CN1804722A - Coloring composite for color filter and color filter - Google Patents
Coloring composite for color filter and color filter Download PDFInfo
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- CN1804722A CN1804722A CN 200510133802 CN200510133802A CN1804722A CN 1804722 A CN1804722 A CN 1804722A CN 200510133802 CN200510133802 CN 200510133802 CN 200510133802 A CN200510133802 A CN 200510133802A CN 1804722 A CN1804722 A CN 1804722A
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Abstract
The blue colored composition for a color filter contains a photosensitive transparent resin, a non-photosensitive transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a blue colorant, wherein molality of ethylenically unsaturated double bonds in the blue colored composition is 3.0*10<SP>-3</SP>to 7.0*10<SP>-3</SP>mol/g based on the total weight of the photosensitive transparent resin, non-photosensitive transparent resin and polyfunctional monomer. The color filter has filter segments formed from the blue colored composition for a color filter.
Description
Technical field
The present invention relates to the photosensitive coloring composition of high sensitivity, the color composition for color filter that particularly relates to the high sensitivity that in the manufacturing of the color filter that is used for color liquid crystal display arrangement, colour pick-up tube element etc., uses, and the color filter that uses said composition to form.
Background technology
Color filter is fine band (bar) the shape color filter of two or more different colors joint (filter segment) to be carried out parallelly or arranged in a crossed manner on the surface of transparency carriers such as glass, or color filter that will be fine saves and forms by the constant arrangement setting of length and width.The color filter joint is fine to several microns～hundreds of microns, and every kind of color arrangement in accordance with regulations is provided with in order.
Usually, in color liquid crystal display arrangement, on color filter, be formed for driving the transparency electrode of liquid crystal, and then be formed for alignment films that liquid crystal is orientated by certain orientation thereon by evaporation or sputter.In order fully to obtain the performance of these transparency electrodes and alignment films, its form usually must 200 ℃ or more than, preferably under 230 ℃ or above high temperature, carry out.
Therefore, at present as the manufacture method of the color composition for color filter that in the manufacturing of color filter, uses, adopt mostly with the pigment of photostability, excellent heat resistance method as the so-called pigment dispersing method of coloured material.
In the pigment dispersing method, the photosensitive coloring composition (pigment anticorrosive additive material) that is dispersed with pigment in photosensitive polymer combination can be coated on the transparency carriers such as glass, dry except that after desolvating, carry out a kind of pattern exposure of crossing colour filter, then unexposed portion is removed the pattern that forms first kind of color by developing procedure, heat again as required etc. handle after, by all colour filters of crossing are operated successively repeatedly equally, thereby produce color filter.
Contain the photosensitive coloring composition of pigment and form color filter when joint in use, high photosensitivity, non-image part are important characteristics for the dissolubility of developer solution and the chemical resistance of image section.In recent years, the requirement of the higher black matrix" (black matrix) of the higher color filter of color depth and optical concentration (OD value) is improved gradually, and there is the tendency that increases in the concentration of coloured material in the photosensitive coloring composition.Yet,, can cause that exposed portion can't fully solidify owing to the increase of coloured material self light absorption etc. other characteristics are exerted an influence if coloured material concentration rises.Therefore, the rising of coloured material concentration is a kind of compromise relation with the characteristic of keeping based on photonasty from photosensitive polymer combination.
In order to improve photonasty and for the dissolubility of developer solution, known use side chain have the photonasty transparent resin of ethylenical unsaturated double bonds and carboxyl and the color filter that obtains with photosensitive coloring composition (reference example such as TOHKEMY 2002-014468 communique).For with this photonasty transparent resin as photosensitive polymer combination, must be by adjusting the kind and the ratio of the monomer that constitutes the photonasty transparent resin, and satisfy the design of multifrequency natures such as stable, dissolubility and chemical resistance.
In addition, in photosensitive coloring composition, should keep the dispersion stabilization of coloured material, high sensitivityization and the good pattern of realizing the photosensitive coloring composition that produces along with high concentrationization again form property (shape maintains of the dissolubility of unexposed portion, photocuring part etc.), and this requirement is to be beyond one's reach by the design alteration of photonasty transparent resin only.
Summary of the invention
Therefore, the present invention aim to provide a kind ofly have both high sensitivity and excellent dispersion stability, pattern forms the color composition for color filter of rerum naturas such as property, chemical resistance, and uses the color filter of said composition.
Color composition for color filter of the present invention contains photonasty transparent resin, non-photosensitive transparent resin, have the polyfunctional monomer and the coloured material of 3 or more a plurality of ethylenical unsaturated double bonds, wherein, general assembly (TW) with photonasty transparent resin, non-photosensitive transparent resin and polyfunctional monomer is a benchmark, and the weight-molality of the ethylenical unsaturated double bonds in this coloured composition is 1.0 * 10
-3Mol/g～7.0 * 10
-3Mol/g.
In addition, color filter of the present invention has the color filter joint that uses above-mentioned color composition for color filter and form.
Color composition for color filter of the present invention is owing to be neccessary composition with photonasty transparent resin, non-photosensitive transparent resin and polyfunctional monomer, and the concentration at photoreactivity position is under control, so can realize that dispersion stabilization, high sensitivity, good pattern as color composition for color filter form property, chemical resistance.
In addition, color composition for color filter of the present invention, its solvent resistance is than present color composition for color filter height, and because therefore high sensitivity can fully solidify under a spot of exposure, productivity is also good.Therefore the application of the invention color composition for color filter forms the color filter joint, and the look that can make stable high-quality transmission-type and Reflexible color LCD and solid-state imager decomposes uses color filter.
Embodiment
At first, color composition for color filter of the present invention is described.
Color composition for color filter of the present invention contains photonasty transparent resin, non-photosensitive transparent resin, have the polyfunctional monomer and the coloured material of 3 or more a plurality of ethylenical unsaturated double bonds.
In addition, with photonasty transparent resin, non-photosensitive transparent resin and polyfunctional monomer (below, the composition that photonasty transparent resin, non-photosensitive transparent resin and polyfunctional monomer are constituted is called photosensitive polymer combination) general assembly (TW) be benchmark, the ethylenical unsaturated double bonds weight-molality in the coloured composition of the present invention is 1.0 * 10
-3Mol/g～7.0 * 10
-3Mol/g.
Ethylenical unsaturated double bonds weight-molality in the coloured composition is calculated as follows:
(ethylenical unsaturated double bonds weight-molality)=(two key equivalents of the weight/polyfunctional monomer of two key equivalent+polyfunctional monomers of the weight of photonasty transparent resin/photonasty transparent resin)/(weight of the weight+polyfunctional monomer of the weight of photonasty transparent resin+non-photosensitive transparent resin)
In addition, so-called pair of key equivalent is meant by following formula definition, and becomes the yardstick of weighing contained double key number amount in the molecule that if the compound of same molecular amount, the numerical value of two key equivalents is more little, and then the import volume of two keys is just many more.
[two key equivalent]=[molecular weight of constitutional repeating unit]/[the double key number amount in the constitutional repeating unit]
Ethylenical unsaturated double bonds weight-molality in coloured composition is lower than 1.0 * 10
-3Under the situation of mol/g, photonasty reduces, and can't obtain enough curable when forming painted filming.In addition, the ethylenical unsaturated double bonds weight-molality in coloured composition surpasses 7.0 * 10
-3Under the situation of mol/g, sensitivity improves, but exists dispersion stabilization to reduce and can't obtain uniformly painted film or development reduction, pattern form the situation of property reduction.
The coloured material that uses in coloured composition of the present invention is under any one the situation among redness, magenta, the yellow, consider that from the viewpoint of sensitivity, dispersion stabilization, development, pattern formation property the ethylenical unsaturated double bonds weight-molality in this redness, magenta or the yellow coloring composition is preferably 1.0 * 10
-3Mol/g～4.0 * 10
-3Mol/g, more preferably 2.0 * 10
-3Mol/g～4.0 * 10
-3Mol/g, more preferably 3.0 * 10
-3Mol/g～4.0 * 10
-3Mol/g.
The coloured material that uses in coloured composition of the present invention is under the situation of green, and the viewpoint that forms property from sensitivity, dispersion stabilization, development, pattern considers that the ethylenical unsaturated double bonds weight-molality in this green coloring composition is preferably 2.5 * 10
-3Mol/g～5.0 * 10
-3Mol/g, more preferably 3.0 * 10
-3Mol/g～5.0 * 10
-3Mol/g.
In addition, the coloured material that uses in coloured composition of the present invention is under the situation of blueness, consider that from the viewpoint of sensitivity, dispersion stabilization, development, pattern formation property the ethylenical unsaturated double bonds weight-molality in this blue colored composition is preferably 3.0 * 10
-3Mol/g～7.0 * 10
-3Mol/g, more preferably 4.0 * 10
-3Mol/g～7.0 * 10
-3Mol/g.
Among the present invention preferred photonasty transparent resin that uses and non-photosensitive transparent resin the transmissivity in the whole wavelength field of the visible region of 400～700nm be preferably 80% or more than, more preferably 95% or more than.
The photonasty transparent resin is the resin that contains ethylenical unsaturated double bonds; for example can enumerate: make have isocyanate group, aldehyde radical, epoxy radicals, carboxyl isoreactivity substituent (methyl) acyclic compound or cinnamic acid and have hydroxyl, carboxyl, the substituent macromolecule of amino isoreactivity and react, thereby imported in above-mentioned macromolecule that (methyl) acryloyl group, styryl etc. have the functional group of ethylenical unsaturated double bonds and the resin that forms.Have particularly: make to have that the multipolymer that can have the ethylenically unsaturated monomer of hydroxyl and other ethylenically unsaturated monomers with the compound of the functional group of hydroxyl reaction and ethylenical unsaturated double bonds, with copolymerization and obtain reacts and the resin that obtains.As can with the functional group of hydroxyl reaction, can enumerate isocyanate group, carboxyl etc., consider from reactive viewpoint, special preferred isocyanate base, as compound with isocyanate group and ethylenical unsaturated double bonds, specifically, can enumerate 2-acryloyl ethyl isocyanate, 2-methacryl ethyl isocyanate.In addition, the macromolecule that can also use acid anhydrides such as will containing styrene-maleic anhydride copolymer or alpha-olefin-copolymer-maleic anhydride (methyl) acyclic compound of having a hydroxyl with (methyl) acrylic acid hydroxyalkyl acrylate etc. carries out half esterization and the compound that obtains.
The amount of the ethylenical unsaturated double bonds that imports by hydroxyl etc. in the photonasty transparent resin is by " two key equivalent " expression of the photonasty transparent resin that obtains.
Two key equivalents of the photonasty transparent resin among the present invention are preferably 200～1200, and more preferably 300～900.Under the situation of quantity not sufficient 200, the ratio with ethylenically unsaturated monomer of the reactive substituents that can import ethylenical unsaturated double bonds uprises at two keys of photonasty transparent resin, other ethylenically unsaturated monomers that are used to keep each characteristic of can't copolymerization fully measuring.Under 1200 the situation of surpassing,, thereby can't obtain enough sensitivity because the quantity of ethylenical unsaturated double bonds is few.
In addition, consider that from the viewpoint of the favorable dispersibility of coloured material the weight-average molecular weight of photonasty transparent resin (Mw) is preferably 2000～200000, more preferably 5000～50000.
The non-photosensitive transparent resin is the resin that does not contain ethylenical unsaturated double bonds, and thermoplastic resin, thermoset resin are arranged.As thermoset resin, can enumerate for example butyral resin, styrene-maleic acid copolymer, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, polyurethanes resin, vibrin, acrylic resin, alkyd resin, styrene resin, polyamide, rubber resin, thermoprene resinoid, cellulose family, polybutadiene, polyimide resin etc.In addition, as thermoset resin, can enumerate for example epoxy resin, benzoguanamine resin, Abietyl modified maleic acid resin, Abietyl modified fumaric resin, phenolics, melamine resin, urea resin etc.
Using coloured composition of the present invention to form under the situation of color filter joint,, preferably use the resin of the solvable type of alkali as the non-photosensitive transparent resin by the alkali development.The non-photosensitive transparent resin of the solvable type of so-called alkali, be meant to have character that can be dissolved in alkaline aqueous solution and the transparent resin that does not contain ethylenical unsaturated double bonds, the weight-average molecular weight that can enumerate acidic functionalities such as for example having carboxyl, sulfonic group is 1000～500000, be preferably 5000～100000 non-photosensitive transparent resin.In acidic functionality, preferred carboxyl.In order to make the color composition for color filter decentralized stabilization, and raising developing performance, the acid number of non-photosensitive transparent resin is preferably than the acid number height of photonasty transparent resin, in this balance, the painted pattern formation property of filming that is formed by color composition for color filter becomes well, has obtained the color filter joint of dimensionally stable.Non-photosensitive transparent resin as the solvable type of alkali, specifically, can enumerate acryl resin with acidic functionality, alpha-olefin/maleic acid (acid anhydride) multipolymer, styrene/maleic acid (acid anhydride) multipolymer, styrene/styrene sulfonic acid multipolymer, ethene/(methyl) acrylic copolymer, isobutylene/maleic acid (acid anhydride) multipolymer etc.Wherein, be selected from least a resin among acryl resin, alpha-olefin/maleic acid (acid anhydride) multipolymer, styrene/maleic acid (acid anhydride) multipolymer and the styrene/styrene sulfonic acid multipolymer with acidic functionality, particularly have the acryl resin of acidic functionality, therefore preferred the use because thermotolerance, the transparency are high.
In addition, pigment is being used as under the situation of coloured material, is considering that from the viewpoint that improves dispersing of pigments stability preferred photonasty transparent resin or non-photosensitive transparent resin contain as the ethylenically unsaturated monomer (a) shown in the following formula (1) of polymerization composition.
In formula (1), R
1Expression hydrogen atom or methyl, R
2The expression carbon number is 2～10 alkylidene, R
3The carbon number that the expression hydrogen atom maybe can contain phenyl ring is 1～20 alkyl.N represents 1～15 integer.
In following formula (1), R
2The carbon number of alkylidene is preferably 2～3.In addition, R
3The carbon number of alkyl is 1～20, more preferably 1～10, and R
3Alkyl can also contain phenyl ring.At R
3The carbon number of alkyl is 1～10 o'clock, alkyl becomes obstacle and suppresses approaching mutually between the resin, promotes the absorption/orientation towards pigment, if but carbon number above 10, then the steric hindrance effect of alkyl improves, and demonstrates and also can hinder the tendency of phenyl ring towards pigment adsorption/orientation.This tendency is along with R
3The increase of the carbon atom chain length of alkyl and becoming significantly, if carbon number surpasses 20, the absorption/orientation of the phenyl ring extreme difference that becomes then.As R
3The alkyl that contains phenyl ring of expression can be enumerated benzyl, 2-phenyl (different) propyl group etc.
As ethylenically unsaturated monomer (a), can enumerate oxirane (EO) modification (methyl) acrylate of phenol, to the EO of cumylphenol or epoxypropane (PO) modification (methyl) acrylate, EO modification (methyl) acrylate of nonyl phenol, PO modification (methyl) acrylate of nonyl phenol etc.In these compounds, EO or PO modification (methyl) acrylate to cumylphenol not only have the pi-electron effect of above-mentioned phenyl ring, also have its stereoeffect, can form more good adsorption/oriented surface, so dispersion effect is better painted materials such as pigment.
As can with other ethylenically unsaturated monomer compounds (b) of ethylenically unsaturated monomer (a) copolymerization, can list (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid (different) propyl ester, (methyl) acrylic acid (different) butyl ester, (methyl) acrylic acid (different) pentyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid Isobornyl, acid phosphorus oxygen base ethyl (methyl) acrylate (acid phosphoxy ethyl-(meth) acrylate), acid phosphorus oxygen base propyl group (methyl) acrylate (acid phosphoxy propyl-(meth) acrylate), 3-chloro-2-acid phosphorus oxygen base ethyl (methyl) acrylate, acid phosphorus oxygen base polyethyleneglycol (methyl) acrylate etc., these compounds can use a kind or two or more.
The photonasty transparent resin that the ethylenically unsaturated monomer (a) of the above-mentioned general formula of copolymerization (1) expression and other the monomeric compound with ethylenical unsaturated double bonds (b) obtain or the copolymerization ratio of the monomer (a) in the non-photosensitive transparent resin, with (a) and monomer total amount (b) is benchmark, be preferably and account for 0.1～50 weight %, more preferably 10～35 weight %.If the copolymerization ratio of monomer (a) is less than 0.1 weight %, then the dispersing of pigments effect reduces.In addition, if more than 50 weight %, then hydrophobicity increases, development reduction that might coloured composition or become the reason of generation residue.
Photonasty transparent resin and non-photosensitive transparent resin, with respect to 100 weight portion coloured materials, can be preferably by amounting to 20～400 weight portions, more preferably using by the amount that amounts to 50～250 weight portions.
In coloured composition of the present invention, also use photonasty transparent resin and non-photosensitive transparent resin in order to improve sensitivity, but in order fully to improve sensitivity, general assembly (TW) with photonasty transparent resin and non-photosensitive transparent resin is a benchmark, and the content of photonasty transparent resin preferably accounts for 15～80 weight %.In redness or magenta or yellow coloured composition, be benchmark with the general assembly (TW) of photonasty transparent resin and non-photosensitive transparent resin, the content of photonasty transparent resin is 15～65 weight % more preferably.In the coloured composition of green, be benchmark with the general assembly (TW) of photonasty transparent resin and non-photosensitive transparent resin, the content of photonasty transparent resin is 20～50 weight % more preferably.In addition, in the coloured composition of blueness, be benchmark with the general assembly (TW) of photonasty transparent resin and non-photosensitive transparent resin, the content of photonasty transparent resin is 45～80 weight % more preferably.
Content at the photonasty transparent resin is less than under the situation of 15 weight %, the photonasty of coloured composition reduces, when forming painted filming, there is the situation that can't obtain sufficient curable, even replenish curable by polyfunctional monomer, also have the inadequate situation of painted solvent resistance of filming.In addition, under the situation of content more than 80 weight % of photonasty transparent resin, the sensitivity of coloured composition improves, but exists can't obtain even color because dispersion stabilization reduces painted to film or development reduction or pattern form the situation of property reduction.
Typical example as the polyfunctional monomer with 3 or more a plurality of ethylenical unsaturated double bonds can list various acrylate such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, ethylene oxide modification trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate and methacrylate etc.Consider that from the viewpoint of the sensitivity that improves coloured composition polyfunctional monomer preferably has 3～12 ethylenical unsaturated double bonds.The polyfunctional monomer with 3 or more a plurality of ethylenical unsaturated double bonds can use separately, also but two or more mix and use.
With respect to 100 weight portion coloured materials, have the polyfunctional monomer of 3 or more a plurality of ethylenical unsaturated double bonds can be preferably by 10～300 weight portions, more preferably use by the amount of 10～200 weight portions.
Ethylenical unsaturated double bonds weight-molality (weight with photosensitive polymer combination is benchmark) with polyfunctional monomer of 3 or more a plurality of ethylenical unsaturated double bonds is preferably 2～35 times of ethylenical unsaturated double bonds weight-molality (weight with photosensitive polymer combination is benchmark) of photonasty transparent resin, at coloured composition is under the situation of redness or magenta or yellow coloured composition, more preferably 2～25 times, more preferably 2～20 times, be preferably 2～15 times especially, under the situation of coloured composition that is green, more preferably 3～30 times, more preferably 3～25 times, under the situation of coloured composition that is blueness, more preferably 5～25 times, more preferably 5～15 times.When the molal ratio of the ethylenical unsaturated double bonds of monomer was less than 2 times, the sensitivity of coloured composition reduced, and can't obtain sufficient curable when forming painted filming.In addition, more than 35 times the time, the sensitivity of coloured composition improves, but has the situation that causes that dispersion stabilization reduces and pattern formation property is not good.
As the coloured material that is contained in the color composition for color filter of the present invention, can use separately, also can 2 kinds or multiple mixing use the pigment of organic or inorganic.As pigment, preferred colour rendering height and the high pigment of thermotolerance, the high pigment of preferred especially heat-resisting decomposability uses organic pigment usually.Below, represent the concrete example of operable organic pigment in the coloured composition of the present invention with colour index.
Use coloured composition of the present invention to form under the situation of red color filter joint, for example can use C.I. paratonere 7,14,41,48:1,48:2,48:3,48:4,81:1,81:2,81:3,81:4,146,168,177,178,184,185,187,200,202,208,210,246,254,255,264,270,272, red pigments such as 279.In red composition, can and use orange pigment and following illustrative yellow uitramarines such as C.I. pigment orange 43,71,73.
In addition, under the situation that forms the magenta color filter joint, for example can use C.I. pigment violet 1,19, C.I. pigment red 81,122,144,146,169,177, violet pigment and red pigments such as 207.
In addition, under the situation that forms the yellow color filter joint, can use for example C.I. pigment yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,126,127,128,129,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,198,199,213,214 yellow uitramarines such as grade.
As inorganic pigment, can enumerate yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red etc.For in the balance that obtains chroma and brightness, guarantee good coating, sensitivity, development etc., inorganic pigment can be used in combination with organic pigment.
Use coloured composition of the present invention to form under the situation of green color filter joint, for example can use C.I. pigment Green 7,10,36, viridine greens such as 37.In green coloring composition, can be also with above-mentioned illustrative yellow uitramarine.
As inorganic pigment, can enumerate chrome oxide green, cobalt green etc., in the balance that obtains chroma and brightness, guarantee good coating, sensitivity, development etc., inorganic pigment can be used in combination with organic pigment.
Use coloured composition of the present invention to form under the situation of blue color filter joint, for example can use C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:5,15:6,16,22,60, blue pigments such as 64.In blue colored composition, can and with C.I. pigment violet 1, violet pigments such as 19,23,27,29,30,32,37,40,42,50.
In addition, under the situation that forms dark green color filter joint, can use for example C.I. pigment blue 15: 1,15:2,15:3,15:4,15:6,16, blue pigments such as 81.
As inorganic pigment, when can enumerate the balance of ultramarine, Prussian blue acquisition chroma and brightness, guarantee good coating, sensitivity, development etc., inorganic pigment can be used in combination with organic pigment.
In coloured composition of the present invention, in order to mix colours, can contain dyestuff not reducing stable on heating scope.
Coloured composition of the present invention can adopt various diverting devices such as three roller attrition mills, two roller attrition mills, sand mill, kneader, vertical ball mill, paint regulator that coloured material is dispersed in the photosensitive polymer combination imperceptibly and make.
Coloured material is being used as under the situation of pigment, can using resin type pigment dispersing agent, pigment derivative, surfactant etc. to disperse auxiliary agent aptly.Dispersing aid for make dispersing of pigments become good and prevent to disperse after pigment again aggegation have positive effect, therefore when using the coloured composition that pigment dispersing is obtained by dispersing aid in photosensitive polymer combination, can obtain the good color filter of the transparency.With respect to 100 weight portion coloured materials, dispersing aid can preferably be pressed 0.1～40 weight portion, more preferably use by the amount of 0.1～30 weight portion.
The resin type pigment dispersing agent has following two kinds of positions: have the pigment compatibility position of the character that is adsorbed on the pigment and have the position of intermiscibility with photonasty transparent resin and non-photosensitive transparent resin, it is adsorbed on the pigment, plays the effect that makes the decentralized stabilization of pigment in photosensitive polymer combination.As the resin type pigment dispersing agent, can use polycarboxylates such as polyurethane, polyacrylate, unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, poly carboxylic acid ammonium salt, poly carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, the polycarboxylate that contains hydroxyl and their modifier, by poly-(rudimentary alkyleneimines) with have the acid amides of reaction formation of polyester of free carboxy and salt etc.In addition, can also use water soluble resins such as (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), polyvinylpyrrolidone and water-soluble high-molecular compound, polyesters, modified polyacrylate, ethylene oxide/propylene oxide addition product etc.These materials can use separately, but also two or more mix use.
As commercially available resin type pigment dispersing agent, can enumerate the Disperbyk-101 that PVC Star Network ケ ミ-company makes, 103,107,108,110,111,116,130,140,154,161,162,163,164,165,166,170,171,174,180,181,182,183,184,185,190,2000,2001 or Anti-Terra-U, 203,204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykumen etc., the SOLSPERSE-3000 that ア PVC シ ア company makes, 9000,13240,13650,13940,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32600,34750,36600,38500,41000,41090,53095 etc., the EFKA-46 that エ Off カ ケ ミ カ Le ズ company makes, 47,48,452, LP4008,4009, LP4010, LP4050, LP4055,400,401,402,403,450,451,453,4540,4550, LP4560,120,150,1501,1502,1503 etc.
Pigment derivative is to import the compound that forms behind the substituting group in organic pigment.Organic pigment also comprises flaxen aromatic series polycyclic compunds such as the naphthalene class that usually is not called as pigment, anthraquinone class.As pigment derivative, can use the material of records such as Japanese kokai publication sho 63-305173 communique, Japanese Patent Publication 57-15620 communique, Japanese Patent Publication 59-40172 communique, Japanese Patent Publication 63-17102 communique, the special fair 5-9469 communique of Japan, these materials can use separately, but also two or more mix use.
As surfactant, can enumerate alkali metal salt, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, dodecyl sulphate monoethanolamine, dodecyltriethanolamine sulfate, ammonium lauryl sulfate, stearic acid monoethanolamine, odium stearate, the lauryl sodium sulfate of polyethylene oxide alkyl ethers sulfate, neopelex, styrene-propene acid copolymer, the anionic surfactants such as monoethanolamine of styrene-propene acid copolymer; Non-ionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene sorbitan monostearate, polyethyleneglycol dodecyl ester; Cationic surfactant such as alkyl quaternary ammonium salts and ethylene oxide adduct thereof; Amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as alkyl dimethyl aminoacetic acid betaine, these surfactants can use separately, but also two or more mix use.
For make composition through the time change viscosity and keep stable, in coloured composition of the present invention, can contain the storage-stable agent.As the storage-stable agent, can enumerate for example organic phosphine, phosphite etc. such as organic acid such as aliquat such as benzyl trimethyl chloride, diethyl hydramine, lactic acid, oxalic acid and their methyl ether, tert-butyl catechol, tetraethyl phosphine, tetraphenyl phosphine.With respect to 100 weight portion coloured materials, the storage-stable agent can preferably be used by the amount of 0.1～10 weight portion.
In addition, for coloured material is well dispersed in the photosensitive polymer combination, and said composition is coated on to make dry film thickness on the transparency carrier such as glass substrate be 0.2～5 μ m, thus form the color filter joint, in coloured composition of the present invention, can contain solvent.As solvent, can enumerate for example cyclohexanone, ethyl cellulose acetate, butyl cellulose acetate, 1-methoxyl-2-propyl group acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, dimethylbenzene, ethyl cellulose, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, MEK, ethyl acetate, methyl alcohol, ethanol, isopropyl alcohol, butanols, isobutyl ketone, petroleum-type solvent etc., these materials can be used alone or as a mixture.With respect to 100 weight portion coloured materials, solvent can preferably be pressed 800～4000 weight portions, more preferably use by the amount of 1000～2500 weight portions.
When coloured composition of the present invention is solidified, in said composition, add Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater; can use 4-phenoxy group dichloroacetophenone; the 4-tert-butyl group-dichloroacetophenone; diethoxy acetophenone; 1-(4-cumenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-hydroxy-cyclohexyl benzophenone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine propane-acetophenones Photoepolymerizationinitiater initiaters such as 1-ketone; benzoin; benzoin methylether; benzoin ethyl ether; benzoin iso-propylether; benzoin class Photoepolymerizationinitiater initiaters such as benzyl dimethyl ketal; benzophenone; the benzoyl benzoic acid; benzoyl benzoic acid methyl esters; the 4-phenyl benzophenone; dihydroxy benaophenonel; the acrylated benzophenone; 4-benzoyl-4 '-benzophenone Photoepolymerizationinitiater initiaters such as methyldiphenyl base sulfide; thioxanthones; the 2-clopenthixal ketone; 2-methyl thioxanthones; isopropyl thioxanthone; 2; thioxanthene ketone Photoepolymerizationinitiater initiaters such as 4-diisopropyl thioxanthones; 2; 4; 6-three chloro-s-triazines; 2-phenyl-4; two (the trichloromethyl)-s-triazines of 6-; 2-(p-methoxyphenyl)-4; two (the trichloromethyl)-s-triazines of 6-; 2-(p-methylphenyl)-4; two (the trichloromethyl)-s-triazines of 6-; two-piperonyl-4; two (the trichloromethyl)-s-triazines of 6-; 2; two (the trichloromethyl)-6-styryls of 4--s-triazine; 2-(naphtho--1-yl)-4; two (the trichloromethyl)-s-triazines of 6-; 2-(4-methoxyl-naphtho--1-yl)-4; two (the trichloromethyl)-s-triazines of 6-; 2; 4-trichloromethyl-(piperonyl)-6-triazine; 2,4-trichloromethyl (4 '-methoxyl-styrene)-triazines Photoepolymerizationinitiater initiaters such as 6-triazine; the borate ester Photoepolymerizationinitiater initiater; the carbazoles Photoepolymerizationinitiater initiater; imidazoles Photoepolymerizationinitiater initiater etc.With respect to 100 weight portion coloured materials, Photoepolymerizationinitiater initiater can preferably be pressed 5～200 weight portions, more preferably use by the amount of 10～150 weight portions.
These Photoepolymerizationinitiater initiaters can use separately; also but two or more mix use; as sensitizer; also can and use alpha-acyloxy ester, acylphosphine oxide, aminomethyl phenyl glyoxylic ester, benzyl-9,10-phenanthrenequione, camphorquinone, EAQ, 4, phenyl-diformyl base benzene, 3 between 4 '-diethyl; 3 '; 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 4, compounds such as 4 '-diethylin benzophenone.With respect to 100 weight portion Photoepolymerizationinitiater initiaters, sensitizer can preferably use with the amount of 0.1～60 weight portion.
Preferably the ratio with 0.5～10 weight % contains coloured material in coloured composition (coloured composition that also contains all the components such as initiating agent and solvent except transparent resin, polyfunctional monomer, coloured material).In addition, in final color filter joint, preferably with 10～60 weight %, more preferably the ratio with 20～50 weight % contains coloured material, its remainder is made of photonasty transparent resin, non-photosensitive transparent resin and polyfunctional monomer in fact.
Preferred adopt devices such as centrifuging, sintered filter, membrane filter from coloured composition of the present invention with 5 μ m or above big particle, be preferably 1 μ m or above big particle, more preferably 0.5 μ m or above big particle and the dust of sneaking into are removed.
Below, color filter of the present invention is described.
Color filter of the present invention has the color filter joint that is formed by color composition for color filter of the present invention.Color filter has following type: the additive color mixing type with at least one red color filter joint, at least one green color filter joint and at least one blue color filter joint, with the substractive color mixing type with at least one magenta color filter joint, at least one dark green color filter joint and at least one yellow color filter joint, and the color filter of at least a color joint is to use coloured composition of the present invention to form.
Color filter joint beyond the color filter joint that uses coloured composition of the present invention and form can use the common coloured composition of all kinds that contains pigment of all kinds, above-mentioned non-photosensitive transparent resin, above-mentioned polyfunctional monomer to form.Consider that from the viewpoint of pattern formation property, solvent resistance preferred whole color filter joints all use coloured composition of the present invention to form.
Color filter of the present invention can form color filter joint of all kinds by photoetch method, use coloured composition of the present invention and common coloured composition of all kinds and prepare on substrate.
As substrate, use resin plates such as the high glass plate of visible light transmissivity, polycarbonate, polymethylmethacrylate, polyethylene terephthalates.
Adopting photoetch method to form color filter joint of all kinds carries out as follows.Promptly, with coating processes such as spraying, spin coating, slot coated, roller coat, the coloured composition of all kinds that above-mentioned solvent develop type that will solidify because of rayed as meeting or the painted anticorrosive additive material of alkali developable are modulated is coated on the transparency carrier, and making dry film thickness is 0.2～5 μ m.As required, on the film of drying, by contact with this film or non-contacting state under the mask that is provided with predetermined pattern carry out ultraviolet exposure., be impregnated in solvent or the alkaline developer thereafter, or by spray developing liquid such as sprayers removing uncured portion, thereby form required pattern, thereafter other colors are carried out same operation repeatedly, make color filter.In addition, in order to promote the polymerization of painted anticorrosive additive material, can also heat as required.Can produce than the more high-precision color filter of print process by photoetch method.
When developing, the aqueous solution of using sodium carbonate, NaOH etc. also can be used organic bases such as dimethyl benzyl amine, triethanolamine as alkaline developer.In addition, also can in developer solution, add defoamer or surfactant.
In addition, in order to improve the ultraviolet exposure sensitivity, also can be behind the dry above-mentioned painted anticorrosive additive material of coating, the dry water-soluble or alkali soluble resin of coating, for example polyvinyl alcohol (PVA) or water soluble acrylic resin etc., formation can prevent that block causes hindering the film of polymerization, carries out ultraviolet exposure thereafter.
Embodiment
Below the present invention will be described based on embodiment, but the invention is not restricted to these embodiment.In addition, in following embodiment and comparative example, " part " expression " weight portion ".The molecular weight of resin is the weight-average molecular weight of measuring by GPC (gel permeation chromatography) that is converted into polystyrene.
The synthesis example 1 of photonasty transparent resin
In reaction vessel, add 560 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 34.0 parts of methacrylic acids, 23.0 parts of methyl methacrylates, 23.0 parts of n-BMAs, 22.0 parts of oxirane modification acrylates (" ア ロ ニ Star Network ス M110 " that Toagosei Co., Ltd makes), 47.0 parts of glycerin monomethyl acrylic esters to cumylphenol as monomer (a), 4.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 55 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain transparent resin solution.
Then,, under 70 ℃, in 3 hours, splash into the potpourri of 32.0 parts of 2-methacryl ethyl isocyanates, 0.4 part of dibutyl tin laurate, 120.0 parts of cyclohexanone, obtain the photonasty transparent resin solution with respect to 338 parts of transparent resin solutions that obtain.After being cooled to room temperature, get about 2g photonasty transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining photonasty transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required photoresist solution.The weight-average molecular weight Mw of the photonasty transparent resin 1 that obtains is 21000, and two key equivalents are 470.
The synthesis example 2 of photonasty transparent resin
In reaction vessel, add 570 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 23.0 parts of methacrylic acids, 23.0 parts of methyl methacrylates, 35.0 parts of benzyl methacrylates, 22.0 parts of oxirane modification acrylates (" ア ロ ニ Star Network ス M110 " that Toagosei Co., Ltd makes), 48.0 parts of glycerin monomethyl acrylic esters to cumylphenol as monomer (a), 3.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 50 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain transparent resin solution.
Then,, under 70 ℃, in 3 hours, splash into the potpourri of 33.0 parts of 2-methacryl ethyl isocyanates, 0.4 part of dibutyl tin laurate, 130.0 parts of cyclohexanone, obtain the photonasty transparent resin solution with respect to 336 parts of transparent resin solutions that obtain.After being cooled to room temperature, get about 2g photonasty transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining photonasty transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required photoresist solution.The weight-average molecular weight Mw of the photonasty transparent resin 2 that obtains is 32000, and two key equivalents are 460.
The synthesis example 3 of photonasty transparent resin
In reaction vessel, add 520 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 7.0 parts of methacrylic acids, 7.0 parts of methyl methacrylates, 63.0 parts of 2-hydroxyethyl methacrylates, 66.0 parts of glycerin monomethyl acrylic esters, 4.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 70 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain transparent resin solution.
Then,, under 70 ℃, in 3 hours, splash into the potpourri of 56.0 parts of 2-methacryl ethyl isocyanates, 0.4 part of dibutyl tin laurate, 220.0 parts of cyclohexanone, obtain the photonasty transparent resin solution with respect to 220 parts of transparent resin solutions that obtain.After being cooled to room temperature, get about 2g photonasty transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining photonasty transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required photoresist solution.The weight-average molecular weight Mw of the photonasty transparent resin 3 that obtains is 20000, and two key equivalents are 270.
The synthesis example 4 of photonasty transparent resin
In reaction vessel, add 480 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 32.0 parts of methacrylic acids, 24.0 part methyl methacrylate, 16.0 part n-BMA, 29.0 part benzyl methacrylate, 19.0 part oxirane modification acrylate (" ア ロ ニ Star Network ス M110 " that Toagosei Co., Ltd makes) to cumylphenol as monomer (a), 15.0 part glycerine methyl mono acrylic ester, 4.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 80 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain transparent resin solution.
Then,, under 70 ℃, in 3 hours, splash into the potpourri of 14.0 parts of 2-methacryl ethyl isocyanates, 0.4 part of dibutyl tin laurate, 55.0 parts of cyclohexanone, obtain the photonasty transparent resin solution with respect to 445 parts of transparent resin solutions that obtain.After being cooled to room temperature, get about 2g photonasty transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining photonasty transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required photoresist solution.The weight-average molecular weight Mw of the photonasty transparent resin 4 that obtains is 21000, and two key equivalents are 1000.
The synthesis example 5 of photonasty transparent resin
In reaction vessel, add 560 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 22.0 parts of methacrylic acids, 22.0 parts of n-BMAs, 104.0 parts of 2-hydroxyethyl methacrylates, 4.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 50 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain transparent resin solution.
Then,, under 70 ℃, in 3 hours, splash into the potpourri of 33.0 parts of 2-methacryl ethyl isocyanates, 0.4 part of dibutyl tin laurate, 130.0 parts of cyclohexanone, obtain the photonasty transparent resin solution with respect to 338 parts of transparent resin solutions that obtain.After being cooled to room temperature, get about 2g photonasty transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining photonasty transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required photoresist solution.The weight-average molecular weight Mw of the photonasty transparent resin 5 that obtains is 20000, and two key equivalents are 470.
The synthesis example 6 of photonasty transparent resin
In reaction vessel, add 570 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 7.0 parts of methacrylic acids, 11.0 parts of methyl methacrylates, 32.0 parts of benzyl methacrylates, 101.0 parts of 2-hydroxyethyl methacrylates, 3.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 50 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain transparent resin solution.
Then,, under 70 ℃, in 3 hours, splash into the potpourri of 33.0 parts of 2-methacryl ethyl isocyanates, 0.4 part of dibutyl tin laurate, 130.0 parts of cyclohexanone, obtain the photonasty transparent resin solution with respect to 337 parts of transparent resin solutions that obtain.After being cooled to room temperature, get about 2g photonasty transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining photonasty transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required photoresist solution.The weight-average molecular weight Mw of the photonasty transparent resin 6 that obtains is 30000, and two key equivalents are 460.
The synthesis example 1 of non-photosensitive transparent resin
In reaction vessel, add 370 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 1 hour, splash into 20.0 parts of methacrylic acids, 10.0 parts of methyl methacrylates, 55.0 parts of n-BMAs, 15.0 parts of 2-hydroxyethyl methacrylates, 4.0 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 1.0 parts of solution that azoisobutyronitrile obtains in 50 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain the non-photosensitive transparent resin solution.
After being cooled to room temperature, get about 2g non-photosensitive transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining non-photosensitive transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required non-photosensitive resin solution.The weight-average molecular weight Mw of the non-photosensitive transparent resin 1 that obtains is 40000.
The synthesis example 2 of non-photosensitive transparent resin
In reaction vessel, add 70 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 2 hours, splash into 12.3 parts of n-BMAs, 4.6 parts of 2-hydroxyethyl methacrylates, 5.3 parts of methacrylic acids, 7.4 parts of oxirane modification acrylates (" ア ロ ニ Star Network ス M110 " that Toagosei Co., Ltd makes) to cumylphenol as monomer (a), 0.4 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 0.2 part of solution that azoisobutyronitrile obtains in 10 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain the non-photosensitive transparent resin solution.
After being cooled to room temperature, get about 2g non-photosensitive transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining non-photosensitive transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required non-photosensitive resin solution.The weight-average molecular weight Mw of the non-photosensitive transparent resin 2 that obtains is 27000.
The synthesis example 3 of non-photosensitive transparent resin
In reaction vessel, add 70 parts of cyclohexanone, nitrogen injection in container, be warming up to 80 ℃ simultaneously, under same temperature, in 2 hours, splash into 14.4 parts of n-BMAs, 4.6 parts of 2-hydroxyethyl methacrylates, 3.2 parts of methacrylic acids, 7.4 parts of oxirane modification acrylates (" ア ロ ニ Star Network ス M110 " that Toagosei Co., Ltd makes) to cumylphenol as monomer (a), 0.4 part 2, the potpourri of 2 '-azoisobutyronitrile carries out polyreaction.After splashing into end, reacted 3 hours down at 80 ℃ again, be added on then and dissolved 0.2 part of solution that azoisobutyronitrile obtains in 10 parts of cyclohexanone, continue reaction 1 hour down at 80 ℃ again, obtain the non-photosensitive transparent resin solution.
After being cooled to room temperature, get about 2g non-photosensitive transparent resin solution, measure its nonvolatile component after 20 minutes at 180 ℃ of following heat dryings as sample.Based on this measurement result, in above-mentioned remaining non-photosensitive transparent resin solution, add cyclohexanone so that nonvolatile component reaches 20 weight %, be mixed with required non-photosensitive resin solution.The weight-average molecular weight Mw of the non-photosensitive transparent resin 3 that obtains is 25000.
Weight-average molecular weight Mw, two key equivalent and the acid number of the non-photosensitive transparent resin 1～3 that the photonasty transparent resin 1～6 that obtains in the synthesis example 1～6 of the transparent resin of photonasty shown in the table 1 and the synthesis example 1～3 of non-photosensitive transparent resin obtain.In addition, acid number is measured according to JIS-K-0070, calculates.
Table 1
| Synthesis example | Molecular weight Mw | Two key equivalents | Acid number (mgKOH/g) | |
| The photonasty transparent resin | 1 | 21000 | 470 | 98 |
| 2 | 32000 | 460 | 65 | |
| 3 | 20000 | 270 | 13 | |
| 4 | 21000 | 1000 | 125 | |
| 5 | 20000 | 470 | 65 | |
| 6 | 30000 | 460 | 20 | |
| The non-photosensitive transparent resin | 1 | 40000 | 0 | 130 |
| 2 | 27000 | 0 | 117 | |
| 3 | 25000 | 0 | 70 | |
Embodiment 1
The preparation of＜pigment dispersion 〉
After the potpourri of following component evenly mixed, use the zirconium oxide bead of diameter as 1mm, after disperseing 2 hours by Eiger mill (ア イ ガ-ミ Le) (" ミ ニ モ デ Le M-250 MKII " that ア イ ガ-ジ ヤ パ Application company makes), use the filtrator of 5 μ m to filter, be mixed with pigment dispersion.
Red pigment: diketopyrrolopyrroles pigment (C.I. paratonere 254) (" イ Le ガ Off オ-レ Star De B-CF " that チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes): 11.0 parts
Diketopyrrolopyrroles pigment derivative (following formula (2)): 1.0 parts
Photonasty transparent resin 1 solution: 10.0 parts
Non-photosensitive transparent resin 1 solution: 30.0 parts
Cyclohexanone: 50.0 parts
The preparation of＜red colored composition 〉
After the potpourri of following component mixed, use the filtrator of 1 μ m to filter, obtain having photosensitive red colored composition.
The pigment dispersion of above-mentioned preparation: 37.5 parts
Photonasty transparent resin 1 solution: 11.8 parts
Non-photosensitive transparent resin 1 solution: 12.2 parts
Pentaerythritol triacrylate hexamethylene diisocyanate: 4.1 parts
Photoepolymerizationinitiater initiater (チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes " イ Le ガ キ ユ ア-907 "): 1.5 parts
Sensitizer (protecting " EAB-F " that native ケ paddy chemical company makes): 0.1 part
Cyclohexanone: 32.8 parts
Embodiment 2～28 and comparative example 1～5
With the photonasty transparent resin solution shown in the table 3, non-photosensitive transparent resin solution and polyfunctional monomer (with reference to table 2) mix according to the ratio shown in the table 3 (weight ratio of solid constituent), and [embodiment 9: pigment is to be that quinoline a word used for translation ketone pigment (" the Fastgen Super " that big Japanese ink chemical industrial company makes used in 7/3 mixing by weight to obtain having photosensitive redness or magenta similarly to Example 1, Pigment Red 207) and quinoline a word used for translation ketone pigment (" the CINQUASIA Violet RNRT-201-D " that チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes C.I., C.I. pigment violet 1 9).Pigment derivative is used quinoline a word used for translation ketone pigment derivative (following formula (3))] or yellow [embodiment 24: pigment uses isoindoline pigment (" イ Le ガ Off オ ア イ エ ロ-2R-CF ", C.I. pigment yellow 13 9 that チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes).Pigment derivative is used azo class pigment derivative (using following formula (4)).] coloured composition (redness or magenta or yellow anticorrosive additive material).Photonasty transparent resin solution, non-photosensitive transparent resin solution be mixed with make photonasty transparent resin and non-photosensitive transparent resin become the ratio shown in the table 3 with polyfunctional monomer.In the coloured composition that 100 weight portions obtain, the shared toatl proportion of these 3 kinds of compositions is identical in embodiment 1～28 and comparative example 1～5.
Calculate respectively with the general assembly (TW) in photonasty transparent resin and the non-photosensitive transparent resin is content (weight %) ratio with respect to the photonasty transparent resin of all resins of benchmark; General assembly (TW) with photonasty transparent resin contained in the coloured composition, non-photosensitive transparent resin and polyfunctional monomer is a benchmark, and contained ethylenical unsaturated double bonds weight-molality (Cb) is with respect to the ratio (Cb/Ca) of ethylenical unsaturated double bonds volumetric molar concentration (Ca) contained in this photonasty transparent resin in this polyfunctional monomer; General assembly (TW) with photonasty transparent resin contained in the coloured composition, non-photosensitive transparent resin and polyfunctional monomer is a benchmark, the weight-molality of the ethylenical unsaturated double bonds in this coloured composition (density of functional group) (mol/g), the result is shown in the table 3.(in addition, in comparative example 3, use two key equivalents of bifunctional monomer, the ethylenical unsaturated double bonds mole of polymerized concentration that bifunctional monomer weight calculates coloured composition.)
Quinoline a word used for translation ketone pigment derivative:
Azo class pigment derivative:
Table 2
| Be called for short | The polyfunctional monomer title | Number of functional groups | Molecular weight |
| TPGDA | Tripropylene glycol diacrylate | 2 | 300 |
| TMPTA | Trimethylolpropane triacrylate | 3 | 296 |
| PE4A | Tetramethylol methane tetraacrylate | 4 | 352 |
| DPHA | Dipentaerythritol acrylate | 6 | 578 |
| PE3AH | The pentaerythritol triacrylate hexamethylene diisocyanate | 6 | 764 |
| DPPAH | Dipentaerythritol five acrylate hexamethylene diisocyanates | 10 | 1216 |
Table 3
| The photonasty transparent resin | The non-photosensitive transparent resin | Polyfunctional monomer | Weight ratio | The content of photonasty transparent resin (%) | Cb/Ca | Functional group densities (mol/g) | ||||
| The photonasty transparent resin | The non-photosensitive transparent resin | Polyfunctional monomer | ||||||||
| Embodiment | 1 | 1 | 1 | PE3AH | 6 | 9 | 8 | 40.0 | 4.9 | 3.3E-03 |
| 2 | 2 | 1 | PE3AH | 6 | 9 | 8 | 40.0 | 4.8 | 3.3E-03 | |
| 3 | 3 | 1 | PE3AH | 6 | 9 | 8 | 40.0 | 2.8 | 3.7E-03 | |
| 4 | 4 | 1 | PE3AH | 6 | 8 | 8 | 42.9 | 10.5 | 3.1E-03 | |
| 5 | 5 | 1 | PE3AH | 6 | 9 | 8 | 400 | 4.9 | 3.3E-03 | |
| 6 | 6 | 1 | PE3AH | 6 | 9 | 8 | 40.0 | 4.8 | 3.3E-03 | |
| 7 | 1 | 1 | PE3AH | 6 | 10 | 5 | 37.5 | 3.1 | 2.5E-03 | |
| 8 | 1 | 1 | PE3AH | 5 | 10 | 3 | 33.3 | 2.2 | 1.9E-03 | |
| 9 | 1 | 1 | PE3AH | 9 | 6 | 8 | 60.0 | 3.3 | 3.6E-03 | |
| 10 | 1 | 1 | TMPTA | 6 | 9 | 6 | 40.0 | 4.8 | 3.5E-03 | |
| 11 | 1 | 1 | PE4A | 6 | 9 | 6 | 40.0 | 5.3 | 3.9E-03 | |
| 12 | 1 | 1 | DPHA | 6 | 9 | 6 | 40.0 | 4.9 | 36E-03 | |
| 13 | 1 | 1 | DPPAH | 6 | 8 | 6 | 42.9 | 3.9 | 3.1E-03 | |
| 14 | 1 | 1 | PE3AH | 14 | 6 | 8 | 70.0 | 2.1 | 3.3E-03 | |
| 15 | 1 | 1 | PE3AH | 1 | 6 | 4 | 14.3 | 14.8 | 3.0E-03 | |
| 16 | 1 | 1 | PE3AH | 13 | 3 | 8 | 81.3 | 2.3 | 3.8E-03 | |
| 17 | 1 | 1 | PE3AH | 2 | 9 | 9 | 18.2 | 16.6 | 37E-03 | |
| 18 | 1 | 1 | PE3AH | 2 | 10 | 11 | 16.7 | 20.3 | 3.9E-03 | |
| 19 | 1 | 1 | PE3AH | 10 | 4 | 5 | 71.4 | 1.8 | 3.2E-03 | |
| 20 | 4 | 1 | PE3AH | 3 | 11 | 10 | 21.4 | 26.2 | 3.4E-03 | |
| 21 | 1 | 2 | PE3AH | 6 | 9 | 8 | 40.0 | 4.9 | 3.3E-03 | |
| 22 | 2 | 2 | PE3AH | 6 | 9 | 8 | 40.0 | 4.9 | 3.3E-03 | |
| 23 | 3 | 2 | PE3AH | 6 | 9 | 8 | 40.0 | 2.8 | 3.7E-03 | |
| 24 | 2 | 3 | PE3AH | 6 | 9 | 8 | 40.0 | 4.8 | 3.3E-03 | |
| 25 | 5 | 2 | PE3AH | 6 | 9 | 8 | 40.0 | 4.9 | 3.3E-03 | |
| 26 | 6 | 3 | PE3AH | 6 | 9 | 8 | 40.0 | 4.8 | 3.3E-03 | |
| 27 | 1 | 3 | PE3AH | 6 | 9 | 7 | 40.0 | 4.3 | 3.1E-03 | |
| 28 | 4 | 2 | PE3AH | 6 | 8 | 8 | 42.9 | 10.5 | 3.1E-03 | |
| Comparative example | 1 | 1 | 1 | PE3AH | 1 | 15 | 2 | 6.3 | 7.4 | 9.9E-04 |
| 2 | 1 | 1 | PE3AH | 5 | 5 | 8 | 50.0 | 5.9 | 4.1E-03 | |
| 3 | 1 | 1 | TPGDA | 6 | 4 | 8 | 60.0 | 4.2 | 3.7E-03 | |
| 4 | - | 1 | PE3AH | 0 | 10 | 8 | 0.0 | - | 3.5E-03 | |
| 5 | 4 | - | PE3AH | 11 | 0 | 8 | 100.0 | 5.7 | 3.9E-03 | |
To the coloured composition that in embodiment 1～28 and comparative example 1～5, obtains, use following method to estimate viscosity stability, sensitivity, pattern formation property and solvent resistance.
＜viscosity stability evaluation 〉
Use E type viscosity meter (" ELD type viscosity meter " that eastern machine industry company makes) under 25 ℃, at revolution be measure under the condition of 20rpm prepare second day initial stage viscosity of coloured composition and under 40 ℃ during 1 week in along with the time change take place through the time variation viscosity.Use following formula calculate from this initial stage viscosity to through the time change the viscosity change rate, the result is shown in the table 4.
[resist inefficacy viscosity rate of change]=| ([initial stage viscosity]-[through the time change viscosity])/[initial stage viscosity] * 100|
＜sensitivity evaluation 〉
Use spin coater that coloured composition is coated on the thick glass substrate of 100mm * 100mm, 1.1mm, forming thickness is filming of 2.0 μ m.Then, after 20 minutes, carry out ultraviolet exposure 70 ℃ of following prebake by mask with 50 μ m thread patterns.With at 10mJ/cm
2～200mJ/cm
2Between the exposure of 8 grades expose.After the exposure, developed 90 seconds, thereby the color filter that forms strip saves with alkaline developer.In addition, as alkaline developer, use the developer solution that constitutes by 1.5 weight % sodium carbonate, 0.5 weight % sodium bicarbonate, 8.0 weight % anionic species surfactants (" ペ リ レ Star Network ス NBL " that KAO. Corp. SA makes) and 90 weight % water.
Will be to the unexposed and undeveloped part of thickness of the color filter that obtains joint as 100, calculate exposure under each higher exposure levels and the residual film ratio after the development.By the residual film ratio curve that obtains, the exposure when residual film ratio is reached capacity is decided to be saturation exposure, and residual film ratio at this moment is decided to be saturated residual film ratio.At saturation exposure that obtains shown in the table 4 and saturated residual film ratio.
＜pattern formation property evaluation 〉
In sensitivity is estimated, except ultraviolet exposure is saturation exposure+50mJ/cm
2Development time in alkaline developer is that each resist of flush away unexposed portion of filming is beyond the required suitable time, make substrate in the same way, afterwards 230 ℃ of following heat treated 60 minutes, with the live width precision of (1) pattern (form with respect to the pattern of the live width of mask after numerical value), the section shape of (2) pattern is estimated to the shape of its thread pattern.For (1), use optical microscope to estimate.Evaluation result is shown in the table 4.The grade of estimating is zero: with the difference of the live width of mask pattern be 5% or following, △: be 5～10% with the difference of the live width of mask pattern, *: with the difference of the live width of mask pattern be 10% or more than.For (2), use scanning electron microscope (SEM) to estimate.The grade of estimating is zero: positive taper, △: non-taper, *: back taper.
＜solvent resistance evaluation 〉
Similarly make filming after the prebake with the sensitivity evaluation, use extra-high-pressure mercury vapour lamp, by mask with 50 μ m thread patterns at saturation exposure+50mJ/cm
2Under carry out ultraviolet exposure.After the exposure, developed 90 seconds, on substrate, form the color filter joint of all kinds of strip with alkaline developer.Substrate after the development was 230 ℃ of following heat treated 60 minutes.The part of substrate flooded 30 minutes in N-Methyl pyrrolidone (NMP) after, use the state of observation by light microscope patterned surfaces.Confirm that the substrate not have to change is zero, confirm to have the △ that is in slight crack etc., confirm to have obvious crack etc. be *.The result is shown in the table 4.
Table 4
| The timeliness rate of change % of resist viscosity | Saturated residual film ratio % | Saturation exposure mJ/cm 2 | Pattern formation property | Solvent resistance | |||
| The live width precision | Section shape | ||||||
| Embodiment | 1 | 7.1 | 95 | 50 | ○ | ○ | ○ |
| 2 | 6.5 | 95 | 50 | ○ | ○ | ○ | |
| 3 | 14.0 | 95 | 50 | ○ | ○ | ○ | |
| 4 | 5.9 | 95 | 50 | ○ | ○ | ○ | |
| 5 | 14.4 | 95 | 50 | ○ | ○ | ○ | |
| 6 | 16.8 | 95 | 50 | ○ | ○ | ○ | |
| 7 | 6 | 90 | 80 | △ | ○ | ○ | |
| 8 | 4.9 | 90 | 80 | △ | ○ | △ | |
| 9 | 10.1 | 95 | 50 | ○ | ○ | ○ | |
| 10 | 9.4 | 95 | 50 | ○ | ○ | ○ | |
| 11 | 7.3 | 95 | 50 | ○ | ○ | ○ | |
| 12 | 6.6 | 95 | 50 | ○ | ○ | ○ | |
| 13 | 6.6 | 95 | 50 | ○ | ○ | ○ | |
| 14 | 12.4 | 95 | 50 | ○ | △ | ○ | |
| 15 | 7.4 | 90 | 80 | ○ | △ | △ | |
| 16 | 17.0 | 95 | 30 | △ | △ | ○ | |
| 17 | 6.6 | 95 | 50 | ○ | ○ | △ | |
| 18 | 7.6 | 100 | 30 | △ | ○ | △ | |
| 19 | 13.3 | 80 | 100 | △ | △ | ○ | |
| 20 | 6.6 | 95 | 50 | △ | △ | △ | |
| 21 | 0.7 | 95 | 50 | ○ | ○ | ○ | |
| 22 | 0.6 | 95 | 50 | ○ | ○ | ○ | |
| 23 | 6.6 | 95 | 50 | ○ | ○ | ○ | |
| 24 | 0.8 | 95 | 50 | ○ | ○ | ○ | |
| 25 | 5.1 | 95 | 50 | ○ | ○ | ○ | |
| 26 | 5.8 | 95 | 50 | ○ | ○ | ○ | |
| 27 | 5.5 | 95 | 50 | ○ | △ | ○ | |
| 28 | 6.6 | 95 | 50 | ○ | △ | ○ | |
| Comparative example | 1 | 4.3 | 80 | 180 | × | △ | × |
| 2 | 8.6 | 100 | 30 | × | × | ○ | |
| 3 | 7.5 | 80 | 150 | × | × | ○ | |
| 4 | 13.7 | 95 | 50 | ○ | ○ | × | |
| 5 | 22.9 | 95 | 50 | × | × | ○ | |
As shown in table 4, in photonasty transparent resin, non-photosensitive transparent resin, mixing ratio with each composition of polyfunctional monomer of 3 or more a plurality of ethylenical unsaturated double bonds is under inappropriate situation, particularly in functional group densities not under the situation in suitable scope, the sensitivity of coloured composition is insufficient, and pattern formation property is not good.On the other hand, the mixing ratio of each composition is under the suitable situation in coloured composition, and high sensitivityization forms property with good pattern and can have both.The dispersion stabilization of coloured composition and pattern form property and also are subjected to the photonasty transparent resin and the characteristic of non-photosensitive transparent resin and the influence of ratio that mix in the coloured composition greatly, in embodiment 21,22,24 etc., by using dispersed good photonasty transparent resin and non-photosensitive transparent resin, and the good photonasty transparent resin that balancedly mixes appropriate amount, thereby dispersion stabilization and good pattern formation property have been had both.In addition, by in coloured composition, mixing the photonasty transparent resin of appropriate amount, can obtain good redness of the unexistent solvent resistance of prior art or magenta or yellow filming.
Embodiment 29
The preparation of＜pigment dispersion 〉
After the potpourri of following composition mixed equably, use the zirconium oxide bead of diameter as 1mm, after disperseing 2 hours by Eiger mill (ア イ ガ-ミ Le) (" ミ ニ モ デ Le M-250 MKII " that ア イ ガ-ジ ヤ パ Application company makes), use the filtrator of 5 μ m to filter, be mixed with pigment dispersion.
Viridine green: C.I. pigment green 36 (" リ オ-Le グ リ-Application 6YK " that Toyo Ink manufacturing company makes): 7.1 parts
Yellow uitramarine: C.I. pigment yellow 150 (" E4GN-GT " that Bayer company makes): 3.9 parts
The azo class pigment derivative of following formula (4): 1.0 parts
Photonasty transparent resin 1 solution: 10.0 parts
Non-photosensitive transparent resin 1 solution: 30.0 parts
Cyclohexanone: 50.0 parts
The preparation of＜green coloring composition 〉
After the potpourri of following composition mixed, use the filtrator of 1 μ m to filter, obtain having photosensitive green coloring composition.
The pigment dispersion of above-mentioned preparation: 67.0 parts
Photonasty transparent resin 1 solution: 2.0 parts
Non-photosensitive transparent resin 1 solution: 3.0 parts
Dipentaerythritol acrylate: 4.0 parts
Photoepolymerizationinitiater initiater (" イ Le ガ キ ユ ア-907 " that チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes): 1.4 parts
Sensitizer (protecting " EAB-F " that native ケ paddy chemical company makes): 0.2 part
Cyclohexanone: 22.4 parts
Embodiment 30～55 and comparative example 6～10
Photonasty transparent resin solution shown in the mixture table 5, non-photosensitive transparent resin solution and polyfunctional monomer (with reference to table 2), making the ratio in the photosensitive polymer combination is the ratio shown in the table 5 (weight ratio of solid constituent), obtains having photosensitive green coloring composition similarly to Example 29 (green anticorrosive additive material).Photonasty transparent resin solution, non-photosensitive transparent resin solution are mixed with and make photonasty transparent resin and non-photosensitive transparent resin become the ratio shown in the table 5 with polyfunctional monomer.In the green coloring composition that 100 weight portions obtain, the shared toatl proportion of these 3 kinds of compositions is identical in embodiment 29～45 and comparative example 6～10.The same with table 3, in table 5, calculate content (weight %) ratio, the Cb/Ca of photonasty transparent resin, the density of functional group respectively, and the result is shown.(in addition, in comparative example 8, use two key equivalents of bifunctional monomer, the weight of bifunctional monomer to calculate the ethylenical unsaturated double bonds mole of polymerized concentration of green coloring composition.)
Table 5
| The photonasty transparent resin | The non-photosensitive transparent resin | Polyfunctional monomer | Weight ratio | The content of photonasty transparent resin (%) | Cb/Ca | Functional group densities (mol/g) | ||||
| The photonasty transparent resin | The non-photosensitive transparent resin | Polyfunctional monomer | ||||||||
| Embodiment | 29 | 1 | 1 | DPHA | 3 | 8 | 7 | 27.3 | 11.4 | 4.4E-03 |
| 30 | 2 | 1 | DPHA | 3 | 8 | 7 | 27.3 | 11.1 | 4.4E-03 | |
| 31 | 3 | 1 | DPHA | 3 | 8 | 7 | 27.3 | 6.5 | 4.7E-03 | |
| 32 | 4 | 1 | DPHA | 3 | 8 | 7 | 27.3 | 24.2 | 4.2E-03 | |
| 33 | 5 | 1 | DPHA | 3 | 8 | 7 | 27.3 | 11.4 | 4.4E-03 | |
| 34 | 6 | 1 | DPHA | 3 | 8 | 7 | 27.3 | 11.1 | 4.4E-03 | |
| 35 | 1 | 1 | DPHA | 4 | 8 | 3 | 33.3 | 3.7 | 2.6E-03 | |
| 36 | 1 | 1 | DPHA | 5 | 6 | 7 | 27.3 | 11.4 | 4.4E-03 | |
| 37 | 1 | 1 | TMPTA | 3 | 8 | 7 | 27.3 | 11.1 | 4.3E-03 | |
| 38 | 1 | 1 | PE4A | 3 | 8 | 7 | 27.3 | 12.5 | 4.8E-03 | |
| 39 | 1 | 1 | PE3AH | 3 | 8 | 7 | 27.3 | 8.6 | 3.4E-03 | |
| 40 | 1 | 1 | DPPAH | 3 | 8 | 7 | 27.3 | 9.0 | 3.6E-03 | |
| 41 | 1 | 1 | DPHA | 9 | 6 | 8 | 60.0 | 4.3 | 4.4E-03 | |
| 42 | 1 | 1 | DPHA | 1 | 6 | 4 | 14.3 | 19.5 | 4.0E-03 | |
| 43 | 1 | 1 | DPHA | 13 | 3 | 9 | 81.3 | 3.4 | 4.8E-03 | |
| 44 | 4 | 1 | DPHA | 3 | 8 | 8 | 27.3 | 27.7 | 4.5E-03 | |
| 45 | 4 | 1 | DPHA | 3 | 8 | 9 | 27.3 | 31.1 | 4.8E-03 | |
| 46 | 1 | 1 | DPHA | 11 | 6 | 4 | 64.7 | 1.8 | 3.1E-03 | |
| 47 | 4 | 1 | DPHA | 3 | 11 | 11 | 21.4 | 38.1 | 4.7E-03 | |
| 48 | 1 | 2 | DPHA | 3 | 8 | 7 | 27.3 | 11.4 | 4.4E-03 | |
| 49 | 2 | 2 | DPHA | 3 | 8 | 7 | 27.3 | 11.4 | 4.4E-03 | |
| 50 | 3 | 2 | DPHA | 3 | 8 | 7 | 27.3 | 6.5 | 4.7E-03 | |
| 51 | 2 | 3 | DPHA | 3 | 8 | 7 | 27.3 | 11.1 | 4.4E-03 | |
| 52 | 5 | 2 | DPHA | 3 | 8 | 7 | 27.3 | 11.4 | 4.4E-03 | |
| 53 | 6 | 3 | DPHA | 3 | 8 | 7 | 27.3 | 11.1 | 4.4E-03 | |
| 54 | 1 | 3 | DPHA | 3 | 8 | 7 | 27.3 | 11.4 | 4.4E-03 | |
| 55 | 4 | 2 | DPHA | 3 | 8 | 7 | 27.3 | 24.2 | 4.2E-03 | |
| Comparative example | 6 | 1 | 1 | DPHA | 4 | 15 | 4 | 21.1 | 4.9 | 2.2E-03 |
| 7 | 1 | 1 | DPHA | 5 | 6 | 9 | 45.5 | 8.8 | 5.2E-03 | |
| 8 | 1 | 1 | TPGDA | 3 | 8 | 18 | 27.3 | 18.8 | 4.4E-03 | |
| 9 | - | 1 | DPHA | 0 | 11 | 7 | 0.0 | - | 4.0E-03 | |
| 10 | 4 | - | DPHA | 11 | 0 | 7 | 100.0 | 6.6 | 4.6E-03 | |
With above-mentioned the same, the green coloring composition that obtains in embodiment 29～55 and the comparative example 6～10 is estimated viscosity stability, sensitivity, pattern formation property and solvent resistance.In result shown in the table 6.
Table 6
| The timeliness rate of change % of resist viscosity | Saturated residual film ratio % | Saturation exposure mJ/cm 2 | Pattern formation property | Solvent resistance | |||
| The live width precision | Section shape | ||||||
| Embodiment | 29 | 9.6 | 95 | 50 | ○ | ○ | ○ |
| 30 | 8.8 | 95 | 50 | ○ | ○ | ○ | |
| 31 | 18.5 | 95 | 50 | ○ | ○ | ○ | |
| 32 | 8.0 | 95 | 50 | ○ | ○ | ○ | |
| 33 | 19.1 | 95 | 50 | ○ | ○ | ○ | |
| 34 | 22.3 | 95 | 50 | ○ | ○ | ○ | |
| 35 | 8.1 | 90 | 80 | △ | ○ | ○ | |
| 36 | 13.4 | 95 | 50 | ○ | ○ | ○ | |
| 37 | 12.5 | 95 | 50 | ○ | ○ | ○ | |
| 38 | 9.8 | 95 | 50 | ○ | ○ | ○ | |
| 39 | 8.9 | 90 | 50 | ○ | ○ | ○ | |
| 40 | 8.9 | 95 | 50 | ○ | ○ | ○ | |
| 41 | 16.5 | 95 | 50 | ○ | △ | ○ | |
| 42 | 9.9 | 90 | 50 | ○ | △ | △ | |
| 43 | 22.3 | 100 | 30 | △ | △ | ○ | |
| 44 | 8.9 | 95 | 50 | ○ | ○ | △ | |
| 45 | 10.2 | 100 | 50 | △ | ○ | △ | |
| 46 | 17.7 | 80 | 80 | △ | △ | ○ | |
| 47 | 8.9 | ＞100 | 50 | △ | △ | △ | |
| 48 | 0.9 | 95 | 50 | ○ | ○ | ○ | |
| 49 | 0.8 | 95 | 50 | ○ | ○ | ○ | |
| 50 | 8.9 | 95 | 50 | ○ | ○ | ○ | |
| 51 | 1.0 | 95 | 50 | ○ | ○ | ○ | |
| 52 | 7.0 | 95 | 50 | ○ | ○ | ○ | |
| 53 | 7.9 | 95 | 50 | ○ | ○ | ○ | |
| 54 | 7.5 | 95 | 50 | ○ | △ | ○ | |
| 55 | 8.9 | 95 | 50 | ○ | △ | ○ | |
| Comparative example | 6 | 5.9 | 80 | 200 | × | △ | × |
| 7 | 11.5 | 100 | 30 | × | × | ○ | |
| 8 | 10.1 | 90 | 150 | × | × | ○ | |
| 9 | 18.2 | 95 | 50 | ○ | ○ | × | |
| 10 | 30.5 | 100 | 50 | × | × | ○ | |
As shown in table 6, in photonasty transparent resin, non-photosensitive transparent resin, mixing ratio with each composition of polyfunctional monomer of 3 or more a plurality of ethylenical unsaturated double bonds is under inappropriate situation, particularly in functional group densities not under the situation in suitable scope, the sensitivity of green coloring composition is insufficient, and pattern formation property is not good.On the other hand, the mixing ratio of each composition in green coloring composition is under the suitable situation, and high sensitivityization forms property with good pattern and can have both.The dispersion stabilization of green coloring composition and pattern form property and also are subjected to the photonasty transparent resin and the characteristic of non-photosensitive transparent resin and the influence of ratio that mix in the coloured composition greatly, in embodiment 48,49,51 etc., by using dispersed good photonasty transparent resin and non-photosensitive transparent resin, and the good photonasty transparent resin that balancedly mixes appropriate amount, thereby dispersion stabilization and good pattern formation property have been had both.In addition, by in green coloring composition, mixing the photonasty transparent resin of appropriate amount, can obtain the good green coating of the unexistent solvent resistance of prior art.
Embodiment 56
The preparation of＜pigment dispersion 〉
After the potpourri of following composition mixed equably, use the zirconium oxide bead of diameter as 1mm, after disperseing 2 hours by Eiger mill (ア イ ガ-ミ Le) (" ミ ニ モ デ Le M-250 MKII " that ア イ ガ-ジ ヤ パ シ company makes), use the filtrator of 5 μ m to filter, be mixed with pigment dispersion.
Epsilon-copper phthalocyanine (C.I. pigment blue 15: 6) (" ヘ リ オ ゲ Application Block Le-L-6700F " that BASF makes): 11.0 parts
Phthalocyanine pigment derivant (following formula (5)): 1.0 parts
Cu-pc: copper phthalocyanine residue
Photonasty transparent resin 1 solution: 9.9 parts
Non-photosensitive transparent resin 2 solution: 30.1 parts
Cyclohexanone: 48.0 parts
The preparation of＜blue colored composition 〉
After the potpourri of following composition mixed, use the filtrator of 1 μ m to filter, obtain having photosensitive blue colored composition.
The pigment dispersion of above-mentioned preparation: 45.0 parts
Photonasty transparent resin 1 solution: 15.9 parts
Dipentaerythritol acrylate: 5.4 parts
Photoepolymerizationinitiater initiater (" イ Le ガ キ ユ ア-907 " that チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes): 2.0 parts
Sensitizer (protecting " EAB-F " that native ケ paddy chemical company makes): 0.2 part
Cyclohexanone: 31.5 parts
Embodiment 57～83 and comparative example 11～15
Photonasty transparent resin solution shown in the table 7, non-photosensitive transparent resin solution and polyfunctional monomer (with reference to table 2) are mixed according to the ratio shown in the table 7 (weight ratio of solid constituent), similarly obtain having photosensitive blue colored composition (blue anticorrosive additive material) with embodiment 57.Photonasty transparent resin solution, non-photosensitive transparent resin solution are mixed with and make photonasty transparent resin and non-photosensitive transparent resin become the ratio shown in the table 5 with polyfunctional monomer.In the blue colored composition that 100 weight portions obtain, the shared toatl proportion of these 3 kinds of compositions is identical in embodiment 56～83 and comparative example 11～15.The same with table 3, in table 7, calculate content (weight %) ratio, the Cb/Ca of photonasty transparent resin, the density of functional group respectively, and the result is shown.(in addition, in comparative example 13, use two key equivalents of bifunctional monomer, the weight of bifunctional monomer to calculate the ethylenical unsaturated double bonds mole of polymerized concentration of blue colored composition.)
Table 7
| The photonasty transparent resin | The non-photosensitive transparent resin | Polyfunctional monomer | Weight ratio | The content of photonasty transparent resin (%) | Cb/Ca | Functional group densities (mol/g) | ||||
| The photonasty transparent resin | The non-photosensitive transparent resin | Polyfunctional monomer | ||||||||
| Embodiment | 56 | 1 | 1 | DPHA | 6 | 4 | 8 | 60.0 | 5.5 | 5.3E-03 |
| 57 | 2 | 1 | DPHA | 6 | 4 | 8 | 60.0 | 6.4 | 5.3E-03 | |
| 58 | 3 | 1 | DPHA | 6 | 4 | 11 | 60.0 | 5.1 | 6.5E-03 | |
| 59 | 4 | 1 | DPHA | 6 | 4 | 8 | 60.0 | 13.8 | 4.9E-03 | |
| 60 | 5 | 1 | DPHA | 6 | 4 | 8 | 60.0 | 6.5 | 5.3E-03 | |
| 61 | 6 | 1 | DPHA | 6 | 4 | 8 | 60.0 | 6.4 | 5.3E-03 | |
| 62 | 1 | 1 | DPHA | 6 | 3 | 9 | 66.7 | 7.3 | 5.9E-03 | |
| 63 | 1 | 1 | DPHA | 6 | 5 | 15 | 54.5 | 12.2 | 6.5E-03 | |
| 64 | 1 | 1 | DPHA | 5 | 8 | 6 | 38.5 | 5.9 | 3.8E-03 | |
| 65 | 1 | 1 | TMPTA | 6 | 4 | 8 | 60.0 | 6.4 | 5.2E-03 | |
| 66 | 1 | 1 | PE4A | 6 | 4 | 8 | 60.0 | 7.1 | 5.8E-03 | |
| 67 | 1 | 1 | PE3AH | 6 | 4 | 9 | 60.0 | 5.5 | 4.4E-03 | |
| 68 | 1 | 1 | DPPAH | 6 | 4 | 8 | 60.0 | 5.2 | 4.4E-03 | |
| 69 | 1 | 1 | DPHA | 4 | 6 | 8 | 40.0 | 9.8 | 5.1E-03 | |
| 70 | 1 | 1 | DPHA | 1 | 6 | 4 | 14.3 | 19.5 | 4.0E-03 | |
| 71 | 1 | 1 | DPHA | 8 | 1 | 9 | 88.9 | 5.5 | 6.1E-03 | |
| 72 | 1 | 1 | DPHA | 2 | 3 | 8 | 40.0 | 19.5 | 6.7E-03 | |
| 73 | 1 | 1 | DPHA | 6 | 4 | 5 | 60.0 | 4.1 | 4.3E-03 | |
| 74 | 1 | 1 | DPHA | 10 | 4 | 4 | 71.4 | 2.0 | 3.5E-03 | |
| 75 | 1 | 1 | DPHA | 1 | 4 | 8 | 20.0 | 39.0 | 6.6E-03 | |
| 76 | 1 | 2 | DPHA | 6 | 4 | 8 | 60.0 | 6.5 | 5.3E-03 | |
| 77 | 2 | 2 | DPHA | 6 | 4 | 8 | 60.0 | 6.4 | 5.3E-03 | |
| 78 | 3 | 2 | DPHA | 3 | 3 | 6 | 50.0 | 5.6 | 6.1E-03 | |
| 79 | 2 | 3 | DPHA | 6 | 4 | 8 | 60.0 | 6.4 | 5.3E-03 | |
| 80 | 5 | 2 | DPHA | 6 | 4 | 8 | 60.0 | 6.5 | 5.3E-03 | |
| 81 | 6 | 3 | DPHA | 6 | 4 | 8 | 60.0 | 6.4 | 5.3E-03 | |
| 82 | 1 | 3 | DPHA | 6 | 4 | 8 | 60.0 | 6.5 | 5.3E-03 | |
| 83 | 4 | 2 | DPHA | 6 | 4 | 8 | 60.0 | 13.8 | 4.9E-03 | |
| Comparative example | 11 | 1 | 1 | DPHA | 5 | 14 | 6 | 26.3 | 5.9 | 2.9E-03 |
| 12 | 1 | 1 | DPHA | 5 | 2 | 13 | 71.4 | 12.7 | 7.3E-03 | |
| l3 | 1 | 1 | TPGDA | 6 | 4 | 10 | 60.0 | 5.2 | 4.0E-03 | |
| 14 | - | 1 | DPHA | 0 | 6 | 7 | 0.0 | - | 5.6E-03 | |
| 15 | 1 | - | DPHA | 6 | 0 | 7 | 100.0 | 5.7 | 6.6E-03 | |
With above-mentioned the same, the blue colored composition that obtains in embodiment 56～83 and the comparative example 11～15 is estimated viscosity stability, sensitivity, pattern formation property and solvent resistance.In result shown in the table 8.
Table 8
| The timeliness rate of change % of resist viscosity | Saturated residual film ratio % | Saturation exposure mJ/cm 2 | Pattern formation property | Solvent resistance | |||
| The live width precision | Section shape | ||||||
| Embodiment | 56 | 9.1 | 95 | 50 | ○ | ○ | ○ |
| 57 | 8.5 | 95 | 50 | ○ | ○ | ○ | |
| 58 | 19.0 | 98 | 30 | △ | ○ | ○ | |
| 59 | 7.9 | 95 | 50 | ○ | ○ | ○ | |
| 60 | 16.4 | 95 | 50 | ○ | ○ | ○ | |
| 61 | 18.8 | 95 | 50 | ○ | ○ | ○ | |
| 62 | 10.2 | 95 | 50 | ○ | △ | ○ | |
| 63 | 17.2 | 98 | 30 | △ | ○ | ○ | |
| 64 | 8.0 | 90 | 80 | △ | ○ | △ | |
| 65 | 12.4 | 95 | 50 | ○ | ○ | ○ | |
| 66 | 10.3 | 95 | 50 | ○ | ○ | ○ | |
| 67 | 9.6 | 95 | 50 | ○ | ○ | ○ | |
| 68 | 9.6 | 95 | 50 | ○ | ○ | ○ | |
| 69 | 10.4 | 95 | 50 | ○ | ○ | △ | |
| 70 | 9.4 | 90 | 100 | △ | ○ | △ | |
| 71 | 19.0 | 100 | 50 | △ | △ | ○ | |
| 72 | 66.9 | 100 | 30 | △ | ○ | △ | |
| 73 | 4.8 | 95 | 80 | △ | △ | ○ | |
| 74 | 6.3 | 70 | 150 | △ | △ | ○ | |
| 75 | 46.1 | ＞100 | 30 | △ | △ | △ | |
| 76 | 0.5 | 95 | 50 | ○ | ○ | ○ | |
| 77 | 0.3 | 95 | 50 | ○ | ○ | ○ | |
| 78 | 8.6 | 95 | 50 | ○ | ○ | ○ | |
| 79 | 1.2 | 95 | 50 | ○ | ○ | ○ | |
| 80 | 7.1 | 95 | 50 | ○ | ○ | ○ | |
| 81 | 7.8 | 95 | 50 | ○ | ○ | ○ | |
| 82 | 7.5 | 95 | 50 | ○ | △ | ○ | |
| 83 | 8.6 | 95 | 50 | ○ | △ | ○ | |
| Comparative example | 11 | 8.3 | 70 | 200 | × | △ | ○ |
| l2 | 102 | ＞100 | 30 | × | × | ○ | |
| 13 | 102 | 70 | 150 | × | × | ○ | |
| 14 | 16.7 | 95 | 50 | ○ | ○ | × | |
| 15 | 28.9 | 100 | 30 | × | × | ○ | |
As shown in table 8, in photonasty transparent resin, non-photosensitive transparent resin, mixing ratio with each composition of polyfunctional monomer of 3 or more a plurality of ethylenical unsaturated double bonds is under inappropriate situation, particularly in functional group densities not under the situation in OK range, the sensitivity of blue colored composition is insufficient, and pattern formation property is not good.On the other hand, the mixing ratio of each composition in blue colored composition is under the suitable situation, and high sensitivityization forms property with good pattern and can have both.The dispersion stabilization of blue colored composition and pattern form property and also are subjected to the photonasty transparent resin and the characteristic of non-photosensitive transparent resin and the influence of ratio that mix in the coloured composition greatly, in embodiment 76,77,79 etc., by using dispersed good photonasty transparent resin and non-photosensitive transparent resin, and the good photonasty transparent resin that balancedly mixes appropriate amount, thereby dispersion stabilization and good pattern formation property have been had both.In addition, by in blue colored composition, mixing the photonasty transparent resin of appropriate amount, can obtain the good blueness of the unexistent solvent resistance of prior art and film.
Claims (13)
1, color composition for color filter, said composition contains photonasty transparent resin, non-photosensitive transparent resin, have the polyfunctional monomer and the coloured material of 3 or more a plurality of ethylenical unsaturated double bonds, wherein, general assembly (TW) with described photonasty transparent resin, described non-photosensitive transparent resin and described polyfunctional monomer is a benchmark, and the weight-molality of the ethylenical unsaturated double bonds in this coloured composition is 1.0 * 10
-3Mol/g～7.0 * 10
-3Mol/g.
2, color composition for color filter according to claim 1, wherein, two key equivalents of described photonasty transparent resin are 200～1200.
3, color composition for color filter according to claim 1 wherein, is a benchmark with the general assembly (TW) of described photonasty transparent resin and described non-photosensitive transparent resin, and the content of described photonasty transparent resin is 15～80 weight %.
4, color composition for color filter according to claim 1, wherein, described photonasty transparent resin or described non-photosensitive transparent resin contain the ethylenically unsaturated monomer (a) shown in the following formula (1) as copolymer composition,
In formula (1), R
1Expression hydrogen atom or methyl, R
2The expression carbon number is 2～10 alkylidene, R
3The carbon number that the expression hydrogen atom maybe can contain phenyl ring is 1～20 alkyl, and n represents 1～15 integer.
5, color composition for color filter according to claim 1, wherein, the acid number of described photonasty transparent resin is lower than the acid number of described non-photosensitive transparent resin.
6, color composition for color filter according to claim 1, wherein, general assembly (TW) with described photonasty transparent resin, described non-photosensitive transparent resin and described polyfunctional monomer is a benchmark, and the weight-molality of the ethylenical unsaturated double bonds of described polyfunctional monomer is molal 2～35 times of ethylenical unsaturated double bonds of described photonasty transparent resin.
7, according to each described color composition for color filter in the claim 1～6, wherein, described coloured material is redness, magenta or yellow, general assembly (TW) with described photonasty transparent resin, described non-photosensitive transparent resin and described polyfunctional monomer is a benchmark, and the weight-molality of the ethylenical unsaturated double bonds in this coloured composition is 1.0 * 10
-3Mol/g～4.0 * 10
-3Mol/g.
8, according to each described color composition for color filter in the claim 1～6, wherein, described coloured material is green, general assembly (TW) with described photonasty transparent resin, described non-photosensitive transparent resin and described polyfunctional monomer is a benchmark, and the weight-molality of the ethylenical unsaturated double bonds in this coloured composition is 2.5 * 10
-3Mol/g～5.0 * 10
-3Mol/g.
9, according to each described color composition for color filter in the claim 1～6, wherein, described coloured material is blue, general assembly (TW) with described photonasty transparent resin, described non-photosensitive transparent resin and described polyfunctional monomer is a benchmark, and the weight-molality of the ethylenical unsaturated double bonds in this coloured composition is 3.0 * 10
-3Mol/g～7.0 * 10
-3Mol/g.
10, color filter, it has the color filter joint that is formed by the described color composition for color filter of claim 1.
11, color filter, it has the color filter joint that is formed by the described color composition for color filter of claim 7.
12, color filter, it has the color filter joint that is formed by the described color composition for color filter of claim 8.
13, color filter, it has the color filter joint that is formed by the described color composition for color filter of claim 9.
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| JP2004372974 | 2004-12-24 | ||
| JP372974/2004 | 2004-12-24 | ||
| JP030352/2005 | 2005-02-07 | ||
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| JP030353/2005 | 2005-02-07 |
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| CN100543585C CN100543585C (en) | 2009-09-23 |
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| CN101563632B (en) * | 2006-12-19 | 2011-03-30 | 凸版印刷株式会社 | Color filter evaluation method, color filter, and liquid crystal display device |
| CN101743514B (en) * | 2007-07-20 | 2013-09-11 | 东洋油墨制造株式会社 | Color composition and color filter using the same |
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| CN101563632B (en) * | 2006-12-19 | 2011-03-30 | 凸版印刷株式会社 | Color filter evaluation method, color filter, and liquid crystal display device |
| CN101743514B (en) * | 2007-07-20 | 2013-09-11 | 东洋油墨制造株式会社 | Color composition and color filter using the same |
| CN105278242A (en) * | 2014-07-15 | 2016-01-27 | 东京应化工业株式会社 | Sensitive composition |
| CN108139666A (en) * | 2015-09-29 | 2018-06-08 | 默克专利有限公司 | Photosensitive composition and color conversion coatings film |
| US11269255B2 (en) | 2015-09-29 | 2022-03-08 | Merck Patent Gmbh | Photosensitive composition and color converting film |
| CN107015435A (en) * | 2015-11-05 | 2017-08-04 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter and manufacturing method and application thereof |
| CN107015435B (en) * | 2015-11-05 | 2019-12-13 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter and manufacturing method and application thereof |
| CN108333872A (en) * | 2017-01-19 | 2018-07-27 | 东友精细化工有限公司 | Green pixel photosensitive composition, colour filter and its application |
| CN108333872B (en) * | 2017-01-19 | 2021-06-29 | 东友精细化工有限公司 | Colored photosensitive resin composition for green pixel, color filter and application thereof |
| CN114736550A (en) * | 2022-04-11 | 2022-07-12 | Tcl华星光电技术有限公司 | Composition, COA display panel, liquid crystal display device and display panel preparation method |
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| CN100543585C (en) | 2009-09-23 |
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