株式会社 | 分散組成物、これを用いた硬化性組成物、透明膜、マイクロレンズ、及び固体撮像素子、並びに高分子化合物 |
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JP5155920B2 (ja) | 2013-03-06 |
US20110039195A1 (en) | 2011-02-17 |
EP2264526B1 (en) | 2019-05-22 |
KR20100133396A (ko) | 2010-12-21 |
EP2264526A1 (en) | 2010-12-22 |
TWI434861B (zh) | 2014-04-21 |
JP2009265642A (ja) | 2009-11-12 |
TW200946548A (en) | 2009-11-16 |
US8883376B2 (en) | 2014-11-11 |
EP2264526A4 (en) | 2011-12-28 |
KR101631543B1 (ko) | 2016-06-17 |
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