CN1570683A - Shielding film for display device - Google Patents

Shielding film for display device Download PDF

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Publication number
CN1570683A
CN1570683A CN 200410034863 CN200410034863A CN1570683A CN 1570683 A CN1570683 A CN 1570683A CN 200410034863 CN200410034863 CN 200410034863 CN 200410034863 A CN200410034863 A CN 200410034863A CN 1570683 A CN1570683 A CN 1570683A
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China
Prior art keywords
display device
light
shielding layer
metal particle
layer
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Granted
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CN 200410034863
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CN100390574C (en
Inventor
畠光晶
后藤英范
伊藤英明
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Fujifilm Corp
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Fujifilm Corp
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Abstract

This invention provides a light shielding film for a display device which is a thin film, which has a high performance of shielding light and which can be manufactured at low cost, and whose color hue is not changed, irrespective of thermal treatment in the process of manufacturing. As for the light shielding film for the display device containing metal particulates, the volume fraction of the metal particulates in the light shielding film for the display device is set to be 0.05 to 0.70.

Description

Light-shielding layer for display device
Technical field
The present invention relates to be used for light-shielding layer for display device and manufacture method thereof that the color filter of liquid crystal indicator etc. uses.
Background technology
Light-shielding layer for display device is that the redness, blueness, the green pixel that are formed on color filter in order to prevent light leak reach the marginal portion of the black around the color filter and the black pattern that is used for the point-like or the wire of TFT shading on every side.
In the color filter that in colour liquid crystal display device etc., uses, on its transparency carrier, be formed with painted pixel layer (R, G, B), and in the gap of each painted pixel of R, G, B (red, green, blue), be formed with light-shielding layer for display device, show contrast etc. so that improve.Particularly in the liquid crystal display cells of the employing driven with active matrix mode of using thin film transistor (TFT) (TFT), for the electric leakage of the thin film transistor (TFT) that prevents to cause and cause decrease in image quality, require it to have high light-proofness (optical density) to light-shielding layer for display device by light.
In order to make light-shielding layer for display device with high light-proofness, considered the method for using metal, as the technology of making light-shielding layer for display device, disclose and used electroplating technology in layer, to generate the technology (referring to Patent Document 1) of nickel particle with metal particle.
But, numerous and diverse operation that this method need make particulate separate out from the electroplate liquid that contains metallic ion, and the processing of electroplating effluent is also numerous and diverse, also heavier to the burden that environment causes.
On the other hand, the disclosed in addition method of not using electroplating technology and making light-shielding layer for display device, Here it is replaces metal particle and forms the technology (referring to Patent Document 2) of light-shielding layer for display device with carbon black.
But, because carbon black is compared the optical density of its per unit coating amount with metal particle low, therefore if guarantee high light-proofness, optical density, then thickness will inevitably thickening, and after forming light-shielding layer for display device, when forming red, blue, green pixel again, there is the shortcoming that is difficult to form uniform pixel.
In addition, form the technology of light-shielding layer for display device as not using electroplating technology, when being light shield layer with metal films such as chromium, can enumerate with behind vapour deposition method or the metallikon making metallic film, on this metallic film, apply photoresist, use then and have light-shielding layer for display device and the photoresist layer is carried out exposure imaging with the photomask of pattern, afterwards the metallic film that exposes is carried out etching, the method (for example, with reference to non-patent literature 1) of the resist layer on the last stripping metal film.
Owing to use metallic film in this method, even also can obtain high shaded effect so thickness is thin, but on the other hand, need to implement vapour deposition method or metallikon equal vacuum film formation process and etching work procedure, cost is uprised, and these operations also can not be ignored to the burden that environment causes.In addition, owing to be metal film, the reflectivity height exists to show the low problem of contrast under strong outer light.At this problem, can adopt the method for using low reflective chrome film (by crome metal and this two-layer film of forming of chromium oxide etc.), but undeniable be that this has further improved cost again.
In addition, be exposed under the high temperature during fabrication owing to contain the light-shielding layer for display device of metal particle, so the color harmony reflectivity can change sometimes, perhaps produce bubble, this also is the problem that needs solution.
Also has the known technology (for example, referring to Patent Document 3) that the use electroplating technology is arranged and make the photomask that contains the metal sulfide particulate.Owing to also used electroplating technology in this method,, therefore also failed satisfactory so have the carrying capacity of environment problem and the problem that need carry out numerous and diverse operation of waste liquid.
[non-patent literature 1]
Upright altogether (strain) distribution " colored TFT LCD " 218-220 page or leaf (on April 10th, 1997) of publishing
[patent documentation 1]
Te Kaiping 5-303090 communique
[patent documentation 2]
The spy opens clear 62-9301 communique
[patent documentation 3]
Te Kaiping 7-218715 communique
Summary of the invention
The present invention proposes in view of aforesaid problem, and its purpose is to provide can be with the low cost manufacturing, film is thin and shading performance height, can not the thermal treatment when making cause the light-shielding layer for display device of the variation of tone etc.
In view of such actual conditions, the inventor has carried out wholwe-hearted research, found that, belongs in the specific scope by making the volume fraction of this metal particle in the light-shielding layer for display device, can solve above-mentioned problem, thereby finish the present invention.And, in the scope of the light-shielding layer for display device of this particular range with inventor's investigation, do not exist in the past.
That is, the invention provides following method.
<1〉a kind of light-shielding layer for display device is that the display device that contains metal particle is used
Photomask is characterized in that, this metal particle in the light-shielding layer for display device
Volume fraction be 0.05-0.70.
<2〉as<1〉described light-shielding layer for display device, it is characterized in that metal is little
The volume fraction of grain is 0.1-0.55.
<3〉as<1〉described light-shielding layer for display device, it is characterized in that metal is little
The volume fraction of grain is 0.2-0.50.
<4〉as<1 〉,<2 or<3〉described light-shielding layer for display device, should
Light-shielding layer for display device at the swelling capacity S of 25 ℃ water below 0.5.
<5〉a kind of transfer materials is used for making<1 〉-<4〉any one is described
Light-shielding layer for display device wherein has to apply on interim supporter and contains
Carry out the photographic layer that drying forms behind the photonasty coating liquid of metal particle.
<6〉use<5〉light-shielding layer for display device made of described transfer materials.
<7〉a kind of composition that contains metal particle is used for making<1 〉-<4〉appoint
What described light-shielding layer for display device wherein contains metal particle.
<8〉use<7〉the described demonstration dress that contains the composition making of metal particle
Put and use photomask.
<9〉have<1 〉-<4〉described light-shielding layer for display device substrate.
<10〉have<9〉described substrate color filter.
Can provide film thin and the shading performance high and can be with the light-shielding layer for display device of the variation low cost manufacturing, that can not the thermal treatment when making cause tone etc. according to the present invention.
Embodiment
The present invention is light-shielding layer for display device and manufacture method thereof, is the light-shielding layer for display device that contains metal particle, it is characterized in that, the volume fraction of this metal particle is 0.05-0.70 in the light-shielding layer for display device.
Be elaborated below.
[metal particle]
Metal as the metal particle that uses among the present invention is not particularly limited, but can enumerate nickel, silver, gold, platinum, copper or their alloy as preferred metal.Wherein, from chemical stability, cost aspect, preferred silver.
The metal particle that uses among the present invention both can be uniform composition, also can be uneven composition.As the example of inhomogeneous composition, can enumerate the particulate that is provided with from the teeth outwards with the coating of inner different compositions.In addition, the shape of the metal particle that uses among the present invention is not particularly limited, can uses the particulate of different shapes such as sphere, unsetting, tabular, cube, regular octahedron, column.
The mean grain size of the metal particle that uses among the present invention is preferably 1-3000nm, preferred especially 5-800nm, further preferred 10-250nm.If the not enough 1nm of mean grain size, then absorbing wavelength can shorten, and tone can occur when surpassing 3000nm, perhaps can make the optical density step-down, so not preferred.
Manufacture method to the metal particle that uses among the present invention is not particularly limited, and can adopt known manufacture method, liquid phase methods such as vapor phase methods such as for example evaporation-condensation method, gas phase reduction process, liquid phase reduction etc.Specifically be recorded in " the up-to-date trend II of ultramicronized technology and application lives ベ テ Network ノ リ サ-チ (strain) distribution, 2002 ".
In addition, for example, when using silver-colored particulate (collargol), also can use known method in the past, for example in No. 2688601 instructions of United States Patent (USP) disclosed in aqueous gelatin solution with the method for quinhydrones reduction soluble silver salt; The method of in No. 1096193 instructions of Deutsche Bundespatent, putting down in writing with hydrazine reduction slightly solubility silver salt; Method of silver being reduced with tannic acid of putting down in writing in No. 2921914 instructions of United States Patent (USP) etc. is carried out the method for electronation to silver ion in solution; Open the method for putting down in writing in the flat 5-134358 communique that electroless plating forms silver particles of passing through with the spy; In inert gases such as helium, make bulk (bulk) evaporation of metal and carry out in the gas phase that cold-trap handles method such as evaporation method with solvent.
[spreading agent]
In the present invention, in order to prevent the gathering of metal particle in coating liquid, preferably use spreading agent to disperse.As being used for spreading agent of the present invention, can be exemplified as surfactant and polymkeric substance.
As surfactant, can use any in anionic property, cationic, nonionic, the amphoteric surfactant, but special preferred anionic, non-ionic tenside.The HLB value of the surfactant that uses among the present invention is water class or oils and difference cannot treat different things as the same according to the solvent of coating liquid, but working as solvent is the water time-like, the solvent about preferably about 8-18, and when solvent is oils, the solvent about preferably about 3-6.Also have, the explanation for HLB value, be recorded in " the surfactant handbook (volume such as Jitian Shi Hang, engineering books (strain) are issued, clear and 62 years) " in.
Object lesson as surfactant, except can being exemplified as propylene glycol monostearate, interior glycol monolaurate, diglycol stearate, Span-20, polyoxyethylene Span-20 etc., can also be exemplified as the material of record in above-mentioned " surfactant handbook ".
The use amount of surfactant is preferably 0.01-30 weight % with respect to metal particle, preferred especially 0.1-20 weight %.
As the dispersed polymeres that uses among the present invention; the polymkeric substance that preferably has protecting colloid; except for example gelatin, polyvinyl alcohol (PVA), methylcellulose, hydroxypropyl cellulose, poly-alkyl amine, polyacrylic part Arrcostab etc.; the polymkeric substance that can also in " topical reference book of pigment (her rattan is levied the youth of department and compiles, and (strain) was towards storehouse academy distribution 2000) ", put down in writing for example.
The use amount of polymkeric substance is preferably 0.01-30 weight % with respect to metal particle, preferred especially 0.1-20 weight %.
[volume fraction]
In light-shielding layer for display device of the present invention, except metal particle, also contain as the polymkeric substance of bonding agent and monomer, polymerization initiator, other any composition.In the manufacturing of light-shielding layer for display device, the part of these compositions disappears in operations such as coating, development, heat drying sometimes.Therefore, in the present invention, the volume fraction of metal particle is as " volume fraction of metal particle " in the film when forming light-shielding layer for display device.
For example, under the situation of silver-colored particulate, volume fraction calculates with following formula.
The volume fraction of silver particulate=(amount of being coated with/10.5 of silver)/thickness
Wherein, Yin the amount of being coated with g/m 2Expression.10.5 be to use g/cm 3The density of the silver of expression.It is consistent when therefore, the value of (amount of being coated with/10.5 of silver) is coated with as uniform film with a silver with the one-tenth-value thickness 1/10 of μ m unit representation.Thickness is represented with μ m in addition.
The invention is characterized in that the volume fraction of this metal particle is 0.05-0.70 in the light-shielding layer for display device, and the preferred 0.1-0.55 of this volume fraction, preferred especially 0.2-0.50.If this volume fraction less than 0.05, then the thickness of light-shielding layer for display device can become excessive, the redness that forms after existing, blueness, the green pixel uneven shortcoming that becomes, and if surpass 0.70, can produce tonal variation when then at high temperature preserving, so not preferred.
The thickness of photomask of the present invention is preferably below 0.9 μ m, more preferably below the 0.6 μ m, further below the preferred 0.4 μ m.In addition, the OD of photomask of the present invention is preferably more than 3.3, more preferably more than 3.5.
Light-shielding layer for display device of the present invention at the swelling capacity S of 25 ℃ water preferably below 0.5.
Said here swelling capacity S is when dry film thickness is d and Δ d with 60 seconds the thickness separate provision of distilled water that impregnated in 25 ℃, defines with S=(Δ d-d)/d.
Light-shielding layer for display device of the present invention can be by carrying out dry method behind the coating liquid that contains metal particle in coating on the substrate, perhaps utilize the recording materials with photosensitive layer that drying forms after coating contains the coating liquid of metal particle on the interim supporter, the method for this photosensitive layer of transfer printing etc. is made on substrate.
(the coating liquid that contains metal particle)
Contain metal particle in the coating liquid that contains metal particle that uses among the present invention, can also contain polymkeric substance as bonding agent, solvent etc. in addition.
[bonding agent]
Below bonding agent is described in detail.
As bonding agent contained in the photomask of the present invention, can be exemplified as following material.
Cellulose family macromolecules such as polyvinyl alcohol (PVA), gelatin, methylcellulose, acrylic compounds or styrene acrylic family macromolecule that methyl methacrylate, ethyl acrylate, benzyl acrylate, acrylic acid, methacrylic acid, styrene etc. are polymerized.
Wherein, can form pattern by the alkali development owing to contain the soluble acrylic compounds of alkali, the styrene acrylic family macromolecule of acrylic acid, methacrylic acid, so preferred.
In these macromolecules, acrylic acid and the methacrylic acid content in macromolecule is preferably 10-60 quality %, more preferably 20-50 quality % in the two total amount.
As these high molecular object lessons, can be exemplified as benzyl methacrylate/methacrylic acid=60/40 (this is than expression mass ratio (following identical)), methyl methacrylate/styrene/methacrylic acid=10/60/30, methyl methacrylate/styrene/acrylic/methacrylic acid=20/50/15/15, benzyl methacrylate/methyl methacrylate/methacrylic acid=40/35/35, styrene/acrylic/methacrylic acid=60/20/20 etc.
In addition, as bonding agent, also can be monomer or oligomer.For object lesson, preferred (methyl) acrylic acid glycol ester, two (methyl) acrylic acid triethyleneglycol ester, two (methyl) acrylic acid 1 of using, 3-butanediol ester, two (methyl) acrylic acid tetramethylene glycol ester, two (methyl) acrylic acid propylene glycol ester, trimethylolpropane tris (methyl) acrylate, two (methyl) acrylic acid 1, polyfunctional group acrylic monomerss such as 4-hexanediol ester, six (methyl) acrylic acid pentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester.
It is crosslinked that these polyfunctional monomers can use light and heat to carry out as described above; in these methods; the preferred use with two [4-[N-[4-(4, the two trichloromethyls of 6--S-triazine-2-yl) phenyl] carbamyl] phenyl] halogenated methyl-S-compound in triazine class such as sebacate is as the light polymerization method of polymerization initiator.
The macromolecule that also can be in photomask of the present invention adds the dispersion stabilization that is used to improve particulate of the present invention again.For the example of these macromolecules (so-called spreading agent), can be exemplified as polyvinyl alcohol (PVA), acrylamide/acrylic acid multipolymer, phenylethylene/maleic anhydride copolymer, sodium polyacrylate, sodium alginate etc.For spreading agent, for example, can use the material in the pigment dispersing technology that is recorded in (technical information association (strain), publisher: high thin is great, distribution in 1999).In these materials, preferred especially hydrophobicity spreading agent.
[solvent]
As solvent, can use known organic solvent.As particularly preferred organic solvent, can be exemplified as methyl alcohol, isopropyl alcohol, MEK, ethyl acetate, toluene etc.In addition, as solvent preferred water also.These solvents also can mix use as required.
[substrate]
Be preferred for the glass substrate of device such as liquid crystal display etc. as substrate.As glass substrate, can be with the glass substrate that has used known glass such as soda-lime glass, glass with lower alkali content, alkali-free glass.The thickness of substrate is preferably about 0.5-3mm, more preferably from about 0.6-2mm.About glass substrate, can for example use the glass substrate that is recorded in " the liquid crystal display engineering is crossed the threshold (Suzuki Ha Na ニ work, Nikkan Kogyo Shimbun's distribution (1998)) ".
(having photosensitive containing metal particulate coating liquid)
The coating liquid that contains metal particle among the present invention also can have photonasty.If will give photonasty, then need add photosensitive polymer combination.As photosensitive polymer combination, can use to be recorded in paragraph 0016 that the spy the opens flat 10-160926 communique material in paragraph 0022 and 0029.
In addition, in the time will being used as water dispersion, need make water class material as above-mentioned photosensitive polymer combination as metal particles such as above-mentioned silver colloids.As such photosensitive polymer combination,, can also be exemplified as " SPP-M20 " of commercially available for example Japan compound probability (strain) system etc. except being recorded in paragraph 0015 that the spy the opens flat 8-271727 communique material in the paragraph 0023.The light-shielding layer for display device manufacture method
Method of the present invention is carried out dry operation after being included in and applying the coating liquid that contains metal particle on the substrate.
Pattern formation method to light-shielding layer for display device is not particularly limited.Enumerate the example of pattern formation method below.
(1) contains the photonasty coating liquid of metal particle and after forming light shield layer (layer that contains metal particle), remove pattern light shield layer in addition in coating on the substrate, form method of patterning thus by exposure imaging.
(2) coating on the substrate contain metal particle non-photosensitive coating liquid and after forming light shield layer, apply photonasty resist liquid in the above and form resist layer, then, by exposure, be developed on the resist layer form pattern after, the non-pattern part of light shield layer below this pattern dissolved, thereby on this light shield layer, form pattern, remove resist layer at last and form the method for light-shielding layer for display device.
(3) part beyond the pattern on substrate forms overlay in advance, and coating in the above contains the non-photosensitive coating liquid of metal particle, forms light shield layer, then overlay that will form at first and the top light shield layer method of removing together.
In the present invention, coating method to substrate is not particularly limited, the mould coating process (die coat) that for example can use special spin-coating method, curtain coating, extrusion (extrusion), the spy who opens flat 5-224011 communique record to open to be put down in writing in the flat 9-323472 communique etc.
Spin-coating method is by coating liquid being dropped on the substrate of rotation, utilizing centrifugal force drawout liquid afterwards and the method that applies.
Curtain coating also is called flow coat method, is a kind of of longitudinal cutting hole (slit orifice) application pattern.This mode is to fall coating liquid from slit with tentiform, thereby it is coated in method on the substrate.By slit or substrate along continuous straight runs are moved, make coating liquid become uniform thin layer and by being spread over above the substrate.
Extrusion is also referred to as the extrusion coating method, is the directly application pattern of drawout on the substrate that moves of the coating liquid extruded from slit.
About the detailed content of above application pattern, for example be recorded in " coating technology (and former rugged brave time prison is repaiied, the distribution of (strain) complex art center, clear and 58 years) " in.
The light source that is used to expose can be selected according to the photonasty of light blocking photosensitive resin bed.For example, can use known light sources such as ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp, argon laser.Such as open the spy in the flat 6-59119 communique record, can and with the light transmission of the above wavelength of 400nm at the optical filter below 2% etc.
As developer solution, can use the dilute aqueous solution of alkaline matter, but also can use a small amount of material that has added the organic solvent that can mix with water.As suitable alkaline matter, (for example can be exemplified as alkali metal hydroxide, NaOH, potassium hydroxide), the alkali carbonate class (for example, sodium carbonate, sal tartari), the alkali metal hydrogencarbonate class (for example, sodium bicarbonate, saleratus), salt (for example for alkali metal silicate (silicic acid), sodium silicate (sodium silicate), potassium silicate (kaliumsilicate)), alkali metal silicate (metasilicic acid) salt (for example, sodium silicate (sodiummetasilicate), potassium silicate (kalium metasilicate)), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetra-alkyl ammonium hydroxide class (for example Tetramethylammonium hydroxide) or tertiary sodium phosphate.The concentration of alkaline matter is 0.01 weight %-30 weight %, the preferred 8-14 of pH.Can regulate according to the character such as oxidation of light blocking photosensitive resin bed of the present invention, change the pH of developer solution etc., so that can utilize the development of membranaceous disengaging of the present invention.
As the above-mentioned The suitable solvent that can mix with water, can be exemplified as methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, MEK, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl-phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone.The concentration of the organic solvent that can mix with water is generally 0.1-30 weight %.
Can also add known surfactant in the developer solution.The preferred 0.01-10 weight of surfactant concentrations %.
Developer solution both can be used as body lotion and had used, and also can be used as spray liquid and used.If the uncured portion that will remove the photosensitive polymer combination layer of light-proofness with solid shape (being preferably membranaceous), then preferably adopt in developer solution with the rotary brush wiping or with methods such as moistening sponge wiping, the method for the spraying pressure when perhaps utilizing the spray developer solution.The temperature of developer solution usually preferably near the room temperature to 40 ℃ scope.Can also increase washing step after the development treatment.
Drying process
Behind developing procedure, carry out heat drying and handle.That is, the supporter of resin bed (hereinafter referred to as photocurable layers) with photocuring by exposure is heated in electric furnace, exsiccator etc., perhaps by photocurable layers irradiation infrared ray is heated.The temperature and time of heating depends on the composition and the formed bed thickness of the polymerizable composition, polymerizable composition of use, but usually in order to obtain sufficient solvent resistance, alkali resistance, preferably heating about 10 minutes-Yue 300 minutes in about 120 ℃-Yue 250 ℃ scope.
(using the method for transfer printing)
Light-shielding layer for display device of the present invention also can adopt following method manufacturing, promptly utilize to have and contain the recording materials of the photosensitive layer that drying forms behind the coating liquid of metal particle (below be sometimes referred to as " photosensitive transfer printing material "), with the method for this photosensitive layer transfer printing on substrate in coating on the interim supporter.
Photosensitive transfer printing material is by having that the photosensitive coating liquid that contains metal particle is provided with the photonasty light shield layer and the material that forms on interim supporter.The thickness of photonasty light shield layer is preferably about 0.3-2.0 μ m.
Interim supporter has chemistry and thermal stability, and preferably is made of the material of flexibility.Be specially sheet material that preferably polytetrafluoroethylene (R), polyethylene terephthalate, PEN, poly-aryl compound, polycarbonate, tygon, polypropylene etc. are thin or their layered product.In addition, when the alkali-soluble thermoplastic resin is set, preferably good material with its fissility.The thickness of interim supporter is preferably 5-300 μ m, preferred especially 20-150 μ m.
In addition, preferably between interim supporter and photonasty light shield layer, the alkali-soluble middle layer is set.
(alkali-soluble middle layer)
Resin as constituting the middle layer just is not particularly limited as long as can be dissolved in above-mentioned alkali.As the example of such resin, can be exemplified as polyvinyl alcohol resin, polyvinylpyrrolidone resinoid, cellulosic resin, third rare amide-type resin, polyoxyethylene resinoid, gelatin, vinethene resinoid, polyamide and these multipolymer.In addition, also can use by having carboxyl and sulfonic monomer and being generally the resin that non-alkali-soluble resin carries out the alkali-soluble that copolymerization forms as polyester etc.
In these resins, polyvinyl alcohol (PVA) preferably.As polyvinyl alcohol (PVA), its saponification degree is preferably more than 80%, more preferably 83-98%.
The resin that constitutes the middle layer preferably mixes more than two kinds and uses, the preferred especially pure and mild polyvinylpyrrolidone of mix polyethylene and using.Preferably both quality are than polyvinylpyrrolidone/polyvinyl alcohol (PVA)=1/99-75/25, more preferably 10/90-50/50.If above-mentioned mass ratio less than 1/99, then the surface configuration in middle layer meeting deterioration produces and is coated with the bad problem of driving fit that is located at the photo-sensitive resin on the middle layer sometimes.In addition, if above-mentioned mass ratio surpasses 75/25, then the oxygen in the middle layer property cut off can descend sometimes, causes the decline of sensitivity.
In the middle layer, also can add various adjuvants such as surfactant as required.
The preferred 0.1-5 μ of the thickness in middle layer m, more preferably 0.5-3 μ m.If above-mentioned thickness less than 0.1 μ m, then oxygen cuts off property and can descend sometimes, and if above-mentioned thickness surpasses 5 μ m, the time that is used to remove the middle layer when then developing will increase.
As the coating solvent in middle layer, as long as can dissolve above-mentioned resin, just do not have other special qualification, but preferably make water, also the mixed solvent that preferably the above-mentioned organic solvent that can mix with water and water is mixed.As the preferred object lesson of coating solvent in middle layer, the material shown in following is arranged.Can be water, water/methyl alcohol=90/10, water/methyl alcohol=70/30, water/methyl alcohol=55/45, water/ethanol=70/30, water/1-propyl alcohol=70/30, water/acetone=90/10, water/first and second bronze medals=95/5.These are than value representation mass ratio.
Owing to be provided with the photonasty light shield layer that the above-mentioned coating liquid by containing metal particle forms in the photosensitive transfer printing material, therefore can make the light-shielding layer for display device that film approached and had the high light shield layer of optical density.
In the light-shielding layer for display device of the present invention, the optical density of preferred per 1 μ m thickness photomask is more than 1.Light-shielding layer for display device of the present invention has and uses the light shield layer contain the coating liquid of metal particle and to make.The thickness of above-mentioned light shield layer is preferably about 0.3-2.0 μ m.Owing to be dispersed with metal particle in the light shield layer in the light-shielding layer for display device that obtains according to the present invention, so even aforesaid film also has sufficient optical density.
In the present invention, after forming light shield layer, before exposure, can be added in the operation that protective layer is set on the light shield layer.Protective layer is an occluded oxygen in order to expose, and is provided with thereby improve sensitivity.Therefore, preferably with the resin of the oxygen property cut off, for example polyvinyl alcohol (PVA) is the layer of main body.And, owing to do not need this layer after forming light-shielding layer for display device, so can remove by development.
[embodiment]
Below, according to embodiment the present invention is described in more details, but the present invention is not limited to these.
Embodiment 1
[making of silver-colored particulate]
(manufacturing of silver-colored dispersed paste)
In the 112g gelatin, add 3488g distilled water, then the mixture heated that obtains is arrived about 47 ℃, with the dissolving gelatin.To wherein adding 4.0g calcium acetate and 2.0g potassium borohydride.Stir apace afterwards at once on one side, add the 6.0g silver nitrate that be dissolved in 1.0L distilled water on one side.By adding distilled water, final weight is adjusted to 5.0kg.Then product is cooled near the gelling temperature it be entered in the water of cooling by aperture, forms fine slice (noodle) thus.These slices are given as being used for directly generating blue silver-colored amplification catalyst supply.For easy to use and prevent to form molten mass by this slice, this slice of dilutable water reaches water: the ratio of slice=1/3.
In 650g borane reduction galactic nucleus, add single sulfonic acid quinhydrones potassium of the 6.5g that is dissolved in 81g distilled water and 0.29gKCl.Slice shape slurry is cooled to about 6 ℃.In different containers, make following 2 kinds of solution A and B respectively.
A 19.5g sodium sulphite (anhydrous)
0.98g sodium bisulfite (anhydrous)
122.0g distilled water
B 9.75g silver nitrate 122.0g distilled water solution
Mix A and B, formed the white precipitate that lasting stirring will disappear.Then and then, at short notice (in 5 minutes) Yi Bian stir apace, Yi Bian this potpourri is joined in the slice shape slurry.Temperature maintenance at 10 ℃, is carried out about 80 minutes amplification then, be reduced on nuclear up to all soluble silver salts.Tap water is situated between with slurry by the blue pulp particle of the gained in the nylon wire pouch, and then makes washings pass through bag about 30 minutes, washing is contained in the blue pulp particle of gained in the nylon wire pouch thus, thereby washes all salt off.The blue silver dispersions that contains the silver of 1.5 weight % concentration when obtaining fusion is eliminated the moisture in the blue silver that is dispersed in the gel slurry and has washed, becomes 412g up to the weight of product.
(making of silver-colored particulate)
In by the 5000g silver dispersed paste that as above operation obtains, add 25g spreading agent (ラ ピ ゾ-Le B-90, Japanese grease (strain) system) and 1000g 5 weight % papain aqueous solution, preserved 24 hours down at 37 ℃.With this solution of 2000rpm centrifuging 5 minutes, thereby make silver-colored particulate deposits.After removing supernatant liquid,, remove with zymolytic gelatin analyte with the distilled water washing.Then with making its drying behind the methanol wash silver particulate deposits thing.Obtained the condensation product of the silver-colored particulate of about 85g.This condensation product of 73.5g and 1.05g spreading agent (ソ Le ス パ-ス 20000, ア PVC シ ア (strain) system), 16.4g MEK are mixed.The 2mm beaded glass of 100g is mixed with it and disperseed 3 hours, thereby obtain silver-colored particle dispersion liquid A-1 with the coating kicker.
(making of light shield layer coating liquid)
In silver-colored particle dispersion liquid A-1, add, mix following material and form light shield layer coating liquid.
Silver particle dispersion liquid A-1 40.0g
Propylene glycol methyl ether acetate 40.0g
MEK 37.6g
Surfactant (F176PF, 20%) 0.2g
Hydroquinone monomethyl ether 0.001g
Dipentaerythritol acrylate can reach table 1, the amount of the volume fraction in 2
Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] carbamyl]
Phenyl] sebacate 0.1g
(making of protective seam coating liquid)
Polyvinyl alcohol (PVA) (Network ラ レ (strain) system, PVA205) 3.0g
Polyvinyl pyrrolidone (GAF コ-Port レ-シ ヨ Application (strain) system PVP-K30)
1.3g
Distilled water 50.7g
Methyl alcohol 45.0g
Mentioned component is mixed, thereby be protected layer coating liquid.
(coating of coating liquid)
On glass substrate, use spin coater to apply above-mentioned light shield layer coating liquid, so that optical density reaches 3.6, and following dry 5 minutes at 100 ℃.Then, use spin coater to apply above-mentioned protective seam coating liquid in the above, and descended dry 5 minutes, make dry film thickness reach 1.5 μ m at 100 ℃.
(exposure, development)
Use ultrahigh pressure mercury lamp, carry out 70mJ/cm from the applicator surface side 2Exposure.Then, carry out development treatment (33 ℃, 20 seconds) with development treatment liquid TCD (Fujiphoto (strain) system alkaline-based developer), thereby obtain light-shielding layer for display device.
The light-shielding layer for display device that obtains is carried out following measurement and evaluation.
(film thickness measuring)
Measure thickness with following method.Use ultrahigh pressure mercury lamp, the sample that has applied light shield layer is carried out 70mJ/cm from the applicator surface side 2Exposure, use contact pin type surfagauge P-1 (TENKOP society system) to measure the thickness of this sample.
(swelling capacity measurement)
The sample that uses in the film thickness measuring flooded for 60 seconds in 25 ℃ distilled water after, wipe the moisture on surface, measure thickness (Δ d) with said method afterwards.Obtain swelling capacity S=(Δ d-d)/d with Δ d that obtains thus and dry film thickness d.The result is 0.05.
(measurement of volume fraction)
At first, measure the amount of being coated with of silver-colored particulate with following method.
Use ultrahigh pressure mercury lamp to carry out 70mJ/cm to the sample that has applied photographic layer from the applicator surface side 2Exposure, use fluorescent X-ray device 3370E ((strain) system of science) to measure the silver amount of being coated with of this sample.
The thickness that uses this measured value and measure in above-mentioned (film thickness measuring) divides rate with above-mentioned method volume calculated.
(measurement of optical density)
Measured the optical density of film with following method.Use ultrahigh pressure mercury lamp, carry out 500mJ/cm from the applicator surface side being coated with the light shield layer that is located on the glass substrate 2Exposure.Use Macbeath densitometer (the system TD-904 of Macbeath society) to measure this optical density (OD) then.Use the same method in addition and measure the optical density (OD of glass substrate 0).From OD, deducting OD 0Value as the optical density of film.
Also have, all samples all are modulated to and reach 3.6 optical density.
(blue, red, the formation of green pixel and the evaluation of pixel bubble)
On the glass substrate that has formed light-shielding layer for display device, use sample R1, G1, the B1 of the embodiment-1 that openly speciallys permit communique 2002-4341127 instructions, formed pixel of all kinds.The method that forms pixel is also used the method for putting down in writing in this communique.
Owing on light-shielding layer for display device concavo-convex, form pixel of all kinds, so between glass substrate and pixel of all kinds, can enter bubble sometimes.Measure the generation degree of this bubble with following method.
For each 100 of the pixels of three kinds of colors of this substrate, amounts to 300 pixels, the use optical microscope has been counted bubble quantity and bubble by range estimation.
(by the tonal variation that heats the light-shielding layer for display device that produces)
Under 220 ℃, the glass substrate that is formed with light-shielding layer for display device is carried out the tonal variation of the light-shielding layer for display device of thermal treatment in 2 hours front and back by visual assessment.
Cannot see fully and change A
Minimum metallic luster B is arranged
Some metallic luster is arranged, but the C that in practicality, allows
Metallic luster D with the degree that can become damage in actual use
Has complete metallic luster E
That wherein permission is gone up in practicality is A-C.
Above the results are shown in the table 1.
[table 1]
Test piece number (Test pc No.) Photographic layer thickness (μ m) Volume fraction Optical density Bubble (individual) Tonal variation
Comparative example 1-1 ?2.9 ?0.02 ?3.6 More than 50 ?A
Embodiment 1-1 ?0.80 ?0.08 ?3.6 ?12 ?A
Embodiment 1-2 ?0.35 ?0.21 ?3.6 ?2 ?A
Embodiment 1-3 ?0.18 ?0.39 ?3.6 ?0 ?A
Embodiment 1-4 ?0.13 ?0.52 ?3.6 ?0 ?B
Embodiment 1-5 ?0.11 ?0.63 ?3.6 ?0 ?C
Comparative example 1-2 ?0.10 ?0.73 ?3.6 ?0 ?E
Embodiment 2
(making of light shield layer coating liquid)
Identical with embodiment 1.
(making of middle layer coating liquid)
Identical with embodiment 1 (making of protective seam coating liquid).
(modulation of thermoplastic resin)
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid=
54/12/5/29 multipolymer (ratio of components is represented mol ratio, number-average molecular weight=80,000)
58 parts
The multipolymer of styrene/acrylic=70/30 (number-average molecular weight=7000)
136 parts
Compound (plastifier: new with 2 equivalent, eight glycol monomethacrylates and bisphenol-A dehydrating condensation
Middle village's chemistry (strain) system, BPE-500) 90 parts
Fluorine class surfactant (big Japanese ink chemical industry (strain) system メ ガ Off ア Star Network F176PF)
1 part
541 parts of MEKs
63 parts of 1-methoxyls-2-propyl alcohol
111 parts of methyl alcohol
Mix above composition and make thermoplastic resin coating liquid.
(making of transfer materials)
On the thick polyethylene terephthalate supporter of 75 μ m of two-way stretch, use slip coating machine coating thermoplastic resin coating liquid, make thickness reach 15 μ m, and 100 ℃ dry 5 minutes down.Then, apply middle layer coating liquid in the above and descended drying 5 minutes, so that dry film thickness is 1.5 μ m at 100 ℃.In addition, apply light shield layer coating liquid in the above and descended drying 5 minutes, so that optical density becomes 3.6 at 100 ℃.
(making of photosensitive material)
Stack glass substrate and transfer materials make glass substrate contact with light shield layer, use laminater (Osaka ラ ミ ネ--(strain) system VP-II) that both are fitted.Lamination is that pressure is 0.8Kg/cm 2, temperature is 130 ℃.Then, peel off the polyethylene terephthalate supporter.
(making of light-shielding layer for display device)
Use ultrahigh pressure mercury lamp to carry out 70mJ/cm from the applicator surface side 2Exposure.Then, carry out following development treatment, obtain light-shielding layer for display device.
(1) development treatment liquid TPD (alkaline-based developer of Fujiphoto (strain) system) development treatment (30 ℃, 40 seconds)
(2) development treatment liquid TCD (alkaline-based developer of Fujiphoto (strain) system) development treatment (33 ℃, 20 seconds)
(3) development treatment liquid TCD (alkaline-based developer of Fujiphoto (strain) system) development treatment (33 ℃, 20 seconds)
This sample is also carried out the evaluation identical with embodiment 1.
The results are shown in the table 2.
[table 2]
Test piece number (Test pc No.) Photographic layer thickness (μ m) Volume fraction Optical density Bubble (individual) Tonal variation
Comparative example 2-1 ?3.1 ?0.02 ?3.6 More than 50 ?A
Embodiment 2-1 ?0.88 ?0.07 ?3.6 ?8 ?A
Embodiment 2-2 ?0.28 ?0.23 ?3.6 ?3 ?A
Embodiment 2-3 ?0.19 ?0.39 ?3.6 ?0 ?A
Embodiment 2-4 ?0.13 ?0.53 ?3.6 ?0 ?B
Embodiment 2-5 ?0.12 ?0.61 ?3.6 ?0 ?C
Comparative example 2-2 ?0.11 ?0.73 ?3.6 ?0 ?E
Comparative example 1
Except changing the addition of dipentaerythritol acrylate, the volume fraction of silver-colored particulate is become beyond the amount shown in the table 1, obtain the light-shielding layer for display device of comparative example 1 according to the method identical with embodiment 1.The evaluation of this light-shielding layer for display device is shown in Table 1.
Comparative example 2
Except changing the addition of dipentaerythritol acrylate, the volume fraction of silver-colored particulate is become beyond the amount shown in the table 2, obtain the light-shielding layer for display device of comparative example 2 according to the method identical with embodiment 2.The evaluation of this light-shielding layer for display device is shown in Table 2.
According to the present invention, can provide the thin and shading performance height of film and can be with the light-shielding layer for display device of the variation low cost manufacturing, that can not the thermal treatment when making cause tone etc.

Claims (10)

1. a light-shielding layer for display device is the light-shielding layer for display device that contains metal particle, it is characterized in that, the volume fraction of this metal particle is 0.05-0.70 in the light-shielding layer for display device.
2. light-shielding layer for display device as claimed in claim 1 is characterized in that the volume fraction of metal particle is 0.1-0.55.
3. light-shielding layer for display device as claimed in claim 1 is characterized in that the volume fraction of metal particle is 0.2-0.50.
4. as claim 1,2 or 3 described light-shielding layer for display device, it is characterized in that, light-shielding layer for display device at the swelling capacity S of 25 ℃ water below 0.5.
5. a transfer materials is used for making each described light-shielding layer for display device of claim 1-4, wherein has after coating on the interim supporter contains the photonasty coating liquid of metal particle to carry out the photographic layer that drying forms.
6. the light-shielding layer for display device that uses the described transfer materials of claim 5 to make.
7. a composition that contains metal particle is used for making each described light-shielding layer for display device of claim 1-4, wherein contains metal particle.
8. the light-shielding layer for display device that uses the described composition that contains metal particle of claim 7 to make.
9. the substrate that has the described light-shielding layer for display device of claim 1-4.
10. the color filter that has the described substrate of claim 9.
CNB2004100348637A 2003-04-18 2004-04-16 Shielding film for display device Expired - Fee Related CN100390574C (en)

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CN101263424B (en) * 2005-09-16 2011-12-14 富士胶片株式会社 Photosensitive composition, transfer material, light shielding film and production method thereof, color filter for display device, substrate for display device, and display device
CN101268151B (en) * 2005-09-16 2012-03-28 富士胶片株式会社 Colored composition and photosensitive transfer material
CN101131540B (en) * 2006-08-23 2012-07-04 富士胶片株式会社 Photonasty composition and shading film of display using the same
CN107452758A (en) * 2017-08-08 2017-12-08 京东方科技集团股份有限公司 Display base plate and its manufacture method and display device
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CN1831646B (en) * 2005-03-09 2011-08-17 富士胶片株式会社 Light-shielding image-carrying substrate, method of forming light-shielding image, transfer material, color filter, and display device
CN101263424B (en) * 2005-09-16 2011-12-14 富士胶片株式会社 Photosensitive composition, transfer material, light shielding film and production method thereof, color filter for display device, substrate for display device, and display device
CN101268151B (en) * 2005-09-16 2012-03-28 富士胶片株式会社 Colored composition and photosensitive transfer material
CN101131540B (en) * 2006-08-23 2012-07-04 富士胶片株式会社 Photonasty composition and shading film of display using the same
CN107452758A (en) * 2017-08-08 2017-12-08 京东方科技集团股份有限公司 Display base plate and its manufacture method and display device
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CN109407195A (en) * 2018-12-18 2019-03-01 武汉华星光电半导体显示技术有限公司 Optical filter, display panel and color filter preparation method

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