CN1573542A - Colored photoresist composition - Google Patents

Colored photoresist composition Download PDF

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Publication number
CN1573542A
CN1573542A CNA2004100475242A CN200410047524A CN1573542A CN 1573542 A CN1573542 A CN 1573542A CN A2004100475242 A CNA2004100475242 A CN A2004100475242A CN 200410047524 A CN200410047524 A CN 200410047524A CN 1573542 A CN1573542 A CN 1573542A
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CN
China
Prior art keywords
acid
photosensitive composition
resin
methyl
enumerate
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Granted
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CNA2004100475242A
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Chinese (zh)
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CN1573542B (en
Inventor
市川幸司
白川政和
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

The colored photosensitive resin composition comprises a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a pigment dispersant (E) and a solvent (F). When the colored photosensitive resin composition is applied on a glass substrate to form a resin layer and this resin layer is prebaked, exposed through a mask, developed and postbaked, a hardness of a hardened resin layer obtained after the postbaking is a pencil hardness of 3H to 9H, and a transmittance (an average at 400-780 nm) of the part of the glass substrate on which an unexposed region of a photosensitive resin layer obtained after the prebaking and the exposure through the mask is dissolved after the lapse of 120 seconds after immersing the photosensitive resin layer in an aqueous alkali solution at 25[deg.]C under stirring at 100 rpm is 98-100%.

Description

Photosensitive composition
Technical field
The present invention relates to photosensitive composition.
Background technology
The chromatic filter that uses in color liquid crystal display arrangement or the imaging apparatus etc. is to be equivalent to the trichromatic dyed layer of red, green and blue by formation on the substrate that makes black matrix formation pattern make.
Usually the dyed layer (colored pixels) that forms with pattern-like is that hardness is inadequate, can make the dyed layer damage in the back operations such as alignment film rubbing processing after chromatic filter is made, perhaps the pressure that interval insulant produced between 2 pieces of substrates makes the dyed layer distortion easily when liquid crystal board is assembled, thereby make gap, liquid crystal pond that local variation take place, be easy to generate problems such as display defect.
This dyed layer can form from colored resin composition.As colored resin composition, the photosensitive composition that contains colorant, resin glue, spreading agent, solvent and ceramic particle is known (opening flat 10-186126 communique with reference to the spy), but said composition prebake, in aqueous alkali, flood and because of containing ceramic particle residue takes place when making the photo-sensitive resin dissolving, transmissivity (mean value of the 400～780nm) reduction that makes the dissolving part is arranged, video picture can not satisfactory such problem through the photo-sensitive resin of non-exposed portion behind the mask exposure.
Disclosure of the Invention
The purpose of this invention is to provide the video picture excellence, can form the photosensitive composition of the hard resin-layer of high surface hardness.
The result that present inventor etc. inquire into has with keen determination found the video picture excellence, can form the photosensitive composition of the hard resin-layer of high surface hardness.
That is, the invention provides following (1)～(11).
(1) a kind of photosensitive composition, comprise colorant (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D), pigment dispersing agent (E) and solvent (F), described photosensitive composition is coated with on glass substrate and forms resin bed, make described resin bed prebake, through mask exposure, video picture, when dry the back, the hardness of the resulting hard resin-layer in back oven dry back be pencil hardness 3H above～below the 9H, and prebake, in 25 ℃ of aqueous alkalis of photo-sensitive resin through obtaining behind the mask exposure under 100rpm stirs the transmissivity (mean value of 400～780nm) of dipping part of the non-exposure of photo-sensitive resin portion dissolving after 120 seconds more than 98%～below 100%.
(2) photosensitive composition of (1) record, wherein, resin glue (B) is the resin that comprises the structural unit of deriving from (methyl) acrylic acid.
(3) photosensitive composition of (1) or (2) record, wherein, the amount of the structural unit of in the general construction unit that constitutes resin glue (B), deriving from (methyl) acrylic acid more than the 16mol%～below the 40mol%.
(4) photosensitive composition of any one record in (1)～(3), wherein, resin glue (B) further comprises the structural unit of deriving from (methyl) benzyl acrylate.
(5) photosensitive composition of any one record in (1)～(4), wherein, resin glue (B) is the resin that further comprises structural unit shown in the formula (I):
R in the formula (I) 1And R 2Represent hydrogen atom or methyl independently of one another.
(6) photosensitive composition of any one record in (1)～(5), wherein, the polystyrene conversion weight-average molecular weight of resin glue (B) more than 5,000～below 35,000.
(7) photosensitive composition of any one record in (1)～(6), wherein, pigment dispersing agent (E) is at least a surfactant of selecting a group that forms from polyester system, polyethyleneimine system, polyurethane series and acrylic acid series.
(8) photosensitive composition of any one record in (1)～(7), wherein, pigment dispersing agent (E) is the acrylic acid series surfactant.
(9) the formation method of colored pattern is characterized in that on substrate forming the resin bed of being made up of the photosensitive composition of any one record in (1)～(8), make this resin bed behind mask exposure, video picture, dry the back then.
(10) the colored pattern method of formationing of (9) record, wherein, the temperature of back oven dry processing is more than 180 ℃～below 250 ℃.
(11) chromatic filter comprises the colored pattern that the method for usefulness (9) or (10) record forms.
The invention example
Photosensitive composition of the present invention is to contain colorant (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D), the photosensitive composition of pigment dispersing agent (E) and solvent (F), described photosensitive composition is coated with on glass substrate and forms resin bed, described resin bed prebake, through mask exposure, video picture, when dry the back, the hardness of the hard resin-layer that obtains after the back oven dry be pencil hardness 3H above～below the 9H, and prebake, in 25 ℃ of alkaline aqueous solutions of photo-sensitive resin through obtaining behind the mask exposure under 100rpm stirs the transmissivity (mean value of 400～780nm) of dipping part of the non-exposure of photo-sensitive resin portion dissolving after 120 seconds more than 98%～below 100%.
The hardness of hard resin-layer (filming) must be pencil hardness 3H above～below the 9H, better 4H above～below the 9H, better 5H is following～below the 9H.Hard resin-layer (filming) though be the part that becomes pixel portions, when its pencil hardness more than 3H～when 9H was following, hard resin-layer (filming) was difficult to damaged in the step of the making of the liquid crystal orientation film that carries out after pixel forms etc., thereby better.Pencil hardness is to measure according to the method for No. 5400, JIS K.
Above-mentioned prebake is preferably and this photosensitive composition is coated on the glass substrate and implemented about 3 minutes at 100 ℃.
Flood in prebake, 25 ℃ of aqueous alkalis of the photo-sensitive resin through obtaining behind the mask exposure under 100rpm stirs.At this, aqueous alkali uses the aqueous solution that does not contain potassium hydroxide 0.05%, sodium butylnaphthalenesulfonate 0.2% by the mass fraction score usually.
The non-exposure portion of this photo-sensitive resin when impregnated in 100rpm and stir in 25 ℃ of aqueous alkalis down, dissolve in 120 seconds more fortunately, better more than 1 second～100 seconds with interior in addition better more than 1 second～80 seconds with interior, also better more than 1 second～60 seconds with interior dissolving.Dissolve the needed time if in described scope, just can suppress the low of chromatic filter throughput rate, thereby better.
In 25 ℃ of aqueous alkalis of non-exposure portion under 100rpm stirs of this photo-sensitive resin the transmissivity (mean value of transmission peak wavelength in 400nm～780nm scope) of dipping part of photo-sensitive resin dissolving after 120 seconds must more than 98%～below 100%, more fortunately more than 99%～below 100%, better more than 99.5%～below 100%.If transmissivity 98% or more～below 100%, then little, thereby better to the influence of dyed layer brightness.
The colorant that uses among the present invention (A) both can be a toner, also can be inorganic colourant.Toner both can be an organic pigment, also can be organic dyestuff.And then toner both can be that synthetic coloring matter also can be a natural colorant.Inorganic colourant also can be the inorganic pigment of inorganic salts (extender pigment) of metal oxide, metal complex salt, barium sulphate etc.In these colorants, better use toner, better use organic pigment.
As organic pigment and inorganic pigment, can enumerate the compound that is categorized as pigment (Pigment) among " Colour Index " (Colour Index, The Society of Dyers and Colourists publish).
Specifically, can enumerate C.I. pigment yellow-1, C.I. pigment yellow-3, C.I. pigment yellow-12, C.I. pigment yellow-13, C.I. pigment yellow-14, C.I. pigment yellow-15, C.I. pigment yellow-16, C.I. pigment yellow-17, C.I. pigment yellow-20, C.I. pigment yellow-24, C.I. pigment yellow-31, C.I. pigment yellow-53, C.I. pigment yellow-83, C.I. pigment yellow-86, C.I. pigment yellow-93, C.I. pigment yellow-94, C.I. pigment yellow-109, C.I. pigment yellow-110, C.I. pigment yellow-117, C.I. pigment yellow-125, C.I. pigment yellow-128, C.I. pigment yellow-137, C.I. pigment yellow-138, C.I. pigment yellow-139, C.I. pigment yellow-147, C.I. pigment yellow-148, C.I. pigment yellow-150, C.I. pigment yellow-153, C.I. pigment yellow-154, C.I. pigment yellow-166, C.I. pigment yellow-173, C.I. pigment yellow-194, C.I. yellow uitramarine such as pigment yellow-214 grade;
C.I. orange pigments such as pigment orange-13, C.I. pigment orange-31, C.I. pigment orange-36, C.I. pigment orange-38, C.I. pigment orange-40, C.I. pigment orange-42, C.I. pigment orange-43, C.I. pigment orange-51, C.I. pigment orange-55, C.I. pigment orange-59, C.I. pigment orange-61, C.I. pigment orange-64, C.I. pigment orange-65, C.I. pigment orange-71, C.I. pigment orange-73;
C.I. paratonere-9, C.I. paratonere-97, C.I. paratonere-105, C.I. paratonere-122, C.I. paratonere-123, C.I. paratonere-144, C.I. paratonere-149, C.I. paratonere-166, C.I. paratonere-168, C.I. paratonere-176, C.I. paratonere-177, C.I. paratonere-180, C.I. paratonere-192, C.I. paratonere-209, C.I. paratonere-215, C.I. paratonere-216, C.I. paratonere-224, C.I. paratonere-242, C.I. paratonere-254, C.I. paratonere-264, C.I. red pigment such as paratonere-265;
C.I. blue pigments such as alizarol saphirol-15, C.I. alizarol saphirol-15:3, C.I. alizarol saphirol-15:4, C.I. alizarol saphirol-15:6, C.I. alizarol saphirol-60;
C.I. violet pigments such as pigment violet-1, C.I. pigment violet-19, C.I. pigment violet-23, C.I. pigment violet-29, C.I. pigment violet-32, C.I. pigment violet-36, C.I. pigment violet-38;
C.I. viridine green such as naphthol green-7, C.I. naphthol green-36;
C.I. brown such as pigment brown-23, C.I. pigment brown-25;
C.I. black pigment such as pigment black-1, C.I. pigment black-7 etc.
Be preferably and contain at least a pigment of from C.I. pigment yellow-138, C.I. pigment yellow-139, C.I. pigment yellow-150, C.I. paratonere-177, C.I. paratonere-209, C.I. paratonere-254, C.I. pigment violet-23, C.I. alizarol saphirol-15:6 and C.I. naphthol green-36, selecting in the middle of these pigment.
These organic pigments and inorganic pigment both can be used alone, can also be two or more kinds in combination separately.
For example, in order to form red pixel, better contain C.I. paratonere-254 and C.I. pigment yellow-139.
In order to form green pixel, better contain at least a kind and C.I. naphthol green-36 selecting one group that forms from C.I. pigment yellow-150 and C.I. pigment yellow-138.
In order to form blue pixel, better contain C.I. alizarol saphirol-15:6 and C.I. pigment violet-23.
Organic pigment in the described pigment also can be implemented rosin in case of necessity and handle, uses the surface treatment of the pigment derivative that imported acidic groups or basic group etc., with macromolecular compound etc. the grafting of surface of pigments is handled, adopted the micronize of sulfuric acid micronize method etc. to handle, removes processing etc. with the carrying out washing treatment of organic solvent or water etc., ionic impurity with ion exchange process etc. for removing impurity.And then, after the photosensitive composition preparation, also can embodiment such as ion exchange process etc. remove processing.
The amount of colorant (A), when being divided into 100 mass parts with the solid shape in the photosensitive composition, normally 25 mass parts above～60 mass parts are following, better 27 mass parts are above～55 mass parts are following, better 30 mass parts are above～below 50 mass parts.If the amount of colorant (A) more than 25 mass parts～below 60 mass parts, colour saturation is gratifying when then making chromatic filter, and can contain the resin glue of necessary amount in the composition, thereby can form the enough patterns of physical strength, thereby better.
At this, the solid shape branch in the photosensitive composition means and remove (F) back rest parts of desolvating from photosensitive composition.
In the photosensitive composition of the present invention,, better be its uniform particle diameter using under the situation of pigment as colorant (A).Contain surfactant and carry out method of dispersion treatment etc. as pigment dispersing agent (E) in order to make pigment that the homogeneous particle diameter be arranged, can to enumerate.
As described pigment dispersing agent (E), can enumerate for example surfactants such as polyoxyethylene alkyl ether system, polyoxyethylene alkyl phenyl ether system, polyester system, acrylic acid series, polyurethane series, polyethyleneimine system, these both can use separately separately, also can be used in combination.
As polyoxyethylene alkyl ether is surfactant, can enumerate following formula structure person (14102 commodity chemical, 1286 pages (chemical industry day newspaper office, on January 29th, 2002 distribution)):
RO(CH 2CH 2O) nH
In the formula, R represents C 12～22Alkyl, n are represented 2～60 number.
As polyoxyethylene alkyl ether is surfactant, can enumerate for example polyoxyethylene decyl ethers, polyoxyethylene lauryl ether, polyoxyethylene cetyl base ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene 2-ethylhexyl ether etc.
As polyoxyethylene alkyl ether is the commercially available product of surfactant, can enumerate BLAUNON-EL series, BLAUNON-CH series, BLAUNON-SR series, BLAUNON-EN series, BLAUNON-EH series, BLAUNON-DAL series, BLAUNON-DAI series, BLAUNON-DAH series, BLAUNON-OX series (be blue or green wood oil fat company make) etc., the equivalence product of other company also can use equally.
As polyoxyethylene alkyl phenyl ether is surfactant, can enumerate following formula structure person and wait (14102 commodity chemical, 1287 pages (chemical industry day newspaper office, distribution on January 29th, 2002));
In the formula, m represents 1～5 integer, and n represents 2～60 number, and R represents C 12～22Alkyl or the phenyl of replacement also can be arranged both can be the same or different but m is 2～5 o'clock R.
As polyoxyethylene alkyl phenyl ether is the commercially available product of surfactant, can enumerate BLAUNON-NK series, BLAUNON-N series, BLAUNON-DP series, BLAUNON-DNP series, BLAUNON-DSP series, BLAUNON-TSP series, BLAUNON-PH series, BLAUNON-BA series etc., the equivalence product of other company can use too.
Polyester is that surfactant has polyester construction.As polyester is surfactant, can enumerate Disperbyk-161, with trade mark 170 (BYKChemie corporate system), PB821 (monosodium glutamate corporate system) etc.
Polyethyleneimine is that surfactant has the aziridine structure.As polyethyleneimine is surfactant, can enumerate Sorsperse 24000 GR (Seneca corporate system) etc., and the equivalence product of other company can use too.
The acrylic acid series surfactant has the acrylic acid copolymer structure.As the acrylic acid series surfactant, can enumerate Disperbyk-352, with trade mark 354, with trade mark 2000, with trade mark 2001 (BYK Chemie corporate system), EFKA-Polymer 401 (EFKA Chemicals corporate system) etc., the equivalent product of other company can be used too.
The polyurethane series surfactant has polyurethane structural.As the polyurethane series surfactant, can enumerate EFKA-Polymer 452, EFKA-47 (EFKA Chemicals corporate system) etc., the equivalent product of other company can be used too.
And then, as the surfactant beyond above-mentioned, can enumerate trade name KP (chemical industrial company of SHIN-ETSU HANTOTAI system), Port リ Off ロ-(common prosperity chemical company system), EFTOP (TochemProducts corporate system), メ ガ Off ア ッ Network ス (big Japanese Ink chemical industrial company system), Off ロ ラ-De (Sumitomo ス リ-エ system corporate system), ア サ ヒ ガ-De, サ-Off ロ Application (more than be the Asahi Glass corporate system) etc.
As pigment dispersing agent (E), better using from polyester is that surfactant, polyethyleneimine are at least a kind of surfactant selecting the surfactant, polyurethane series surfactant, acrylic acid series surfactant form one group, better uses the acrylic acid series surfactant.
The use amount of pigment dispersing agent (E), for per 1 mass parts of colorant (A), normally 1 mass parts following, better be 0.05 mass parts above～below 0.5 mass parts.If the use amount of pigment dispersing agent (E) below 1 mass parts, then has the tendency that can obtain homogeneous particle diameter pigment for per 1 mass parts of colorant (A), thereby better.
The resin glue that uses in the photosensitive composition of the present invention (B) better contains the structural unit of deriving from (methyl) acrylic acid.Resin glue (B) be more preferably the structural unit of deriving from (methyl) acrylic acid and can with the acrylic acid series copolymer of other monomer of its copolymerization.
At this, (methyl) acrylic acid is represented acrylic acid and/or methacrylic acid.The amount of described structural unit of deriving from (methyl) acrylic acid the general construction unit that constitutes resin glue (B) better is more than the 16mol%～below the 40mol%.If the amount of (methyl) acrylic acid units is in described scope, the then favorable solubility of non-pixel portions in resin bed during video picture, and the non-pixel portions after the video picture has residue to be difficult to residual tendency, thereby better.
But, can enumerate the macromonomer class etc. that aromatic ethenyl compound for example, unsaturated carboxylate type, the amino alkane ester of unsaturated carboxylic acid class, unsaturated carboxylic acid ethylene oxidic ester class, vinyl carboxylates class, unsaturated ether, vinyl cyanide based compound, unsaturated acyl amine, unsaturated acid imide, aliphatics conjugated diene class, polymer molecule chain end have an acryloyl group or monomethyl acryloyl group as the monomer of other copolymerization.
As described acrylic acid series copolymer, for example can enumerate methacrylic acid/benzyl methacrylate multipolymer, methacrylic acid/benzyl methacrylate/styrol copolymer, the different norborneol ester copolymer of methacrylic acid/benzyl methacrylate/methacrylic acid, methacrylic acid/styrene/methacrylic acid benzyl ester/N-phenylmaleimide multipolymer and contain multipolymer with constituent shown in the following formula (I) etc.:
R in the formula (I) 1And R 2Represent hydrogen atom or methyl independently of one another.
Wherein, better use constituent (R shown in methacrylic acid/benzyl methacrylate multipolymer, methacrylic acid/benzyl methacrylate/styrol copolymer, the different norborneol ester copolymer of methacrylic acid/benzyl methacrylate/methacrylic acid, the methacrylic acid/described formula (I) 1Be methyl, R 2Be hydrogen atom)/benzyl methacrylate multipolymer and described formula (I) shown in constituent (R 1Be methyl, R 2Be hydrogen atom)/the benzyl methacrylate multipolymer.
The resin glue that constituent shown in the formula (I) is arranged, for example constituent (R shown in methacrylic acid/described formula (I) 1Be methyl, R 2Be hydrogen atom)/the benzyl methacrylate multipolymer can obtain 2 composition polymkeric substance, make resulting 2 composition polymkeric substance and obtain with the method for composition shown in the following formula (II) reaction etc. again by making methacrylic acid and benzyl methacrylate polymerization:
In the formula (II), R 2The expression hydrogen atom.
The acid number of the resin glue that uses among the present invention (B) is 60～135 normally 50～150, better, is more preferably 70～135.If described acid number is 50～150, then the dissolubility to imaging liquid improves, and unexposed portion becomes and dissolves easily, and the susceptibility raising, makes the pattern of exposure portion residual during video picture, and the tendency that improves residual film ratio is arranged, thereby better.At this, acid number is in the conduct and the value of the needed potassium hydroxide quantity of acrylic acid series polymeric compounds 1g (mg) mensuration, usually can be by obtaining with the potassium hydroxide aqueous solution titration.
And then resin glue (B) is that its polystyrene conversion weight-average molecular weight is generally 5,000～35,000, better 6,000～30,000, better 7,000～28,000.If molecular weight is 5,000～35,000, then raisings of the hardness of hard resin-layer (filming), also high, unexposed favorable solubility of residual film ratio to imaging liquid, the tendency that improves resolution is arranged, thereby better.
The mass fraction of described resin glue (B) for the solid shape of photosensitive composition is divided normally more than the 5 quality %～below the 50 quality %, better be more than the 10 quality %～below the 40 quality %, be more preferably more than the 15 quality %～below the 35 quality %.The amount of described resin glue if more than the 5 quality %～below the 50 quality %, then to form be possible to pattern, and resolution and residual film ratio have the tendency of raising, thereby better.
The optical polymerism compound (C) that uses among the present invention is the compound that can come initiated polymerization by irradiation light from the living radical of Photoepolymerizationinitiater initiater generation.As optical polymerism compound (C), can enumerate compound that the polymerism carbon-to-carbon unsaturated bond is for example arranged etc.This compound both can be the optical polymerism compound of simple function, also can be 2 officials can or 3 officials can be above multifunctional optical polymerism compound.
As the optical polymerism compound of simple function, can enumerate for example acrylic acid nonyl phenyl carbitol ester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, acrylic acid 2-ethylhexyl carbitol ester, acrylic acid 2-hydroxy methacrylate, N-vinyl pyrrolidone etc.
Optical polymerism compound as 2 officials energy, can enumerate for example diacrylate 1,6-hexanediol ester, dimethacrylate 1, two (acrylyl oxy-ethyl) ether of 6-hexanediol ester, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, diacrylic acid pentyl diol ester, dimethacrylate DOPCP, diacrylate triethyleneglycol ester, dimethacrylate triethyleneglycol ester, bisphenol-A, diacrylate 3-methyl pentanediol ester, dimethacrylate 3-methyl pentanediol ester etc.
As the above multifunctional optical polymerism compound of 3 officials energy, can enumerate for example three acrylic acid three (methylol) propane esters, trimethyl acrylic acid three (methylol) propane ester, pentaerythritol triacrylate, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, five acrylic acid dipentaerythritol esters, pentamethyl acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol esters, hexamethyl acrylic acid dipentaerythritol ester etc.
Described optical polymerism compound both can use separately separately, also can be used in combination more than 2 kinds.The amount of optical polymerism compound (C), for the solid shape branch of photosensitive composition, by mass fraction, normally 16 quality % above～31 quality % are following, better be 18 quality % above～30 quality % are following, be more preferably 19 quality % above～below the 29 quality %.Optical polymerism compound (C) if amount 16 quality % above～below the 31 quality %, then residual film ratio fully takes place, has improved in sclerosis, thereby better.
As the Photoepolymerizationinitiater initiater that uses among the present invention (D), can enumerate for example acetophenone based compound, triazine based compound, bisglyoxaline based compound, oxime compound, the potpourri in these compounds more than 2 kinds.
As the acetophenone based compound, can enumerate oligomer of for example diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, benzyldimethylketal, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) third-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) third-1-ketone etc.In the middle of these, better use 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) third-1-ketone.And then multiple acetyl benzene series and other Photoepolymerizationinitiater initiater also can be used in combination.
As other Photoepolymerizationinitiater initiater, can enumerate living radical propellant, acid-producing agent of living radical etc. can take place by irradiates light.
As the triazine based compound, for example can enumerate 2,4-two (trichloromethyl)-6-(4-methoxyphenyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl naphthyl)-1,3,5-triazines, 2,4-two (trichloromethyl)-6-(4-methoxyl-styrene)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(2-(4-diethylin-2-aminomethyl phenyl) vinyl)-1,3,5-triazines, 2, (2-(3 for 4-two (trichloromethyl)-6-, the 4-Dimethoxyphenyl) vinyl)-1,3,5-triazines etc.
As united imidazole, can enumerate 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (to carbethoxy phenyl) bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (to bromophenyl) bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (neighbours, right-dichlorophenyl) bisglyoxaline, 2,2 '-two (o-bromophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (neighbours, right-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (m-methoxyphenyl) bisglyoxaline, 2,2 '-two (neighbours, adjacent '-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (ortho-nitrophenyl bases)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (o-methyl-phenyl-)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline etc.
As oxime compound; can enumerate O-acyl group oxime compound; as its concrete example; can enumerate 1-(4-benzenesulfonamido group phenyl) fourth-1; 2-diketone 2-oxime-O-benzoate, 1-(4-benzenesulfonamido group phenyl) suffering-1,2-diketone 2-oxime-O-benzoate, 1-(4-benzenesulfonamido group phenyl) suffering-1-ketoxime-O-acetate, 1-(4-benzenesulfonamido group phenyl) fourth-1-ketoxime-O-acetate etc.
As the living radical propellant, can enumerate for example benzoin based compound, benzophenone based compound, thioxanthones based compound, triazine based compound.
As the benzoin based compound, can enumerate for example benzoin, benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether etc.
As the benzophenone based compound, for example can enumerate benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, sulphurous acid 4-benzoyl-4 '-methyldiphenyl ester, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-trimethyl benzophenone etc.
As the thioxanthones based compound, can enumerate for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As the triazine based compound, can enumerate same as described above those.
As the living radical propellant beyond above-mentioned, for example can enumerate 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 10-butyl-2-chloro-acridine ketone, 2-EAQ, benzil, 9,10-phenanthrenequione, camphorquinone, phenylacetaldehyde acid methyl esters, two cyclopentadiene titanium compounds etc.
As acid-producing agent, can enumerate for example salt or nitrobenzyl toluenesulfonic acid salt, benzoin toluenesulfonic acid salts etc. such as p-toluenesulfonic acid 4-hydroxy phenyl dimethyl sulfonium, hexafluoro-antimonic acid 4-hydroxy phenyl dimethyl sulfonium, p-toluenesulfonic acid 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl methyl benzyl sulfonium, p-toluenesulfonic acid triphenyl sulfonium, hexafluoro-antimonic acid triphenyl sulfonium, p-toluenesulfonic acid diphenyl iodine, hexafluoro-antimonic acid diphenyl iodine.
And then, in above-claimed cpd, the compound that acid takes place is arranged also when free radical takes place as the living radical propellant, for example, triazine is that Photoepolymerizationinitiater initiater also can be used as the acid-producing agent use.
The amount of described Photoepolymerizationinitiater initiater (D), for the total of resin glue (B) and optical polymerism compound (C) is measured 100 mass parts, normally 0.1 mass parts above～30 mass parts are following, better 1 mass parts is above～below 25 mass parts.If the amount of Photoepolymerizationinitiater initiater more than 0.1 mass parts～below 30 mass parts, then susceptibility improves, the time shutter shortens, throughput rate improves, and the tendency that does not make resolution become bad because of susceptibility is too high is arranged, thereby better.
As Photoepolymerizationinitiater initiater (D), better use 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 2,4-two (trichloromethyl)-6-piperonyl-1,3,5-triazines.
Also can use photopolymerization to cause auxiliary agent among the present invention.Photopolymerization causes auxiliary agent and better is used in combination with Photoepolymerizationinitiater initiater, is the polymeric compounds that is used for promoting by the optical polymerism compound of Photoepolymerizationinitiater initiater initiated polymerization.Cause auxiliary agent as photopolymerization, can enumerate amine compound, alkoxy anthracene based compound, thioxanthones based compound etc.
As amine compound, can enumerate for example triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino isoamyl benzoate, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (diethylin) benzophenone, 4,4 '-two (ethyl dimethylamine base) benzophenone etc.In the middle of these, better use 4,4 '-two (diethylin) benzophenone.
As the alkoxy anthracene based compound, for example can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
As the thioxanthones based compound, can enumerate same as described above those.
Photopolymerization causes auxiliary agent and both can use separately also and can multiplely be used in combination.And then, also can use as photopolymerization and cause commercially available those of auxiliary agent, and cause auxiliary agent as commercially available photopolymerization, for example can enumerate trade name " EAB-F " (hodogaya chemical industrial group system) etc.
Cause the combination of auxiliary agent as Photoepolymerizationinitiater initiater and photopolymerization in the photosensitive composition of the present invention, can enumerate for example diethoxy acetophenone/4,4 '-two (diethylin) benzophenone, 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) third-1-ketone/4,4 '-two (diethylin) benzophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone/4,4 '-two (diethylin) benzophenone, benzyldimethylketal/4,4 '-two (diethylin) benzophenone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) third-1-ketone/4,4 '-two (diethylin) benzophenone, 1-hydroxycyclohexylphenylketone/4,4 '-two (diethylin) benzophenone, oligomer/4 of 2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) third-1-ketone, 4 '-two (diethylin) benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone/4,4 '-two (diethylin) benzophenone etc.In the middle of these, better use 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) third-1-ketone/4,4 '-two (diethylin) benzophenone.
Using these photopolymerization to cause under the situation of auxiliary agents, its use amount for per 1 mole of Photoepolymerizationinitiater initiater usually below 10 moles, more fortunately more than 0.01 mole～below 5 moles.
As the solvent that uses among the present invention (F), for example can enumerate ethers, aromatic hydrocarbon based, ketone, alcohols, ester class, amide-type etc.
As ethers, can enumerate for example tetrahydrofuran, oxinane, 1, the 4-diox, glycol monomethyl ether, ethylene glycol monoethyl ether, propyl cellosolve, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monomethyl ether, carbitol, butylcarbitol, diethylene glycol dimethyl ether, diethyl carbitol, the diglycol dipropyl ether, diethylene glycol dibutyl ether, acetate propylene glycol monomethyl ether ester, acetate propylene glycol monoethyl ether ester, acetate propylene glycol one propyl ether ester, the acetic acid methyl cellosolve ester, acetate ethyl cellosolve ester, acetate ethyl carbitol ester, the butyl carbitol acetate ester, acetate propylene glycol monomethyl ether ester, methoxy butyl acetate, acetate methoxyl pentyl ester, anisole, phenetol, methyl anisole etc.
As aromatic hydrocarbon based, for example can enumerate benzene,toluene,xylene, etc.
As ketone, can enumerate for example acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone etc.
As alcohols, can enumerate for example methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.
As the ester class, can enumerate for example ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, acetate 3-methoxyl butyl ester, acetate 3-methyl-3-methoxyl butyl ester, gamma-butyrolacton etc.
As amide-type, can enumerate for example N, dinethylformamide, N,N-dimethylacetamide etc.
As other solvent, can enumerate for example N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc.
Above-mentioned solvent both can use separately separately also and can be used in combination more than 2 kinds.Amount in photosensitive composition, by mass fraction, normally 70 quality % above～95 quality % are following, better 75 quality % are above～below the 90 quality %.If the amount of solvent (F) is in described scope, when then being coated with flatness good and also when forming chromatic filter display characteristic good, thereby better.
Solvent (F) better contains at least a kind that selects one group that forms from acetate propylene glycol monomethyl ether ester and 3-ethoxyl ethyl propionate.And use under the situation of at least a kind of solvent selecting one group that forms from acetate propylene glycol monomethyl ether ester and 3-ethoxyl ethyl propionate and other solvent, its mixture ratio, by mass fraction, for the total solvent use amount, select form from acetate propylene glycol monomethyl ether ester and 3-ethoxyl ethyl propionate one group at least a kind better be 50～100 quality % usually, be more preferably 60～100 quality %.If at least a kind of solvent selecting form from acetate propylene glycol monomethyl ether ester and 3-ethoxyl ethyl propionate one group for total solvent by mass fraction 50～100 quality %, the tendency that then has flatness to become good, thereby better.
In photosensitive composition used in the present invention, also can contain epoxy compound.As epoxy compound, can enumerate for example to handle in (heat treated) to make the crosslinked epoxy compound of resin glue in the back oven dry of video picture after stain pattern.And then, also can be the epoxy compound that can make its independent polymerization by heating.Because this epoxy compound is by making resin glue crosslinked or make himself polymerization make the colored pattern sclerosis, thereby the sublimate from colored pattern is difficult to produce in the oven dry of described back, thereby better uses it.
As described epoxy compound, can enumerate for example fragrant family epoxy resin such as bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, novolac type epoxy resin;
Alicyclic epoxy resin, polycycle epoxy resin, glycidyl ester type resin, glycidic amine type resin, epoxidation wet goods epoxy resin;
The brominated derivative of described epoxy resin;
The epoxide of the epoxide of the epoxide of the epoxide of fatty compound, the epoxide of alicyclic compound, aromatics, butadiene (being total to) polymkeric substance, isoprene (being total to) polymkeric substance, (methyl) glycidyl acrylate (being total to) polymkeric substance, triglycidyl isocyanurate etc.
The amount of epoxy compound in the photosensitive composition, for the solid shape branch of photosensitive composition, by mass fraction, usually below 15%, more fortunately more than 0.5%～below 12%, better more than 1%～below 10%.If the amount of described epoxy compound below 15 quality %, sclerosis just can fully take place and residual film ratio is improved, thereby better.
Also can contain adjuvants such as macromolecular compound beyond the surfactant, filling agent, resin glue, adhesion promotor, antioxidant, ultraviolet light absorber, anti-agglutinant, organic acid, organic amine compound, rigidizer in the photosensitive composition of the present invention.
As surfactant, can use at least a kind that from silicone-based surfactant, fluorine are surfactant and be made up of the silicone-based surfactant of fluorine atom one group, selects.
As the silicone-based surfactant, can enumerate the surfactant of siloxane bond.Specifically, can enumerate Toray Silicone DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified silicon oil SH8400 (trade name, the Toraysilicone corporate system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Silicone of SHIN-ETSU HANTOTAI corporate system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (ジ-イ-シ リ of Toshiba コ-corporate system) etc.
As fluorine is surfactant, can enumerate the surfactant of fluorocarbon chain.Specifically, can enumerate Off ロ リ Na-ト (trade name) FC430, same FC431 (Sumitomo ス リ-エ system corporate system), メ ガ Off ア ッ Network (trade name) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (big Japanese Ink chemical industrial company system), エ Off ト ッ プ (trade name) EF310, same EF303, same EF351, same EF352 (new autumn fields changes into corporate system), サ-Off ロ Application (trade name) S381, same S382, same SC101, same SC105 (Asahi Glass corporate system), E5844 (Da Jin fine chemicals research institute (company) system), BM-1000, BM-1100 (being trade name, BM Chemie corporate system) etc.
As the silicone-based surfactant that fluorine atom is arranged, can enumerate the surfactant of siloxane bond and fluorocarbon chain.Specifically, can enumerate メ ガ Off ア ッ Network (trade name) R08, same BL20, same F475, same F477, same F443 (big Japanese Ink chemical industrial company make) etc.
These surfactants both can use separately separately, also can be used in combination more than 2 kinds.
These surfactants, with respect to for 100 mass parts of the photosensitive composition the surfactant, can be below 0.6 mass parts, more fortunately more than 0.001 mass parts～use in the scope of 0.5 mass parts.If the amount of surfactant is below 0.6 mass parts, the tendency that then has flatness to become good, thereby better.
As filling agent, can enumerate for example particulate of glass, aluminium oxide etc.
As the macromolecular compound beyond the resin glue, can enumerate for example polyvinyl alcohol (PVA), polyacrylic acid, polyglycol one alkyl ether, polyacrylic acid fluoroalkane ester etc.
As adhesion promotor, can enumerate for example vinyl trimethoxy monosilane, the vinyl triethoxyl monosilane, vinyl three (2-methoxy ethoxy) monosilane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxy oxygen base monosilane, N-(2-amino-ethyl)-3-aminopropyl trimethoxy monosilane, 3-aminopropyl triethoxy-silicane, 3-glycidoxy propyl trimethoxy monosilane, 3-glycidoxy propyl group methyl dimethoxy oxygen base monosilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy monosilane, 3-chloropropyl methyl dimethoxy oxygen base monosilane, 3-r-chloropropyl trimethoxyl monosilane, 3-methacryloxypropyl trimethoxy monosilane, 3-sulfydryl propyl trimethoxy monosilane etc.
As antioxidant, for example can enumerate 4,4 '-sulphur two (the 6-tert-butyl group-3-methylphenol), 2,6 di tert butyl 4 methyl phenol etc.
As ultraviolet light absorber, can enumerate for example 2-(the 2-hydroxyl-3-tert-butyl group-5-aminomethyl phenyl)-benzotriazoles such as 5-chlorobenzotriazole system, 2-hydroxyl-benzophenone such as 4-octyloxy benzophenone system, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2, benzoic ethers such as 4-di-t-butyl phenyl ester system, 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-triazine systems such as the own oxygen base of 5-phenol etc.
As anti-agglutinant, can enumerate for example sodium polyacrylate etc.
As organic acid, for example can enumerate:
Formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, aliphatics monocarboxylic acid class such as sad;
Aliphatic dicarboxylic acid classes such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids classes such as tricarballylic acid, aconitic acid, camphoronic acid;
Benzoic acid, toluic acid, cumic acid, 2, aromatic series monocarboxylic acid classes such as 3-mesitylenic acid, woods acid;
Aromatic dicarboxylic acid classes such as phthalic acid, m-phthalic acid, terephthalic acid (TPA);
Aromatic multi-carboxy acid's classes such as trimellitic acid, trimesic acid, inclined to one side benzene tetracarboxylic acid, Pyromellitic Acid etc.
As organic amine compound, for example can enumerate:
Primary monoamines such as n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine;
One naphthenic base amines such as cyclo-hexylamine, 2-methylcyclohexyl amine, 3-methylcyclohexyl amine, 4-methylcyclohexyl amine;
Dialkyl amines such as Methylethyl amine, diethylamide, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, di-n-propyl amine, diisopropylamine, di-n-butyl amine, diisobutyl amine, two sec-butylamine, di-t-butyl amine, two n-pentyl amine, di-n-hexyl amine;
One alkyl, one naphthenic base amines such as methylcyclohexyl amine, ethyl cyclo-hexylamine;
Bicyclic alkyl amines such as dicyclohexyl amine;
Trialkyl amines such as dimethylethyl amine, methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl n-pro-pyl amine, methyl di-n-propyl amine, ethyl di-n-propyl amine, three n-pro-pyl amine, triisopropylamine, tri-n-butyl amine, triisobutyl amine, three sec-butylamine, tri-tert amine, three n-pentyl amine, three n-hexyl amine;
Dialkyl group one naphthenic base amines such as dimethylcyclohexylam,ne, diethyl cyclo-hexylamine;
One alkyl bicyclic alkyl amines such as methyl bicyclic alkyl amine, ethyl bicyclic alkyl amine, thricyclohexyl amine;
The 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-alkanol amines such as 1-hexanol;
4-amino-cyclic alkanol amines such as 1-cyclohexanol;
Dialkanol amines such as diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, two n-hexyl alcohol amine;
Two cyclic alkanol amines such as two (4-cyclohexanol) amine;
Three alkanol amines such as triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, three n-hexyl alcohol amine;
Three cyclic alkanol amines such as three (4-cyclohexanol) amine;
3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol, 4-amino-1,3-butylene glycol, 3-dimethylamino-1,2-propylene glycol, 3-diethylin-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylin-1, amino alkane glycols such as ammediol;
4-amino-1,2-cyclohexane diol, 4-amino-1, amino cycloalkanes glycolss such as 3-cyclohexane diol;
1-amino cyclopentyl ketone methyl alcohol, 4-amino cyclopentyl ketone methyl alcohol etc. contain amino cyclanone methyl alcohol class;
The amino cyclohexanone methyl alcohol of 1-, the amino cyclohexanone methyl alcohol of 4-, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylin cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylin cyclohexane methanol etc. contain amino cycloalkanes methyl alcohol class;
Aminocarboxylic acids such as Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 1-1-aminocyclopropane-1-carboxylic acid, 1-aminocyclohexane carboxylic acid, 4-aminocyclohexane carboxylic acid;
Aniline, o-toluidine, a methylaniline, to methylaniline, to ethylaniline, to n-propylbenzene amine, cumidine, to n-butyl aniline, p-tert-butyl-aniline, N, accelerine, N, the N-diethylaniline, to methyl-N, aromatic amines such as accelerine;
Adjacent aminobenzyl alcohol, an aminobenzyl alcohol, to aminobenzyl alcohol, to dimethylamino benzylalcohol, to aminobenzyl alcohol classes such as diethylin benzylalcohols;
O-aminophenol, m-aminophenol, para-aminophenol, to dimethylamino phenol, to amino phenols such as diethylin phenol;
Gavaculine, p-aminobenzoic acid, to the dimethylamino benzoic acid, to aminobenzoic acids such as diethylin benzoic acid etc.
As rigidizer, thus for example can enumerate can be by heating with resin glue in carboxyl reaction make the crosslinked compound of resin glue.And then, thereby also can enumerate the compound that the independent polymerization of meeting itself makes the colored pattern sclerosis.As described compound, can enumerate for example epoxy compound, oxetane compound etc.
As epoxy compound, can enumerate for example bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, novolac type epoxy resin, other fragrant family epoxy resin, alicyclic epoxy resin, polycycle epoxy resin, the glycidyl ester type resin, the glycidic amine type resin, epoxidation wet goods epoxy resin, or the brominated derivative of these epoxy resin, aliphatics beyond epoxy resin and the brominated derivative thereof, alicyclic or aromatic epoxide, the epoxide of butadiene (being total to) polymkeric substance, the epoxide of isoprene (being total to) polymkeric substance, (methyl) glycidyl acrylate (being total to) polymkeric substance, triglycidyl isocyanurate etc.
As oxetane compound, can enumerate for example carbonic acid dioxane butyl ester, inferior dimethylbenzene dioxetane, hexane diacid dioxane butyl ester, terephthalic acid (TPA) dioxane butyl ester, cyclohexane dicarboxylic acid dioxane butyl ester etc.
Photosensitive composition of the present invention also can contain the compound of the oxetanes skeleton ring-opening polymerization of the epoxy radicals that can make epoxy compound or oxetane compound under situation about containing as the epoxy compound of rigidizer or oxetane compound etc.As described compound, can enumerate for example polybasic carboxylic acid class, polybasic acid anhydride class, acid-producing agent etc.
As the polybasic carboxylic acid class, can for example enumerate
Phthalic acid, 3,4-dimethyl phthalic acid, m-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid, trimellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-aromatic series polybasic carboxylic acid classes such as benzophenone tetrabasic carboxylic acid;
Succinic acid, glutaric acid, hexane diacid, 1,2,3, aliphatics polybasic carboxylic acid classes such as 4-BTCA, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyl tetrahydro phthalic acid, six hydrogen m-phthalic acids, six hydrogen terephthalic acid (TPA)s, 1,2,4-cyclopentane tricarboxylic acids, 1,2,4-cyclohexane tricarboxylic acids, cyclopentane tetrabasic carboxylic acid, 1,2,4, alicyclic polybasic carboxylic acid classes such as 5-cyclohexane tetrabasic carboxylic acid.
As the polybasic acid anhydride class, can for example enumerate
Phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, 3,3 ', 4,4 '-the benzophenone tetracarboxylic dianhydride waits aromatic series polybasic acid anhydride class;
Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, 1,2,3, aliphatics polybasic acid anhydride classes such as 4-butane tetracarboxylic acid dianhydride;
Hexahydrophthalic anhydride, 3,4-dimethyl tetrahydro phthalic anhydride, 1,2,4-cyclopentane tricarboxylic acid anhydride, 1,2,4-cyclohexane tricarboxylic acid anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, Hai Mike (Ha イ ミ ッ Network) acid anhydrides, 4-norborene-1, alicyclic polybasic acid anhydride classes such as 2-dicarboxylic anhydride;
Ethylene glycol bisthioglycolate trimellitic acid ester acid anhydride, glycerine three trimellitic acid ester acid anhydrides etc. contain the carboxyanhydrides of ester group etc.
As the polybasic acid anhydride class, also can use as commercially available those of epoxy resin hardener.As described epoxy resin hardener, can enumerate for example trade name " ア デ カ Ha-De Na-EH-700 " (Asahi Electro-Chemical Co. Ltd's system), trade name " リ カ シ ッ De HH " (new Japanese physics and chemistry corporate system), trade name " MH-700 " (new Japanese physics and chemistry corporate system) etc.
As acid-producing agent, can enumerate same as described above those.
Described rigidizer both can use separately separately also and can be used in combination more than 2 kinds.
As the method that forms chromatic filter with photosensitive composition of the present invention, can enumerate and photosensitive composition of the present invention is coated on substrate or on other photosensitive composition layer of the solid that forms earlier on the substrate (below be called substrate etc.), the resin bed prebake of coating is removed volatile ingredient such as desolvate, make the resin bed exposure of having removed volatile ingredient via photomask, then with imaging liquid video pictures such as aqueous alkalis, carry out the back oven dry to form hard resin-layer, with described step is 1 step, repeat this step with the photosensitive composition that contains other color, finally be formed with the method etc. of the chromatic filter of RGB (RGB) 3 looks.
As substrate, can enumerate the substrate that for example glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, aromatic polyamide substrate, polyamideimide-based plate, polyimide substrate, Al substrate, GaAs substrate etc. have an even surface.On these substrates, also can implement to adopt the pre-treatment such as medicine processing, Cement Composite Treated by Plasma, ion plating processing, spraying plating processing, gas-phase reaction processing, vacuum evapn deposition processes of medicines such as monosilane coupling agent.And then, also can on the surface of described substrate, form TFT (thin film transistor (TFT)), CCD (charge bonded element) etc.
In order on described substrate, to be coated with photosensitive composition, for example, if with photosensitive composition of the present invention with spin-coating method (spincoat method), casting method, rolling method, slit and spin-coating method, gap coating method etc. usually coating process on substrate etc., be coated with, make by heating then volatile ingredient such as solvent volatilize (prebake).So just can on substrate etc., form the resin bed that the solid shape by photosensitive composition is grouped into.
Then, the resin bed exposure that the solid shape by photosensitive composition is grouped into.Exposure is as long as adopt via the method for photomask irradiation light etc.As employed light, can enumerate ultraviolet ray that is commonly referred to g line (wavelength 436nm), i line (wavelength 365nm) etc.Though light shines via photomask, the photomask here is the sort of such as the light shield layer that is provided with shield lights on glass pane surface.The part that light shield layer is not set on the glass plate is the transmittance section of transmissive light, make the exposure of photosensitive composition layer with pattern, just produced not irradiation area that does not have irradiation light and the irradiation area that has shone light according to this transmittance section pattern.The irradiate light amount of irradiation area can cause the kind of auxiliary agent or amount etc. according to the kind of the kind of the weight-average molecular weight of resin glue, monomer ratio, amount, optical polymerism compound or amount, Photoepolymerizationinitiater initiater or amount, photopolymerization and suitably select.
Exposure back video picture.For video picture, as long as, specifically, impregnated in the imaging liquid as long as will form the substrate of the state of resin bed in its surface such as the resin bed after the exposure is contacted with imaging liquid.
As imaging liquid, can enumerate aqueous solution of alkali compounds such as sodium carbonate, sal tartari, NaOH, potassium hydroxide, tetramethylammonium hydroxide for example etc.By video picture, the not irradiation area that does not shine light in the resin bed is removed.On the other hand, the irradiate light zone left behind with its former state, has formed pattern.
Usually wash after the video picture, drying, just can obtain target pattern.And then, after video picture, the drying, can also place and carry out oven dry formation hard resin-layer in back in the device such as drying oven.By the back oven dry, improved the physical strength of pattern.Using under the situation of person as photosensitive composition that further contain the rigidizer, colored pattern further hardens, and its physical strength can further improve.The temperature of back oven dry usually more than 180 ℃～below 250 ℃, more fortunately more than 200 ℃～below 230 ℃.If the back bake out temperature is in described scope, then sclerosis is fully carried out, thereby better.In addition, normally 5～40 minutes time, better 10～36 minutes of back oven dry, better at 15～30 minutes.If the back drying time is in described scope, then sclerosis is fully carried out, thereby better.
Like this, formed the target colored pattern, but changed the color of the colorant that contains in the photosensitive composition, equally carried out with above-mentioned, on substrate, form resin bed once more, make described resin bed exposure back, video picture, carry out the back then and dry, can further form colored pattern.Change the color of the colorant that contains in the photosensitive composition and repeat aforesaid operations, just can further form colored pattern, thus can the manufacturing objective chromatic filter.
Then, on resulting chromatic filter, carry out ITO film vapor deposition and handle.The chromatic filter that obtains like this contains above-mentioned colored pattern, and by using respectively this chromatic filter, just making manufacturing be suitable for liquid crystal indicator becomes possibility.
Video picture excellence, the hard resin-layer that can form high surface hardness and this hard resin-layer also are the solvent resistance excellences to photosensitive composition of the present invention because the residue level is good, section configuration can be formed for along taper and even rectangular-shaped, the no coarse hard resin-layer in surface, colored pattern that uses in color liquid crystal display arrangement or the imaging apparatus etc. and the chromatic filter that uses this pattern can be used to form preferably.
Embodiment
Below illustrate in greater detail the present invention based on embodiment, but the present invention is not limited to these embodiment certainly.
Embodiment 1
(preparation of photosensitive composition 1)
With (A) C.I. pigment blue 15: 6 (1.967 mass parts)
(A) C.I. pigment Violet 23 (0.030 mass parts)
(E) polyester is spreading agent (0.599 mass parts)
(B) multipolymer of methacrylic acid and benzyl methacrylate (methacrylic acid unit is 3: 7 by amount than (mol ratio) with the ratio of components of benzyl methacrylate unit, and weight-average molecular weight (Mw) is 25,000) (1.764 mass parts)
(C) six acrylic acid dipentaerythritol esters (" KAYARAD DPHA ", Japanese chemical drug corporate system) (1.176 mass parts),
(D) 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone (0.353 mass parts),
(D2) 4,4 '-two (diethylin) benzophenone (" EAB-F " (hodogaya chemical industrial group system)) (0.118 mass parts),
Epoxy compound (o-cresol novolac type epoxy resin, " ス ミ エ Port キ シ ESCN-195XL-80 " (Sumitomo Chemical Co. Ltd.'s system)) (0.294 mass parts) and
(F) acetate propylene glycol-methyl ether ester (23.700 mass parts) mixes, and obtains photosensitive composition 1.
(formation of dyed layer)
On the surface of glass substrate (コ-ニ Application ゲ corporate system, " #1737 "),, make volatile ingredient volatilization 3 minutes at 100 ℃ then, form photosensitive composition layer 1A with the above-mentioned photosensitive composition that obtains 1 of spin-coating method coating.After the cooling, this photosensitive composition layer does not just shine i line (wavelength 365nm) all sidedly via photomask.The light source of i line adopts ultrahigh pressure mercury lamp, and the irradiation light quantity is 150mJ/cm 2Then, at 25 ℃ imaging liquids (by mass fraction, the aqueous solution that contains potassium hydroxide 0.05%, sodium butylnaphthalenesulfonate 0.2% respectively) dipping carries out video picture 120 seconds in, after the pure water washing, obtains the blue-colored layer that forms on whole glass baseplate surface.This substrate of filming forms photosensitive composition layer 1B 220 ℃ of oven dry 20 minutes.In addition, after layer 1A cooling, this photosensitive composition layer exposes via photomask irradiation i line (wavelength 365nm).The light source of i line adopts ultrahigh pressure mercury lamp, shines in the directional light mode.The irradiation light quantity is 150mJ/cm 2As photomask, employing be the photomask that is used for forming the wire color pixel of wire spoke 3 μ m, 4 μ m, 5 μ m, 6 μ m, 7 μ m, 8 μ m, 9 μ m, 10 μ m, 20 μ m, 30 μ m, 40 μ m, 50 μ m and 100 μ m.Then, with the exposure after glass substrate (having formed the photosensitive composition layer on the surface) at 25 ℃ imaging liquids (by mass fraction, the aqueous solution that contains potassium hydroxide 0.05%, sodium butylnaphthalenesulfonate 0.2% respectively) floods in and carry out video picture 120 seconds, after the pure water washing, 220 ℃ of heating 20 minutes, form blue pixel 1C.
(evaluation)
Dipping carries out video picture 120 seconds in 1A layer 25 ℃ of imaging liquid (by mass fraction, containing the aqueous solution of potassium hydroxide 0.05%, sodium butylnaphthalenesulfonate 0.2% respectively) under agitation, after the pure water washing, does not observe block in the imaging liquid, is coated with the rete dissolving.The described size-grade distribution that is coated with the imaging liquid of rete マ イ Network ロ ト ラ ッ Network particle size determination device (UPA150,9230UPA (LEED have been dissolved; The NORTHRUP corporate system)) when pressing light scattering determining, maximum particle diameter is below 1.0 μ m.And then, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, according to the test method of JIS K 5400 records, on pencil scratching tester, " the Ha イ ユ ニ of Mitsubishi " do not make the maximum hardness that is coated with membrane damage obtain as measured value when adding loading 9.8N with pencil.The pencil intensity of the 1B layer of filming that forms is by the result of described method mensuration earlier, and its pencil intensity is 4H.
And then in formed blue pixel 1C, its section configuration is along taper, and the surface is no coarse, photosensitive composition 1 functional.
Embodiment 2
(preparation of photosensitive composition 2)
Except that being that the polyester that spreading agent replaces embodiment 1 to use is the spreading agent with polyethyleneimine, equally mix with embodiment 1, obtain photosensitive composition 2.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 2, equally operate with embodiment 1, make in 2A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, the same with embodiment 1, the result of the pencil intensity of mensuration 2B layer, pencil intensity is 4H.In formed blue pixel 2C, its section configuration is along taper, and no coarse on the surface, the performance of photosensitive composition 2 is good.
Embodiment 3
(preparation of photosensitive composition 3)
Except that the polyester that replaces embodiment 1 to use with the polyurethane series spreading agent is the spreading agent, equally mix with embodiment 1, obtain photosensitive composition 3.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 3, equally operate with embodiment 1, make in 3A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, the same with embodiment 1, the result of the pencil intensity of mensuration 3B layer, pencil intensity is 4H.In addition, in formed blue pixel 3C, its section configuration is along taper, and the surface is upward no coarse, and the performance of photosensitive composition 3 is good.
Comparative example 1
(preparation of photosensitive composition 4)
(methacrylic acid unit is counted 3: 7 by amount than (mol ratio) with the ratio of components of benzyl methacrylate unit except that the multipolymer with methacrylic acid and benzyl methacrylate, weight-average molecular weight (Mw) is 36,000) (1.764 mass parts) replaces outside the resin glue (B) of embodiment 1 use, equally mix with embodiment 1, obtain photosensitive composition 4.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 4, equally operate with embodiment 1, make in 4A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving 95%～98%.
Then, the same with embodiment 1, the result of the pencil intensity of mensuration 4B layer, pencil intensity is 5H.In addition, in resulting blue pixel 4C, its section configuration is along taper but can observes the pendulum limit that the performance of photosensitive composition 4 is bad.
Comparative example 2
(preparation of photosensitive composition 5)
(methacrylic acid unit is 3: 7 by amount than (mol ratio) with the ratio of components of benzyl methacrylate unit except that the multipolymer with methacrylic acid and benzyl methacrylate, weight-average molecular weight (Mw) is 4,800) replace outside the resin glue (B) of embodiment 1 use, equally mix with embodiment 1, obtain photosensitive composition 5.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 5, equally operate with embodiment 1, make in 5A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, the same with embodiment 1, the result of the pencil intensity of mensuration 5B layer, pencil intensity is 1H.In addition, the section configuration of formed blue pixel 5C is along taper, but can see rough surface.And residual film ratio is also low, and the performance of photosensitive composition 5 is bad.
Embodiment 4
(preparation of photosensitive composition 6)
Remove and to replace with the acrylic acid series spreading agent that the polyester of embodiment 1 use is a spreading agent, resin glue (B) is changed into the multipolymer of methacrylic acid and benzyl methacrylate, and (methacrylic acid unit is 35: 65 by amount than (mol ratio) with the ratio of components of benzyl methacrylate unit, weight-average molecular weight (Mw) is 10,000) and not adds the epoxy compound beyond the region of objective existence, equally mix with embodiment 1, obtain photosensitive composition 6.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 6, equally operate with embodiment 1, make in 6A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, the same with embodiment 1, the result of the pencil intensity of mensuration 6B layer, pencil intensity is 9H.In addition, in formed blue pixel 6C, its section configuration is along taper, and the surface is no coarse, and the performance of photosensitive composition 6 is good.
Embodiment 5
(preparation of photosensitive composition 7)
Remove with methacrylic acid, benzyl methacrylate and formula (I) (in the formula (I), R 1The expression methyl, R 2The expression hydrogen atom) (ratio of components of composition is 25: 60: 15 by amount than (mol ratio) to the multipolymer of composition shown in shown in methacrylic acid unit and benzyl methacrylate unit and the described formula (I), polystyrene conversion weight-average molecular weight (Mw) is 9,000) replaces the resin glue (B) that embodiment 4 uses and do not add the epoxy compound beyond the region of objective existence, equally mix with embodiment 1, obtain photosensitive composition 7.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 7, equally operate with embodiment 1, make in 7A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, when equally measuring the pencil intensity of 7B layer with embodiment 1, pencil intensity is 9H.And then among the formed blue pixel 7C, its section configuration is along taper, and no coarse on the surface, the performance of photosensitive composition 7 is good.
Embodiment 6
(preparation of photosensitive composition 8)
The resin glue (B) that removes embodiment 4 changes the resin glue (B) of embodiment 5 uses into and does not add the epoxy compound beyond the region of objective existence, equally mixes with embodiment 1, obtains photosensitive composition 8.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 8, equally operate with embodiment 1, make in 8A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, the same with embodiment 1, pencil intensity is 9H when measuring the pencil intensity of 8B layer.In addition, in formed blue pixel 8C, its section configuration is along taper, and no coarse on the surface, the performance of photosensitive composition 8 is good.
Embodiment 7
(preparation of photosensitive composition 9)
Except that (ratio of components of methacrylic acid unit, benzyl methacrylate unit and styrene units is 30: 60: 10 by amount than (mol ratio) with methacrylic acid, benzyl methacrylate and cinnamic multipolymer, polystyrene conversion weight-average molecular weight (Mw) is 16,000) replaces outside the resin glue (B) of embodiment 1, equally mix with embodiment 1, obtain photosensitive composition 9.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 9, equally operate with embodiment 1, make in 9A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, when equally measuring the pencil intensity of 9B layer with embodiment 1, pencil intensity is 6H.And then in formed blue pixel 9C, its section configuration is along taper, and the surface is no coarse, and the performance of photosensitive composition 9 is good.
Embodiment 8
(preparation of photosensitive composition 10)
(ratio of components of methacrylic acid unit, benzyl methacrylate unit and the different norborneol ester units of methacrylic acid is 30: 60: 10 by amount than (mol ratio) except that the multipolymer with the different norborneol ester of methacrylic acid, benzyl methacrylate and methacrylic acid, polystyrene conversion weight-average molecular weight (Mw) is 16,000) replaces outside the resin glue (B) of embodiment 1, equally mix with embodiment 1, obtain photosensitive composition 10.
(evaluation)
Except that the photosensitive composition 1 that replaces embodiment 1 to obtain with the above-mentioned photosensitive composition that obtains 10, equally operate with embodiment 1, make in 10A layer 25 ℃ of imaging liquid under agitation dipping carry out video picture 120 seconds, with after the pure water washing, do not observe block in the imaging liquid, be coated with the rete dissolving.Measure dissolve in the imaging liquid be coated with the size-grade distribution of membranous layer ingredient the time, its maximum particle diameter is below 1.0 μ m.In addition, be coated with glass portion transmissivity (mean value of 400nm～780nm) after the rete dissolving more than 98%.
Then, when equally measuring the pencil intensity of 10B layer with embodiment 1, pencil intensity is 7H.And then in formed blue pixel 10C, its section configuration is along taper, and no coarse on the surface, the performance of photosensitive composition 10 is good.

Claims (11)

1. photosensitive composition, comprise colorant (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D), pigment dispersing agent (E) and solvent (F), described photosensitive composition is coated with on glass substrate and forms resin bed, make described resin bed prebake, through mask exposure, video picture, when dry the back, the hardness of the resulting hard resin-layer in back oven dry back be pencil hardness 3H above～below the 9H, and prebake, in 25 ℃ of aqueous alkalis of photo-sensitive resin through obtaining behind the mask exposure under 100rpm stirs the transmissivity (mean value of 400～780nm) of dipping part of the non-exposure of photo-sensitive resin portion dissolving after 120 seconds more than 98%～below 100%.
2. the photosensitive composition of claim 1 record, wherein, resin glue (B) is the resin that comprises the structural unit of deriving from (methyl) acrylic acid.
3. the photosensitive compositions of claim 1 or 2 records, wherein, the amount of the structural unit of in the general construction unit that constitutes resin glue (B), deriving from (methyl) acrylic acid more than the 16mol%～below the 40mol%.
4. the photosensitive composition of any one record in the claim 1～3, wherein, resin glue (B) further comprises the structural unit of deriving from (methyl) benzyl acrylate.
5. the photosensitive composition of any one record in the claim 1～4, wherein, resin glue (B) is the resin that further comprises structural unit shown in the formula (I):
R in the formula (I) 1And R 2Represent hydrogen atom or methyl independently of one another.
6. the photosensitive composition of any one record in the claim 1～5, wherein, the polystyrene conversion weight-average molecular weight of resin glue (B) more than 5,000～below 35,000.
7. the photosensitive composition of any one record in the claim 1～6, wherein, pigment dispersing agent (E) is at least a surfactant of selecting a group that forms from polyester system, polyethyleneimine system, polyurethane series and acrylic acid series.
8. the photosensitive composition of any one record in the claim 1～7, wherein, pigment dispersing agent (E) is the acrylic acid series surfactant.
9. the formation method of colored pattern is characterized in that forming the resin bed of being made up of the photosensitive composition of any one record in the claim 1～8 on substrate, make this resin bed behind mask exposure, video picture, dry the back then.
10. the colored pattern method of formationing of claim 9 record, wherein, the temperature of back oven dry processing is more than 180 ℃～below 250 ℃.
11. chromatic filter comprises the colored pattern with the method formation of claim 9 or 10 records.
CN2004100475242A 2003-05-23 2004-05-21 Colored photoresist composition Expired - Lifetime CN1573542B (en)

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CN103543605B (en) * 2012-07-10 2016-08-31 东友精细化工有限公司 Photosensitive composition and the colored filter of use said composition
CN105842986A (en) * 2015-01-30 2016-08-10 住友化学株式会社 Coloring photosensitive resin composition

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