CN101852989A

CN101852989A - Photosensitive coloring composition, color filter and autofrettage thereof and liquid crystal indicator

Info

Publication number: CN101852989A
Application number: CN201010144853A
Authority: CN
Inventors: 吉野晴彦
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2009-03-31
Filing date: 2010-03-29
Publication date: 2010-10-06
Also published as: JP2010256887A

Abstract

The invention provides a kind of be used for going up at patterning thing (for example, resin black matrix) form when having the colored pattern of overlapping portion, can reduce the photosensitive coloring composition of projection of the colored pattern of this overlapping portion.Above-mentioned photosensitive coloring composition contains colorant, polymerizable compound, bonding agent and solvent, and to be concentrated into solid component concentration be that viscosity behind the 70 quality % is below the 50Pas in the time of 25 ℃.

Description

Photosensitive coloring composition, color filter and autofrettage thereof and liquid crystal indicator

Technical field

The present invention relates to photosensitive coloring composition, color filter (color filter) and manufacture method and liquid crystal indicator.

Background technology

Color filter is that liquid crystal indicator or solid are scooped up indispensable component parts in the pixel spare.

For example, about liquid crystal indicator (LCD; LCD (Liquid CrystalDisplay)) uses color filter, along with liquid crystal display applications in TV (television) purposes, compare with the present notebook computer (notebook computer) or the color filter of monitor (monitor) purposes, require to have more high-quality image quality.In addition, the substrate size that is used to produce large-scale TV becomes big, and ratio defective product is improved and the increase in demand of cost cutting.

Raising about above-mentioned image quality, when making color filter, there is following problem: in boundary member (overlapping part) the colored pattern projection of black matrix (black matrix) with colored pixels, the uneven image quality reduction (for example with reference to Japanese kokai publication hei 9-113721 communique) that causes thereby color filter becomes.The projection of above-mentioned boundary member causes problems such as contrast (contrast) decline, irregular colour sometimes.

For this reason, in the past, made the back in pixel the surface of color filter was ground, or dealt with forming finishing coat (overcoat) (below be sometimes referred to as " OC layer ") on the pixel.But if grind or form the OC layer, then the manufacturing process of color filter increases, and cost improves.In addition, when grinding, also can produce drawbacks such as color filter is impaired sometimes, wish to have and to omit the method that grinding step and OC layer form operation.

Be directed to this, attempted solving the problem (for example with reference to Japanese kokai publication hei 9-113721 communique and TOHKEMY 2003-161826 communique) of the projection of above-mentioned boundary member by the cone angle (taper angle) that reduces black matrix.

In TOHKEMY 2003-161826 communique, also only in black matrix frame, give coloured composition by ink-jet method.

But,, then, need a large amount of operations in order to obtain having the black matrix of above-mentioned cone angle if adopt the method described in the Japanese kokai publication hei 9-113721 communique.Promptly, to deceive matrix forms with the dark composition of photonasty after coating drying on the substrate, be coated with eurymeric resist (positive-working resist) again, regulate the developing powder of dark composition of this photonasty and eurymeric resist, this is the method that wastes time and energy.And when only regulating cone angle, the effect that suppresses the colored pattern projection is insufficient.In addition, this technology is not at large substrate (for example substrate size is the above large substrate of 1m * 1m).

On the other hand, in TOHKEMY 2003-161826 communique, because giving coloured composition by ink-jet method on substrate forms colored pattern, therefore be unsuitable for suppressing the projection of the colored pattern that following overlapping (overlap) locate, described overlapping black matrix and the equitant overlapping portion of colored pattern that waits when forming colored pattern to be produced for coating, the transfer printing that utilizes coloured composition.Also can be described as the boundary member in black matrix and colored pixels, black matrix is higher than colored pixels and to produce ladder poor, thereby causes the color filter unevenness, produces the problem of same image quality reduction sometimes.

Summary of the invention

The present invention In view of the foregoing finishes, and its technical matters is to finish following purpose.

That is,, provide a kind of photosensitive coloring composition, when it has the colored pattern of overlapping portion on being applied to be formed on patterning thing (for example, resin black matrix), can reduce the projection of the colored pattern of this overlapping portion according to the 1st scheme of the present invention.

In addition, according to the 2nd scheme of the present invention, a kind of manufacture method of color filter is provided, this method can grind or be provided with under the situation of operations such as finishing coat not appending, and has reduced color filter in the colored pattern projection of the overlapping portion of resin black matrix and colored pattern with low-cost and simple method manufacturing.

In addition, according to the 3rd scheme of the present invention, provide a kind of color filter, it has reduced the projection at the colored pattern of the overlapping portion of resin black matrix and colored pattern, and can suppress orientation confusion, the raising contrast of liquid crystal when being applied to liquid crystal indicator.

In addition, according to the 4th scheme of the present invention, provide a kind of liquid crystal indicator with high-contrast.

The result that the inventor concentrates on studies draws following opinion: the viscosity of specific solid state constituent concentration that makes photosensitive coloring composition can address the above problem when specific value is following, according to this opinion, has finished the present invention.

Concrete scheme of the present invention is as described below.

＜1〉a kind of photosensitive coloring composition, it contains colorant, polymerizable compound, bonding agent and solvent, and to be concentrated into solid component concentration be that viscosity behind the 70 quality % is below the 50Pas in the time of 25 ℃.

＜2〉according to＜1〉described photosensitive coloring composition, wherein, described colorant is by the covered pigment of macromolecular compound.

＜3〉according to＜2〉described photosensitive coloring composition, wherein, described pigment is red pigment, and described macromolecular compound is the polymkeric substance that contains following polymerized unit, and described polymerized unit is from the monomer shown in the following general formula (1).

In the described general formula (1), R ¹Expression hydrogen atom or replacement or unsubstituted alkyl; R ²Expression singly-bound or divalent link group; Y represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; Z represents to have the group of nitrogen heterocyclic ring structure.

＜4〉according to＜3〉described photosensitive coloring composition, wherein, in the described general formula (1), R ¹Shown alkyl is that carbon number is 1～12 alkyl, R ²Shown divalent links group for replacing or unsubstituted alkylidene; The carbon number of the nitrogen heterocyclic ring structure shown in the Z is 6～12.

＜5〉according to＜3〉described photosensitive coloring composition, wherein, the nitrogen heterocyclic ring structure shown in the Z is phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure or cyclic imide structure.

＜6〉a kind of manufacture method of color filter comprises:

Resin black matrix forms operation, forms resin black matrix on substrate;

Colored pattern forms operation, be formed with coating＜1 on the substrate of described resin black matrix〉described photosensitive coloring composition formation dyed layer, the formed dyed layer of prebake conditions, dyed layer after the prebake conditions is carried out pattern exposure, dyed layer behind the pattern exposure is being developed, and formation has the colored pattern that is overlapped in the overlapping portion on the described resin black matrix.

＜7〉manufacture method of basis＜6〉described color filter, wherein, between described coating and the described prebake conditions, the dyed layer that has forming by described coating carries out vacuum drying operation.

＜8〉manufacture method of basis＜6〉described color filter, wherein, described colored pattern forms operation and also has the operation of the described colored pattern that forms being carried out the back baking.

＜9〉manufacture method of basis＜8〉described color filter, wherein, the film slip of the caused colored pattern of described back baking is below 25%.

＜10〉according to＜6〉described color filter manufacture method, wherein, be parallel to Width and perpendicular to the cut surface after the described resin black matrix of the plane cutting of real estate in,

The shape of the end of described resin black matrix is the taper of thickness from the distolateral attenuation gradually of the described resin black matrix of described resin black matrix central portion side direction,

Be t at maximum film thickness with described resin black matrix, when being L with the length on the direction that is parallel to substrate surface of described end, ratio (L/t) is below 3.0.

＜11〉by＜6 〉～color filter that＜10〉described color filter manufacture method makes.

＜12〉according to＜11〉described color filter, wherein, on described colored pattern, has the transparent electrode layer that joins with described colored pattern.

＜13〉according to＜11〉described color filter, wherein, when observing the surface with 500 times multiplying powers, the radical of striated damage is 3/cm ²Below.

＜14〉a kind ofly have＜11〉described color filter liquid crystal indicator.

According to the 1st scheme of the present invention, a kind of photosensitive coloring composition is provided, it is being applied to when upward formation has the colored pattern of overlapping portion, can to reduce the projection of the colored pattern of this overlapping portion at patterning thing (for example, resin black matrix).

Description of drawings

Fig. 1 is the sectional view of the projection of illustration colored pattern.

Fig. 2 is the figure of section shape of the end of illustration resin black matrix.

Fig. 3 is the sectional view of the resin black matrix after the approximate rectangular development of illustration.

Fig. 4 is the sectional view of the resin black matrix after the development of illustration undercutting (undercut) shape.

Fig. 5 is the sectional view of the resin black matrix after the development of illustration taper.

Fig. 6 is the sectional view of the resin black matrix after baking (post baking) is handled after the illustration.

Fig. 7 is having the sectional view that has formed colored pattern on the substrate of resin black matrix after the baking processing after the illustration.

Embodiment

Below, photosensitive coloring composition of the present invention, the dark composition of photonasty of suitable formation resin black matrix of the present invention, color filter of the present invention and manufacture method thereof and liquid crystal indicator of the present invention are described.

Photosensitive coloring composition

Photosensitive coloring composition of the present invention contains colorant, polymerizable compound, bonding agent and solvent, and to be concentrated into solid component concentration be that viscosity behind the 70 quality % is below the 50Pas in the time of 25 ℃.

By making photosensitive coloring composition adopt the formation of the invention described above, can carry out keeping flowability to a certain degree in the dry process at dyed layer that forms using photosensitive coloring composition or colored pattern.

Therefore, according to the present invention, be applied to when the last formation of patterning thing (for example resin black matrix) has the colored pattern of overlapping portion, can to reduce the projection of the colored pattern of this overlapping portion.

Below, with reference to Fig. 1 the example of the projection of colored pattern is described.

As shown in Figure 1, on the substrate 2 that is formed with resin black matrix 4, when being formed on the colored pattern 6 that has overlapping O on the resin black matrix 4, colored pattern 6 produces the projection of height h at overlapping O.

At this, the height h of described projection is the surface of the colored pattern 6 in the zone (pixel region) that never forms resin black matrix 4 height to the surperficial middle distance substrate part farthest of the colored pattern 6 of overlapping O.

The formation of colored pattern 6 can be carried out in the following manner: the coating photosensitive coloring composition forms dyed layer on the substrate 2 that is formed with resin black matrix 4, the formed dyed layer of prebake conditions, and with the exposure of the dyed layer after the prebake conditions, development.At this moment, dyed layer (before the coating post-exposure) is utilizing prebake conditions to carry out in the dry process, and the concentration of solid state component raises.

At this, the photosensitive coloring composition of the application of the invention can keep flowability to a certain degree as photosensitive coloring composition in dry run, therefore, can reduce the height of projection h of colored pattern.

More than, the example of colored pattern projection is illustrated during to formation colored pattern on the substrate that is formed with resin black matrix 4, but unquestionable, even on the substrate that has formed resin black matrix 4 patterning thing in addition, form under the situation of colored pattern, also can obtain same effect.

Below, in instructions, the height h with described colored pattern projection is called " height of angle (Hom) " for convenience.From the viewpoint that contrast when the liquid crystal indicator improves, the height at angle is preferably below the 0.5 μ m.More preferably below the 0.4 μ m, be preferably especially below the 0.25 μ m.

Owing to can reduce the angle height when using photosensitive coloring composition of the present invention to form colored pattern, therefore can be easily with the angle height control in above-mentioned preferred range.

In the present invention, viscosity when to be concentrated into solid component concentration be behind the 70 quality % 25 ℃ with photosensitive coloring composition (below, be also referred to as " solid-state component 70% viscosity (25 ℃) ") be to make the typical curve that concerns between demonstration solid component concentration and the viscosity, the value of trying to achieve again according to the typical curve of gained by solid component concentration and the viscosity of measuring photosensitive coloring composition.

Below, describe the method that solid state component is 70% viscosity (25 ℃) of trying to achieve in detail.

Solid component concentration is measured

At first, reclaim the photosensitive coloring composition face before the coating,, measure dry mass (as quality 2) with vacuum drying oven at room temperature dry 3 hours with spoon.

Reclaim the photosensitive coloring composition (with the composition of the photosensitive coloring composition equal volume that is used to measure described dry mass) that faces before the coating separately with spoon, quality measurement when heating (quality X) with hot plate, take out in the time of near the solid component concentration shown in the following formula 1 (quality %) becomes 60 quality %, as sample 1.For the sample 1 that takes out, measure quality X accurately once more, obtain solid component concentration (quality %) accurately according to following formula 1.

Reclaim the photosensitive coloring composition (with the photosensitive coloring composition equal volume that is used to measure described dry mass) that faces before being coated with separately with spoon, quality measurement when heating (quality X) with hot plate, take out in the time of near solid component concentration becomes 70 quality %, as sample 2.For the sample 2 that takes out, measure quality X accurately once more, obtain solid component concentration (quality %) accurately according to following formula 1.

Reclaim the photosensitive coloring composition (with the photosensitive coloring composition equal volume that is used to measure described dry mass) that faces before being coated with separately with spoon, quality measurement when heating (quality X) with hot plate, when becoming 80 quality %, takes out solid component concentration, as sample 3.To the sample 3 that takes out, measure quality X accurately once more, obtain solid component concentration (quality %) accurately according to following formula 1.

Solid component concentration (quality %)=(quality 2/ quality X) * 100 ... formula 1

Viscosimetric analysis

For sample 1, sample 2 and the sample 3 of above-mentioned taking-up, use the determination of viscoelasticity device STRESSTECH of REOLOGICA Instruments AB system respectively, under the condition of 25 ℃ of specimen temperatures, frequency 1Hz, measure viscosity.

Illustrated that after taking out from hot plate 0.5 hour of being determined at of above viscosity is carried out with interior.

According to the solid component concentration and the viscosity of the sample 1 that obtains in the above described manner, sample 2 and sample 3, make the typical curve that concerns between demonstration solid component concentration and the viscosity.According to the typical curve that is made, obtain and be concentrated into solid component concentration the viscosity (solid state component 70% viscosity (25 ℃)) when being behind the 70 quality % 25 ℃.

From the viewpoint of the described angle of further reduction height, solid state component 70% viscosity (25 ℃) of photosensitive coloring composition of the present invention is preferably below the 50Pas, more preferably 40Pas.There is no particular limitation for the lower limit of solid state component 70% viscosity (25 ℃), from reducing the viewpoint of crawling, is preferably 30Pas.

In addition, the solid state component amount of facing coating preceding (being coated with in preceding 1 hour) of photosensitive coloring composition of the present invention, the viewpoint from coating expansion bullet good, when suppressing coating is spattered is preferably 70～95 quality %, more preferably 80～90 quality %.

In addition, photosensitive coloring composition of the present invention face the viscosity (25 ℃) of (being coated with in preceding 1 hour) before the coating, from the viewpoint of coating, be preferably 2.0mPas above, below the 4.0mPas, more preferably 2.5mPas above, below the 3.5mPas.

Photosensitive coloring composition of the present invention be radiation sensitive compositions (for example, under the situation of eurymeric (negative-working) radiation sensitive compositions, be the radiation sensitive compositions that under the effect of light, solidifies), preferably contain colorant, alkali soluble resin, polymerizable compound, Photoepolymerizationinitiater initiater and solvent, also can also contain other adjuvant such as macromolecule dispersing agent or surfactant.

Below, each composition is described.

Colorant

Colorant can suitably be selected from dyestuff and pigment.The pigment that uses as colorant can be inorganic pigment, also can be organic pigment, and from the viewpoint of high-transmission rate, the preferred particle size is as much as possible little.The average particle size of pigment is preferably 10nm～100nm, more preferably the scope of 10nm～50nm.

And then, for color filter of the present invention, in the pigment that in photosensitive coloring composition, contains, the ratio of the pigment of preferred primary particle size less than 0.02 μ m, insufficient total amount 10% with respect to this pigment, and primary particle size surpasses the ratio of the pigment of 0.08 μ m, with respect to the insufficient total amount 5% of this pigment.

For being used for photosensitive coloring composition of the present invention, described later by using by the covered pigment of macromolecular compound (macromolecule dispersing agent), even under the little situation of pigment size, pigment-dispersing, dispersion stabilization are also good, even thereby can form the also good colored pixels of thickness attenuation excitation.

The ratio of pigment

For color filter of the present invention, in the pigment that contains in the photosensitive coloring composition, the ratio of the pigment of preferred primary particle size less than 0.02 μ m, insufficient total amount 10% with respect to this pigment, and primary particle size surpasses the ratio of the pigment of 0.08 μ m, with respect to the insufficient total amount 5% of this pigment.

The ratio less than 10% of the pigment by making primary particle size less than 0.02 μ m can improve thermotolerance and prevent that colourity from changing.By making primary particle size surpass the ratio less than 5% of the pigment of 0.08 μ m, can make the exhibiting excellent stability with time of excellent contrast, photosensitive coloring composition, also can prevent the foreign matter obstacle.

The ratio of the pigment of primary particle size less than 0.02 μ m from thermotolerance and prevent the viewpoint that colourity changes, is preferably less than 5%.

Primary particle size surpasses the ratio of the pigment of 0.08 μ m, from making the viewpoint of excellent contrast, is preferably less than 3%.

The primary particle size of pigment can use TEM (transmission electron microscope) to measure.That is, by graphical analysis TEM photo, the examination size distribution is carried out.For example, the population of the pigment by being determined at all particles number in the observation sample under 30,000 times～100,000 times, less than 0.02 μ m and the population that surpasses the pigment of 0.08 μ m can be grasped size-grade distribution.

About the ratio of the primary particle of less than 0.02 μ m in the primary particle size and the ratio that surpasses the primary particle of 0.08 μ m, can observe the pigment powder with transmission electron microscope, measure the major diameter of each primary particle, and calculate the ratio (number %) of particle of pigment of less than 0.02 μ m respectively and the ratio (number %) of particle that surpasses the pigment of 0.08 μ m obtains.More specifically, observe down the pigment powders and take pictures at 3～100,000 times, measure the major diameter of 1000 primary particles, and calculate less than 0.02 μ m and surpass the ratio of primary particle of the pigment of 0.08 μ m with transmission electron microscope.Change the position of pigment powder, carry out aforesaid operations 3 positions altogether, the result is averaged.

As can be used as the inorganic pigment that colored pattern (colored pixels) forms the colorant of usefulness, can enumerate with represented metallic compounds such as metal oxide and metal complexs.Specifically can enumerate composite oxides of metal oxides such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and above-mentioned metal etc.

In addition, as organic pigment, for example, can enumerate:

C.I. pigment yellow (C.I.Pigment Yellow) 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;

C.I. pigment orange (C.I.Pigment Orange) 36,38,43,71;

C.I. paratonere (C.I.Pigment Red) 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;

C.I. pigment violet (C.I.Pigment Violet) 19,23,32,37,39;

C.I. alizarol saphirol (C.I.Pigment Blue) 1,2,15,15:1,15:3,15:6,16,22,60,66;

C.I. naphthol green (C.I.Pigment Green) 7,36,37;

C.I. pigment brown (C.I.Pigment Brown) 25,28;

C.I. pigment black (C.I.Pigment Black) 1

Deng and following general formula (A) shown in compound.

In the described general formula (A), R represent independently of one another hydrogen atom, methyl, ethyl, propyl group ,-N (CH ₃) ₂,-N (C ₂H ₅) ₂,-CF ₃, chlorine atom, bromine atoms or phenyl.

Wherein, R is chlorine atom, hydrogen atom, methyl or phenyl independently of one another.

Among the present invention, as organic pigment, there is no particular limitation, but more preferably:

Compound shown in the described general formula (A);

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;

C.I. pigment orange 36,71;

C.I. pigment red 122,150,171,175,177,209,224,242;

C.I. pigment violet 19,23,37;

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37.

These organic pigments can use separately or multiple being used in combination in order to improve excitation.The object lesson of combination is as follows.

For example, pigment as red phase (R) usefulness, can use the compound shown in the described general formula (A), anthraquinone (anthraquinone) pigment Yi separately Ji perylene (perylene) pigment, or use mixing of at least a and bisdiazo (bisazo) yellow uitramarine in them, iso-indoles (isoindoline) yellow uitramarine, quinophthalone (quinophthalone) yellow uitramarine Huo perylene red pigment etc.For example, can enumerate C.I. paratonere 177 Zuo as anthraquinone pigment is perylene dye, can enumerate C.I. paratonere 155 or C.I. paratonere 224, as the compound shown in the described general formula (A), can enumerate C.I. paratonere 254 (R in the described general formula (A) is the compound of chlorine atom), as the combination of pigment, from the viewpoint of color reproduction, preferably at least a the and C.I. pigment yellow 13 9 among them mixes.In addition, the mass ratio of red pigment and yellow uitramarine (red pigment: yellow uitramarine), from the viewpoint that obtains sufficient excitation and suppress to depart from mutually from NTSC (National Television System Committee) aim colour, be preferably 100: 5～100: 50, more preferably 100: 10～100: 30 scope.Illustrated, when being combination between the red pigment, can be regulated its mass ratio according to colourity.

In addition, (G) uses pigment as green phase, can use halogenated phthalocyanines (halogenatedphthalocyanine) pigment separately, or itself and the mixing of the yellow pigment of bisdiazo, quinophthalone yellow uitramarine, azomethine (azomethine) yellow uitramarine or iso-indoles yellow uitramarine.For example, as such example, preferred C.I. pigment Green 7,36 or 37 with the mixing of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.The mass ratio of viridine green and yellow uitramarine (viridine green: yellow uitramarine), from the viewpoint that obtains sufficient excitation and suppress to depart from mutually from the NTSC aim colour, be preferably 100: 5～100: 150, be preferably 100: 30～100: 120 scope especially.

(B) uses pigment as blue phase, can use phthalocyanine color separately, or itself Yu the mixing of dioxazine (dioxazine) violet pigment.For example, preferred C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment (blue pigment: violet pigment) be preferably 100: 0～100: 50, more preferably 100: 5～100: 30.

The content of the colorant of photosensitive coloring composition of the present invention (pigment) with respect to all solid state composition (quality) of said composition, is preferably 25 quality %～75 quality %, more preferably 32 quality %～70 quality %.If the content of colorant (pigment) in described scope, then can be guaranteed the look characteristic that colour saturation is fully also excellent effectively.

By the covered pigment of macromolecular compound

Among the present invention,, preferably use by the covered pigment of macromolecular compound as described colorant.

Wherein, preferably use organic pigment as pigment and in the miniaturization operation of pigment or dispersion step one one of pigment or all by the covered colorant of macromolecular compound.

By using the macromolecular compound coverage pigment,, and disperse with the state of 1 particle even the pigment after the miniaturization also can suppress the formation of 2 agglutination bodies.That is,, dispersiveness can be improved, the character (dispersion stabilization) that 1 particle after disperseing is kept can be improved with being stabilized by using the macromolecular compound coverage pigment.The result that dispersiveness and dispersion stabilization improve is that preparation solid state component 70% viscosity (25 ℃) becomes easy for the following photosensitive coloring composition of 50Pas.

In addition, as by the covered pigment of macromolecular compound, when using red pigment (for example, C.I. paratonere 254), can realize the effect that the angle height reduces effectively.

Below, to being described as " coverage pigment " by the covered pigment of macromolecular compound.

Optimal way as " covering " in the described coverage pigment, the mode that is preferably as follows: at the new interface of the high pigment of surfactivity that miniaturization produced, utilize the strong electrostatic interaction between this interface and the macromolecular compound (side chain for example described later has the macromolecular compound of heterocycle), form the firm overlayer of this macromolecular compound, present higher dispersion stabilization.In this manner, promptly use the organic solvent of dissolving macromolecular compound to clean the pigment that covers after handling, the macromolecular compound of covering also can break away from hardly.

Optimal way as " covering " in the above-mentioned coverage pigment, more specifically be preferably as follows mode: pigment particles such as organic pigment are covered by the macromolecular compound that side chain has heterocycle isopolarity base, because part or all of pigment particles surface covered securely by this macromolecular compound, thereby be the mode of performance high dispersion stability effect.This mode is different from the mode that general macromolecule dispersing agent is adsorbed in pigment.

The free amount (ionization rate) of macromolecular compound was confirmed when the covering state of this mode can clean with the organic solvent shown in following by mensuration.Promptly, for the coverage pigment that obtains for making the simple absorption of macromolecular compound, cleaning through organic solvent, the major part of the macromolecular compound that is adsorbed, particularly dissociate more than 65%, remove, but under the situation of the pigment through surface coverage of the present invention, ionization rate is few, is below 30%.

Clean the pigment that covers after handling with 1-methoxyl-2-propyl alcohol, calculate free amount.Particularly, in 1-methoxyl-2-propyl alcohol 100ml, drop into pigment 10g, use bobbing machine at room temperature to vibrate 3 hours.Then, under 80000rpm, spend 8 hours with hydro-extractor and make the pigment precipitation, obtain the solid state component of supernatant part by seasoning.Obtain from the dissociate quality of the macromolecular compound that of pigment, then according to its with initial treatment in the ratio of quality of the macromolecular compound that uses, calculate ionization rate (%).

The ionization rate of the pigment of commercially available grade can be measured with following method.Promptly, after using the solvent (for example dimethyl sulfoxide (DMSO), dimethyl formamide, formic acid, sulfuric acid etc.) that dissolves pigment that pigment is all dissolved, utilize deliquescent difference, with organic solvent it is separated into macromolecular compound and pigment, calculates " quality of employed macromolecular compound in the initial treatment ".In addition, clean pigment, use resulting above-mentioned free amount again, promptly try to achieve ionization rate (%) divided by this " quality of employed macromolecular compound in the initial treatment " with 1-methoxyl-2-propyl alcohol.

Ionization rate is more little, and the coverage rate on pigment is high more, and is dispersed, dispersion stabilization is good more.The preferable range of ionization rate is below 30%, more preferably below 20%, most preferably is below 15%.Desirable is 0%.

Covering the miniaturization operation of handling preferred and pigment carries out simultaneously, particularly, preferably through adding i) pigment, ii) water-soluble inorganic salt, iii) do not dissolve ii) small amounts of water soluble organic solvent and iv) macromolecular compound in fact, carry out the operation (be called salt and grind (salt milling) operation) of mechanically milling with kneader (kneader) etc.; This potpourri is dropped in the water,, make the operation of slurry (slurry) shape with high-speed mixer stirrings such as (high-speed mixer); And, carry out dry operation as required and implement this slurries filtration, washing.

Above-mentioned salt grinder preface is carried out more specific description.At first, at i) add on a small quantity iii) water-miscible organic solvent in the potpourri of organic pigment and ii) water-soluble inorganic salt as wetting agent, with kneader etc. strong mixing after, this potpourri is dropped in water, with stirrings such as high-speed mixers, make pulp-like.Then,, carry out drying more as required with this slurries filtration, washing, obtain miniaturization pigment.Illustrated, when in oil varnish (varnish), disperse using, also can use to be commonly referred to as the method for washing away (flushing) and the processing pigment (being called filter cake (cake)) before dry is removed moisture and to be distributed in the oil varnish.In addition, in the time of in being distributed to water varnish, handle the pigment drying-free, filter cake directly can be distributed in the varnish.

During the salt mill, by in above-mentioned iii) organic solvent, also using iv) partly soluble at least macromolecular compound, the few coverage pigment of aggegation of pigment in the time of can obtaining iv) partly soluble at least macromolecular compound covering of finer and surperficial quilt and drying.

Illustrated, added the iv) opportunity of macromolecular compound, can all be added, also can in salt grinder preface, be added in batches the initial of salt grinder preface.In addition, can also in dispersion step, add.

The macromolecular compound that uses in the covering as pigment, so long as the macromolecular compound that has the absorption base of pigment gets final product, but preferred especially side chain has the macromolecular compound of heterocycle.

The polymkeric substance that more preferably contains the polymerized unit of the monomer that constitutes from the monomer shown in the following general formula (1) or by maleimide or maleimide derivatives.Especially preferably contain polymkeric substance from the polymerized unit of the monomer shown in the following general formula (1).

Particularly from obtaining the viewpoint of effect of the present invention more effectively, most preferably described pigment is red pigment, and described macromolecular compound is for containing the polymkeric substance from the polymerized unit of the monomer shown in the following general formula (1).

In the described general formula (1), R ¹Expression hydrogen atom or replacement or unsubstituted alkyl.R ²Expression singly-bound or divalent link group.Y represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.Z represents to have the group of nitrogen heterocyclic ring structure.

As R ¹Alkyl, preferred carbon number is 1～12 alkyl, more preferably carbon number is 1～8 alkyl, preferred especially carbon number is 1～4 alkyl.

R ¹When shown alkyl has substituting group,, can enumerate for example hydroxyl, alkoxy (preferred carbon number is 1～5 alkoxy, and more preferably carbon atom is 1～3 alkoxy), methoxyl, ethoxy, cyclohexyloxy etc. as this substituting group.

As R ¹Shown preferred alkyl particularly for example can be enumerated methyl, ethyl, propyl group, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl.

R ¹Most preferably hydrogen atom or methyl.

In the general formula (1), R ²Expression singly-bound or divalent link group.Link group as this divalent, preferably replace or unsubstituted alkylidene.As this alkylidene, preferred carbon number is 1～12 alkylidene, and more preferably carbon number is 1～10 alkylidene, and more preferably carbon number is 1～8 alkylidene, and preferred especially carbon number is 1～4 alkylidene.

R ²Shown alkylidene can be the group that connects the alkylidene more than 2 by heteroatoms (for example oxygen atom, nitrogen-atoms or sulphur atom).

As R ²Shown preferred alkylidene particularly, for example can be enumerated methylene, ethylidene, propylidene, trimethylene, tetramethylene.

Work as R ²When shown preferred alkylidene has substituting group,, for example can enumerate hydroxyl etc. as this substituting group.

As R ²Shown divalent links group, can have at the end of above-mentioned alkylidene be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-and-heteroatoms among the NHCO-or contain heteroatomic part-structure, by this heteroatoms or contain heteroatomic part-structure and Z links.

In the general formula (1), Z represents to have the group of heterocycle structure.As group, for example can enumerate the pigment structure of phthalocyanines, insoluble azo class, azo lake (azolake) class, anthraquinone class, quinacridine ketone, dioxazines, diketopyrrolopyrrolecocrystals (diketopyrrolopyrrole) class, anthra pyridines, anthanthrone (anthanthrone) class, indanthrone (indanthrone) class, yellow anthrone (flavanthrone) class, purple cyclic ketones (perinone) class, perylene class, thioindigo class with heterocycle structure; Or thiophene for example, furans, xanthene, the pyrroles, pyrrolin (pyrroline), pyrrolidine, dioxolanes (dioxolane), pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane (trithiane), isoindoline, isoindolinone, benzimidazole alkane ketone, benzothiazole, succinimide, phthalimide, naphthalimide (naphthalimide), hydantoins (hydantoin), indoles, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazolium, phenothiazine phenoxazine, benzimidazole, benzotriazole, cyclic amide, ring-type urea, heterocycle structures such as cyclic imide.These heterocycle structures can have substituting group, as this substituting group, for example can enumerate alkyl, alkoxy, halogen atom, aliphatics ester group, aromatic series ester group, alkoxy carbonyl etc.

Z further preferably has the group that carbon number is the nitrogen heterocyclic ring structure more than 6, and especially preferably having carbon number is the group of the nitrogen heterocyclic ring structure more than 6, below 12.As carbon number is nitrogen heterocyclic ring structure more than 6, particularly, preferred phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure, the structure shown in especially preferably following (2), (3) or (4).

In the general formula (2), X represent to be selected from singly-bound, alkylidene (for example methylene, ethylidene, propylidene, trimethylene, tetramethylene etc.) ,-O-,-S-,-NR ^A-and-C (=O)-in any.Here, R ^AExpression hydrogen atom or alkyl.Work as R ^AAlkyl during the expression alkyl, preferred carbon number is 1～18 alkyl, further preferred carbon number is 1～6 alkyl, for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, n-octyl, 2-ethylhexyl, positive stearyl etc.

In above-mentioned, as the X of general formula (2), preferred singly-bound, methylene ,-O-or-C (=O)-, especially preferred-C (=O)-.

In the general formula (4), X and Z respectively independently expression-N=,-NH-,-N (R ^B)-,-S-or-O-.R ^BThe expression alkyl is worked as R ^BAlkyl during the expression alkyl, preferred carbon number is 1～18 alkyl, further preferred carbon number is 1～6 alkyl, for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, n-octyl, 2-ethylhexyl, positive stearyl etc.

In above-mentioned, independent separately as the Y in the general formula (4) and Z, especially preferred-N=,-NH-and-N (R ^B)-.As the combination of Y and Z, the either party that can enumerate among Y and the Z is-N=and the opposing party combination for-NH-, i.e. imidazole radicals.

In general formula (2), (3) and (4), ring A, ring B, ring C and ring D represent aromatic ring respectively independently.As this aromatic ring, for example can enumerate phenyl ring, naphthalene nucleus, indenes ring, Azulene (azulene) ring, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring etc., wherein preferred phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, preferred especially phenyl ring, naphthalene nucleus, pyridine ring.

Particularly, as ring A in the above-mentioned general formula (2) and ring B, for example can enumerate phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.As the ring C in the general formula (3), for example can enumerate phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.As the ring D in the general formula (4), for example can enumerate phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.

As the aromatic ring that contains in the structure shown in general formula (2), (3) and (4), from the viewpoint of the ageing stability of dispersed, dispersion liquid, further preferred phenyl ring, naphthalene nucleus, in general formula (2) and (4), more preferably phenyl ring, in general formula (3), more preferably naphthalene nucleus.

As these concrete compounds, can enumerate following MA-1～MA-13 and following M-1～M-33, but the invention is not restricted to these.

In addition, as the example of macromolecular compound, except that above-mentioned MA-1～MA-13 and M-1～M-33, also can enumerate following compound.

Even state in the use through under the situation that covers the pigment of handling, also preferably use at least a kind in the spreading agent and come dispersed color, thereby as pigment dispensing composition.By containing this spreading agent, can improve dispersing of pigments.

As spreading agent, can suitably select for example known pigment dispersing agent or surfactant.

Particularly, can use multiple compound, for example can enumerate organic siloxane polymer (organosiloxane polymer) KP341 (SHIN-ETSU HANTOTAI's chemical industry (Co., Ltd.) (Shin-EtsuChemical Co., Ltd.) system), (methyl) acrylic acid series (being total to) polymkeric substance Port リ Off ロ one (POLYFLOW) No.75, No.90, No.95 (common prosperity society chemical industry (Co., Ltd.) (Kyoeisha Chemical Co., Ltd.) system), W001 (abundant merchant (Co., Ltd.) society cationic surfactants such as (YushoCo., Ltd.) systems); Non-ionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid ester; W004, W005, W017 anionic surface active agent such as (abundant merchant (Co., Ltd.) society systems); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (be vapour refine company (Ciba Japan K.K.) system), DISPERSE AID (デイスパ one スエイ De) 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSEAID9100 macromolecule dispersing agents such as (by San Nopco Limited systems); Various SOLSPERSE spreading agents (Japanese road Bao Run (Co., Ltd.) (The Lubizol Corporation) system) such as SOLSPERSE (ソ Le スパ one ス) 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; Adeka Pluronic (アデカプ Le ロニ Star Network) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification (Co., Ltd.) (ADEKA Corporation) system) and IONET (イオネ Star ト) S-20 (Sanyo changes into (Co., Ltd.) (Sanyo Chemical Industries Ltd.) system), Disperbyk101,103,106,108,109,111,112,116,130,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (Bi Ke chemistry (Co., Ltd.) (BYK Japan KK) systems).In addition, can also enumerate acrylic copolymer etc. has polar group at molecular end or side chain oligomer or polymkeric substance.

The content of spreading agent in pigment dispensing composition with respect to the quality of above-mentioned pigment, is preferably 1～100 quality %, more preferably 3～70 quality %.

Above-mentioned pigment dispensing composition also can add pigment derivative as required.Make to have imported and have the part of compatibility with spreading agent or the pigment derivative of polar group is adsorbed on surface of pigments, adsorption site used as pigment dispersing agent, thereby pigment is dispersed in the photosensitive composition as fine particle, can prevent its aggegation again, help to constitute the color filter of contrast height, transparency excellence.

Pigment derivative particularly is to be precursor skeleton with the organic pigment, has imported acidic groups or basic group, aromatic series base as substituent compound at side chain.Organic pigment can be enumerated quinacridone pigment, phthalocyanine color, AZO pigments, quinophthalone pigment, isoindoline pigment, isoindolinone pigment, quinoline pigment, diketo-pyrrolo pyrrole pigments, benzimidazolone pigment etc. particularly.Usually also comprise flaxen aromatic series polycyclic compunds such as the naphthalene class that is not called as pigment, anthraquinone class, triazines, quinolines.As pigment derivative, can use the compound of record in Japanese kokai publication hei 11-49974 communique, Japanese kokai publication hei 11-189732 communique, Japanese kokai publication hei 10-245501 communique, TOHKEMY 2006-265528 communique, Japanese kokai publication hei 8-295810 communique, Japanese kokai publication hei 11-199796 communique, TOHKEMY 2005-234478 communique, TOHKEMY 2003-240938 communique, the TOHKEMY 2001-356210 communique etc.

As the content of pigment derivative of the present invention in pigment dispensing composition, with respect to the quality of pigment, be preferably 1～30 quality %, more preferably 3～20 quality %.Described content is in above-mentioned scope the time, can disperse well in lower in that viscosity is suppressed, and can improve dispersion stabilization after disperseing, the transmitance height obtains good color characteristics, and can form the high-contrast with good color characteristics when making color filter.

About the method for disperseing, for example can use following method: use and to have utilized pearl dispersion machine that zirconium oxide bead (zirconium beads) wait etc., to pigment and pigment dispersing agent is pre-mixed and with homogenizer (homogenizer) wait prior dispersion and the material that obtains to carry out differential diffusing.

Among the present invention, the viewpoint of solid state component 70% viscosity (25 ℃) below 50Pas of calm photosensitive coloring composition easy to control set out, preferred especially following process for dispersing.

Promptly, preferred especially following method: with coverage pigment, spreading agent and solvent, use that homogenizer etc. disperses more than 2 hours in advance, (more preferably more than 3 hours, below 5 hours) below 6 hours, then, use utilized the differential such as pearl dispersion machine of zirconium oxide bead etc. loose (be preferably more than 6 hours, below 10 hours, more preferably more than 7 hours, below 9 hours).

Polymerizable compound

The photosensitive coloring composition that uses among the present invention contains at least a kind of polymerizable compound.

The polymerizable compound that the present invention can use is selected from following compound, and described compound is the addition polymerization compound with at least 1 olefinic unsaturated double-bond, wherein has at least 1, preferred terminal olefinic unsaturated link more than 2.This compound group is widely known by the people in this area, all can not have particular restriction ground in the present invention and uses.They for example can be that monomer, prepolymer are dipolymer, trimer and oligomer or their potpourri and their chemical modes such as multipolymer.As the example of monomer and multipolymer thereof, can enumerate unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and ester class thereof, amide-type.The preferred amide-type that uses ester class, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and aliphatic polyol compound.In addition, can also preferably use the addition reaction product of the substituent unsaturated carboxylate types of nucleophilicity such as having hydroxyl, amino or sulfydryl or unsaturated carboxylic acid amide-type and simple function or polyfunctional isocyanate's class or simple function or multi-functional epoxy's class; The dehydration condensation product of above-mentioned unsaturated carboxylate type or unsaturated carboxylic acid amide-type and simple function or polyfunctional carboxylic acids etc.In addition, also preferably have the addition reaction of substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group or epoxy radicals or unsaturated carboxylic acid amide-type and simple function or multifunctional alcohols, amine, thio-alcohol, and the substituted reactant with the unsaturated carboxylate type of the substituents of leaving away such as halogen, tosyloxy or unsaturated carboxylic acid amide-type and simple function or multifunctional alcohols, amine, thio-alcohol.As other examples, can also use the compound group that above-mentioned unsaturated carboxylic acid is replaced as unsaturated phosphonic acids, styrene, vinyl ether etc. and obtains.

Object lesson as the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, can enumerate glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanuric acid ester, the polyester acrylic ester oligomer, cyamelide EO modification triacrylate etc.

As methacrylate, can enumerate butanediol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two (right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl) dimethylmethane, two (right-(methacryloxy ethoxy) phenyl) dimethylmethane etc.

As itaconate, can enumerate ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, butylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.As crotonates, can enumerate ethylene glycol bisthioglycolate crotonates, butylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four crotonatess etc.As the iso-crotonic acid ester, can enumerate ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc.As maleate, can enumerate ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc.

As the example of other esters, for example preferably use the aliphatic alcohol of putting down in writing in Japanese Patent Publication 51-47334 communique, the Japanese kokai publication sho 57-196231 communique be put down in writing in the ester class put down in writing in ester class, Japanese kokai publication sho 59-5240 communique, Japanese kokai publication sho 59-5241 communique, the Japanese kokai publication hei 2-226149 communique, the Japanese kokai publication hei 1-165613 communique with aromatic series pastern bone frame contain amino ester etc.In addition, above-mentioned ester monomer can also use as potpourri.

Object lesson as the monomer of the acid amides of aliphatic polyamine compound and unsaturated carboxylic acid, can enumerate methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1,6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, diethylene triamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.As the example of other preferred amide-type monomers, can enumerate the acid amides of putting down in writing in the Japanese Patent Publication 54-21726 communique with cyclohexylidene structure.

In addition, also preferably use the urethanes class addition polymerization compound of the addition reaction manufacturing of isocyanates and hydroxyl, as its object lesson, for example can enumerate the vinyl urethane compounds that contains 2 above polymerism vinyl in 1 molecule that the vinyl monomer addition that contains hydroxyl of the polyisocyanate compounds that has 2 above isocyanate group in 1 molecule putting down in writing in the Japanese Patent Publication 48-41708 communique and following general formula (V) expression obtains etc.

CH ₂＝C(R ⁴)COOCH ₂CH(R ⁵)OH (V)

(R ⁴And R ⁵Represent H or CH respectively independently ₃)

The urethanes esters of acrylic acid of putting down in writing in preferred Japanese kokai publication sho 51-37193 communique, the special fair 2-32293 communique of Japan, the special fair 2-16765 communique of Japan, the urethane compound class of putting down in writing in Japanese Patent Publication 58-49860 communique, Japanese Patent Publication 56-17654 communique, Japanese Patent Publication 62-39417 communique, the Japanese Patent Publication 62-39418 communique with ethylene oxide skeleton.In addition, by using the addition polymerization compounds that has amino structure or sulfide structure in the molecule of putting down in writing in Japanese kokai publication sho 63-277653 communique, Japanese kokai publication sho 63-260909 communique, the Japanese kokai publication hei 1-105238 communique, can obtain the poly-property composition of the extraordinary light of film speed thus.

As other examples, can enumerate polyester acrylate class, epoxy resin and (methyl) acrylic acid of putting down in writing in each communique of Japanese kokai publication sho 48-64183 communique, Japanese Patent Publication 49-43191 communique, Japanese Patent Publication 52-30490 communique and react polyfunctional acrylic ester and the methacrylates such as epoxy acrylate class that obtains.In addition, can also enumerate the vinyl phosphonic acid compounds put down in writing in specific unsaturated compound that Japanese Patent Publication 46-43946 communique, the special fair 1-40337 communique of Japan, Japan put down in writing in the special fair 1-40336 communique, the Japanese kokai publication hei 2-25493 communique etc.In some cases, preferably use the structure of putting down in writing in the Japanese kokai publication sho 61-22048 communique that contains perfluoroalkyl.In addition, can also use photo-curable monomer and the oligomer of following record in association's will (Journal of the Adhesion Society of Japan) vol.20, No.7,300～308 pages (1984) in Japan.

About the structure of these polymerizable compounds, use separately or share, the detailed content of using method such as addition, can set arbitrarily according to the performance design of final photosensitive material.For example, can select based on following viewpoint.

Aspect sensitivity, preferred many structures of the unsaturated group mass contg of each molecule are more than in most cases preferred 2 official's energy.In order to improve the intensity that rendered image portion is a dyed layer, can be advisable by above polymerizable compound with 3 officials, in addition, it is very effective that have different functional number by share/different polymerizable groups polymerizable compound of (for example acrylate, methacrylate, styrene compound, vinyl ethers compound) is regulated the two method of sensitivity and intensity.From solidifying the viewpoint of sensitivity, the preferred compound that contains (methyl) acrylate structural more than 2 that uses further preferably uses the compound that contains more than 3, most preferably uses the compound that contains more than 4.Viewpoint from the development of solidifying sensitivity and unexposed portion preferably contains EO modification body.From solidifying the viewpoint of sensitivity and exposure portion intensity, preferably contain urethane bonds.

For with dyed layer in intermiscibility, the dispersiveness of other compositions (for example alkali soluble resin, initiating agent, colorant (pigment, dyestuff etc.)), the selection of polyaddition compounds and using method also are key factors, for example, by using the low-purity compound or share more than 2 kinds, can improve intermiscibility sometimes.In addition, in order to improve the adaptation with substrate, can also select specific structure.

Based on above viewpoint, can preferably enumerate bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc.As commercially available product, preferred urethane oligomers (urethane oligomer) UAS-10, UAB-140 (Nippon Paper chemical company (Nippon pater chemicals) system), DPHA (Japanese chemical drug (the Nippon kayaku Co. of company, Ltd.) system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (chemical industry Co., Ltd. of common prosperity society (Kyoeisha ChemicalCo., Ltd) system).

Wherein, further preferred bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc. and as DPHA (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, the AI-600 (chemical industry Co., Ltd. of common prosperity society system) of commercially available product.

The content of described polymerizable compound preferably accounts for the 5 quality %～55 quality % of all solid state components in the photosensitive color composition layer of the present invention, more preferably 10 quality %～50 quality %, more preferably 15 quality %～45 quality %.

Bonding agent

Described photosensitive coloring composition of the present invention contains at least a bonding agent.

As described bonding agent,, be preferably alkali soluble resin from improving the epithelium characteristic, giving viewpoint such as developing property.

As described alkali soluble resin, be the wire organic high molecular polymer, can from the alkali soluble resin that molecule (being preferably acrylic copolymer, styrol copolymer molecule), has at least 1 group (for example carboxyl, phosphate, sulfonic group, hydroxyl etc.) that promotes alkali-soluble, suitably select as main chain.

As above-mentioned alkali soluble resin, preferred side chain has the polymkeric substance of carboxylic acid.For example can enumerate Japanese kokai publication sho 59-44615 number, Japanese Patent Publication 54-34327 number, Japanese Patent Publication 58-12577 number, Japanese Patent Publication 54-25957 number, Japanese kokai publication sho 59-53836 number, the methacrylic acid copolymer of putting down in writing in each communique of Japanese kokai publication sho 59-71048 number, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, maleic acid, partial esterification (partiallyesterified) maleic acid etc., and side chain has the acid cellulose derivant of carboxylic acid, addition acid anhydrides in having the polymkeric substance of hydroxyl and acrylic acid series copolymer of obtaining etc.

The acid number of above-mentioned alkali soluble resin is preferably 10mgKOH/g～200mgKOH/g, is preferably 30mgKOH/g～180mgKOH/g, more preferably the scope of 50mgKOH/g～150mgKOH/g.

About the concrete formation unit of alkali soluble resin, preferred especially (methyl) acrylic acid and can with the multipolymer of other monomer of its copolymerization.Need to prove, as can with other monomer of described (methyl) acrylic acid copolymer, can enumerate (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.Here, the hydrogen atom of alkyl and aryl also can be substituted the base replacement.

As described (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, expression CH ₂=C (R ¹) (COOR ³) (R here, ¹Expression hydrogen atom or carbon number are 1～5 alkyl, R ³The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aralkyl).As concrete example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) CA, (methyl) acrylic acid naphthalene ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid hydroxyalkyl acrylate (alkyl is that carbon number is 1～8 alkyl), methacrylic acid hydroxyl ethylene oxidic ester, tetrahydrofurfuryl methacrylate etc.

In addition, also preferred molecular side chain has the resin of polyalkylene oxide chain.As above-mentioned polyalkylene oxide chain, can adopt polyethylene oxide chain, polypropyleneoxide chain, polytetramethylene glycol chain or they are share, end is the alkyl of hydrogen atom, straight or branched.

The repetitive of polyethylene oxide chain, polypropyleneoxide chain is preferably 1～20, and more preferably 2～12.Have the acrylic copolymer of polyalkylene oxide chain as above-mentioned side chain, for example can enumerate that for example methoxy poly (ethylene glycol) list (methyl) acrylate, ethoxy polypropylene glycol list (methyl) acrylate, single (methyl) acrylate etc. of methoxyl poly-(ethylene glycol and 1,2-propylene glycol) are the acrylic copolymer of copolymer composition by the compound after alkyl-blocked with polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate etc. and their terminal OH base.

As above-mentioned vinyl compound, can enumerate CH ₂=CR ¹R ²[R here, ¹Expression hydrogen atom or carbon number are 1～5 alkyl, R ²The expression carbon number is 6～10 aromatic hydrocarbon ring], specifically can enumerate styrene, α-Jia Jibenyixi, vinyltoluene, vinyl cyanide, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer etc.

Other monomers of energy copolymerization can use a kind separately, or are used in combination more than 2 kinds.Wherein, the multiple copolymer of preferred especially (methyl) benzyl acrylate/(methyl) acrylic copolymer and (methyl) benzyl acrylate/(methyl) acrylic acid/other monomers formation.

As mentioned above, aforesaid propylene acid is the acid number that resin preferably has the scope of 20mgKOH/g～200mgKOH/g.If acid number is below 200mgKOH/g, then the dissolubility of acrylic resin in alkali can be not excessive, and the optimum range that can prevent to develop (development latitude (latitude)) narrows down.On the other hand, if more than 20mgKOH/g, then, can prevent that development time is elongated because the dissolubility in alkali is difficult for reducing.

Acid is the weight-average molecular weight Mw (with the polystyrene conversion value of GPC method (GelPermeation Chromatography) mensuration) of resin about aforesaid propylene, in order to realize being easy to the range of viscosities that on operations such as coating photosensitive coloring composition, uses and guaranteeing film strength, be preferably 2000～100000, more preferably 3000～50000.

In order to improve the cross-linking efficiency of photosensitive coloring composition of the present invention, can use the resin that in alkali soluble resin, has polymerizable group separately or share, also can adopt polymkeric substance that contains aryl, (methyl) acrylic, aryloxy alkyl etc. at side chain etc. with the alkali soluble resin that does not contain polymerizable group.Alkali soluble resin with the two keys of polymerism can develop in alkaline developer, also has photo-curable and Thermocurable.These examples of polymkeric substance that contain polymerizable group are as follows, as long as contain alkali-soluble group and carbon-to-carbon unsaturated bonds such as COOH base or OH base in 1 molecule, are not limited to following substances.

(1) compound that makes isocyanate group and OH reaction and residual 1 unreacted isocyanate group in advance and contain at least 1 (methyl) acryloyl group obtain with containing the reactive acrylic resin of carboxyl through the urethane-modified acryl resin that contains the two keys of polymerism

(2) contain the reaction of the compound that has epoxy radicals and the two keys of polymerism in the acryl resin of carboxyl and the molecule simultaneously and the acryl resin that contains unsaturated group that obtains,

(3) ACID-PENDANT type Epocryl,

(4) acryl resin that contains the OH base reacts the acryl resin that contains the two keys of polymerism that obtains with the dibasic acid anhydride with the two keys of polymerism.

The resin of preferred especially (1) and (2) in the above-mentioned resin.

As object lesson, can use for example acrylic acid-2-hydroxyl ethyl ester with OH base and contain the COOH base for example methacrylic acid and can with the multipolymer of monomers such as the acrylic compounds of their copolymerization or vinylic chemical compound, the OH base is had compound compounds such as (for example) the glycidyl acrylates reaction of reactive epoxide ring and carbon carbon unsaturated link and the compound that obtains etc. with containing.With the reaction of OH base in, except that epoxide ring, can also use acid anhydrides, have the compound of isocyanate group or acryloyl group.

In addition, can also use the compound of putting down in writing in Japanese kokai publication hei 6-102669 communique, the Japanese kokai publication hei 6-1938 communique that obtains by the reaction of the unsaturated carboxylic acid of the compound with epoxide ring and acrylic acid and so on to react and the reactant that obtains with saturated or unsaturated multi-anhydride.

As the compound of alkali-soluble group that has COOH base and so on concurrently and carbon carbon unsaturated group, for example can enumerate DIANAL (ダイヤ Na one Le) NR series (Mitsubishi Rayon Co., Ltd (Mitsubishi Rayon Co., Ltd.) system; Photomer 6173 (the polyurethane acroleic acid oligomer, the Diamond Shamrock Co.Ltd. system that contain the COOH base); VISCOTE (PVC スコ one ト) R-264, KS RESIST 106 (being Osaka Organic Chemical Industry Co., Ltd.'s system (Osaka Organic Chemical Industry Ltd.) system)); CYCLOMER (サイ Network ロマ one) P series, PLACCEL (プラ Network セ Le) CF200 series (being Daisel chemical industry Co., Ltd's system (DICEL Chemical Industries, Ltd.) system)); Ebecryl3800 (the special company of Daicel cyanogen (DAICEL-CYTEC COMPANY Ltd.) system) etc.

As the addition of alkali soluble resin, be preferably the scope of 3～30 quality % in total solid state component of dyed layer, more preferably 5～20 quality %.

When the preparation photosensitive coloring composition, as binder polymer, except that above-mentioned alkali soluble resin, the following epoxy resin of preferred further interpolation.As epoxy resin, can enumerate the compound that has 2 above epoxide rings in bisphenol A type epoxy resin, cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, the alicyclic epoxy compound equimolecular.

For example, as bisphenol A type epoxy resin, can enumerate EPOTOHTO (エ Port ト one ト) YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (more than, Dongdu changes into (Co., Ltd.) (Tohto Kasei Co., Ltd.) system), DENACOL (デ Na コ one Le) EX-1101, EX-1102, EX-1103 etc. (more than, long rapids changing into (Co., Ltd.) (NagaseChemteX Corporation) system), PLACCEL GL-61, GL-62, G101, G102 (more than, Daicel chemical industry (Co., Ltd.) (DICEL Chemical Industries, Ltd.) system) etc.In addition, can also enumerate and they similar bisphenol f type epoxy resins, bisphenol-s epoxy resin.

In addition, also can use the epoxy acrylate of Ebecryl3700,3701,600 (more than, Daicel cyanogen spy (Co., Ltd.) system) etc.The example of cresols phenolic resin varnish type epoxy resin, can enumerate EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (more than, Dongdu changes into (Co., Ltd.) system), DENACOLEM-125 etc. (more than, Nagase chemical Co., Ltd (Co., Ltd.) system), the example of biphenyl type epoxy resin, can enumerate 3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl etc.Example as the ester ring type epoxy compounds, can enumerate CELLOXIDE (セロキサイ De) 2021,2081,2083,2085, EPOLEAD (エ Port リ one De) GT-301, GT-302, GT-401, GT-403, EHPE-3150 (more than, Daicel chemical industry (Co., Ltd.) system), SANTOHTO (サ Application ト one ト) ST-3000, ST-4000, ST-5080, ST-5100 etc. (more than, Dongdu changes into (Co., Ltd.) system), Epiclon430, with 673, with 695, same 850S, with 4032 (more than, big Japanese ink chemical industry (Co., Ltd.) (DIC Corporation) system) etc.In addition, 1,1,2, carry out dimer acid modified in 2-four (p-glycidyl oxygen base phenyl) ethane, three (p-glycidyl oxygen base phenyl) methane, triglycidyl group three (hydroxyethyl) isocyanates, o-phthalic acid diglycidyl ester, terephthalic acid (TPA) diglycidyl ester, the skeleton and glycidyl esters of obtaining etc. as EPOTOHTO YH-434, the YH-434L of other amine type epoxy resin, bisphenol A type epoxy resin.

Wherein, preferred " quantity of molecular weight/epoxide ring " is more than 100, more preferably 130～500.If " quantity of molecular weight/epoxide ring " little, curable height then, the contraction during curing is big, if excessive, then curable deficiency, less reliable or flatness variation.

Example as concrete preferred compound, can enumerate EPOTOHTO YD-115,118T, 127, YDF-170, YDPN-638, YDPN-701, PLACCEL GL-61, GL-62,3,5,3 ', 5 '-tetramethyl-4,4 ' diglycidyl biphenyl, CELLOXIDE 2021,2081, EPOLEAD GT-302, GT-403, EHPE-3150 etc.

Solvent

Photosensitive coloring composition of the present invention contains at least a solvent.

Example as described solvent, preferred ester class, ethyl acetate for example, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate and 3-oxygen base methyl propionate, 3-oxygen base alkyl propionates such as 3-oxygen base ethyl propionate (3-methoxypropionic acid methyl esters for example, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc.), 2-oxygen base methyl propionate, 2-oxygen base ethyl propionate, 2-oxygen base alkyl propionates such as 2-oxygen base propyl propionate (2-methoxypropionic acid methyl esters for example, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester etc.) and methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, 1,3 butylene glycol diacetate esters etc.;

Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran (tetrahydrofuran), glycol monoethyl ether, ethylene glycol monomethyl ether, methylcellosolve acetate (methyl cellosolve acetate), ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propylene glycol monopropyl ether acetic acid esters, diethyl carbitol, the diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, the diethylene glycol monobutyl ether acetic acid esters, propylene glycol positive propyl ether acetic acid esters, propylene-glycol diacetate, the propylene glycol n-butyl ether acetic acid esters, propylene glycol phenyl ether, propylene glycol phenyl ether acetic acid ester, the dipropylene glycol monomethyl ether acetic acid esters, dipropylene glycol positive propyl ether acetic acid esters, dipropylene glycol n-butyl ether acetic acid esters, the tripropylene glycol mono-n-butyl ether, tripropylene glycol methyl ether acetate etc.;

Ketone, for example acetone, MEK, cyclohexanone (cyclohexanone), 2-heptanone, 3-heptanone etc.;

Alcohols, for example ethanol, isopropyl alcohol, methyl proxitol, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether;

Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.

Wherein, preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, methyl proxitol, methyl proxitol acetate, propylene glycol ethylether acetic acid esters etc.

Solvent may be used alone, two or more kinds can also be used in combination.

Among the present invention, be under the condition below the 50Pas in solid state component 70% viscosity (25 ℃), there is no particular limitation for solvent types, for example unrestrictedly uses above-mentioned solvent.

Photoepolymerizationinitiater initiater

Photosensitive color composition of the present invention preferably contains Photoepolymerizationinitiater initiater.

Described Photoepolymerizationinitiater initiater is that the effect at light issues estranged separating, and causes and promote described polymerizable compound polymeric compounds, preferably has the compound of absorption in the zone of wavelength 300～500nm.In addition, described Photoepolymerizationinitiater initiater can use two or more uses also capable of being combined separately.

As Photoepolymerizationinitiater initiater, for example can enumerate organic halogenation compound oxadiazole (oxidiazole) compound; carbonyls; acetal (ketal) compound; benzoin (benzoin) compound; acridine (acridine) compound; organic peroxide; azo-compound; coumarin compound; triazo-compound (azide); metallocene (metallocene) compound; six aryl bisglyoxaline (hexaarylbiimidazole) compounds; organic boron-oxygen; two sulphones; oxime ester (oxime ester) compound; salt (onium salt) compound; acylphosphanes (oxide) (acylphosphine oxide) compound.

As the organic halogenation compound, specifically can enumerate if " Bull Chem Soc Japan " 42 such as woodss, 2924 (1969), No. 3905815 instructions of United States Patent (USP), Japanese Patent Publication 46-4605 communique, Japanese kokai publication sho 48-36281 communique, Japanese kokai publication sho 55-32070 communique, Japanese kokai publication sho 60-239736 communique, Japanese kokai publication sho 61-169835 communique, Japanese kokai publication sho 61-169837 communique, Japanese kokai publication sho 62-58241 communique, Japanese kokai publication sho 62-212401 communique, Japanese kokai publication sho 63-70243 communique, Japanese kokai publication sho 63-298339 communique, M.P.Hutt " Journal of Heterocyclic Chemistry " 1 (No3), (1970) etc. the compound of record in can be enumerated especially by trihalomethyl and replaces De oxazole compound, s-triazine.

As s-triazine, more preferably on the s-triazine ring, combine by at least 1 list, two, or three methyl that replaced of halogen and the Striazine derivative that obtains, for example specifically can enumerate 2,4,6-three (monochloro methyl) s-triazine, 2,4,6-three (dichloromethyl) s-triazine, 2,4,6-three (trichloromethyl) s-triazine, 2-methyl-4,6-two (trichloromethyl) s-triazine, 2-n-pro-pyl-4,6-two (trichloromethyl) s-triazine, 2-(α, α, β-three chloroethyl)-4,6-two (trichloromethyl) s-triazine, 2-phenyl-4,6-two (trichloromethyl) s-triazine, 2-(p-methoxyphenyl)-4,6-two (trichloromethyl) s-triazine, 2-(3, the 4-epoxy-phenyl)-4,6-two (trichloromethyl) s-triazine, 2-(rubigan)-4,6-two (trichloromethyl) s-triazine, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4,6-two (trichloromethyl) s-triazine, 2-styryl-4,6-two (trichloromethyl) s-triazine, 2-(to methoxyl-styrene)-4,6-two (trichloromethyl) s-triazine, 2-(to the isopropoxystyrene base)-4,6-two (trichloromethyl) s-triazine, 2-(p-methylphenyl)-4,6-two (trichloromethyl) s-triazine, 2,4-(methoxyl naphthyl)-4,6-two (trichloromethyl) s-triazine, 2-thiophenyl-4,6-two (trichloromethyl) s-triazine, 2-benzylthio-4,6-two (trichloromethyl) s-triazine, 4-(adjacent bromo-is right-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (trichloromethyl) s-triazine, 2,4,6-three (two bromomethyls) s-triazine, 2,4,6-three (trisbromomethyl) s-triazine, 2-methyl-4,6-two (trisbromomethyl) s-triazine, 2-methoxyl-4,6-two (trisbromomethyl) s-triazine etc.

Zuo Wei oxadiazole compound, can enumerate 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole etc.

As carbonyls, can enumerate benzophenone derivates such as benzophenone (benzophenone), Michler's keton (micher ' s ketone), 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone; 2,2-dimethoxy-2-phenyl acetophenone, 2, the 2-diethoxy acetophenone, the 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-methyl phenyl ketone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl isophthalic acid-(4 '-(methyl mercapto) phenyl)-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 1,1,1-trichloromethyl-(to butyl phenyl) ketone, 2-benzyl-2-dimethylamino-acetophenone derivs such as 4-morpholinyl bromo benzophenone; Thioxanthones (thioxanthone), 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, thioxanthone derivates such as 4-diisopropyl thioxanthones; The ESCAROL 507 ethyl ester, to benzoate derivatives such as diethylamino ethyl benzoate etc.

As acetal compound, can enumerate benzyl dimethyl acetal, benzyl-'beta '-methoxy ethyl diethyldithiocarbamate acetal etc.

As the benzoin compound, can enumerate a benzoin iso-propylether, benzoin isobutyl ether, benzoin methylether, methyl-o-benzoyl yl benzoic acid ester etc.

As the acridine compound, can enumerate the 9-phenylacridine, 9-pyridine radicals acridine, 9-pyrazinyl acridine, 1,2-two (9-acridinyl) ethane, 1,3-two (9-acridinyl) propane, 1,4-two (9-acridinyl) butane, 1,5-two (9-acridinyl) pentane, 1,6-two (9-acridinyl) hexane, 1,7-two (9-acridinyl) heptane, 1,8-two (9-acridinyl) octane, 1,9-two (9-acridinyl) nonane, 1,10-two (9-acridinyl) decane, 1,11-two (9-acridinyl) undecane, 1,12-two (9-acridinyl) dodecane etc. two (9-acridinyl) alkane etc.

Example as organic peroxide; can enumerate trimethyl hexanone peroxide; acetylacetone peroxide; 1; two (tert-butyl hydroperoxide)-3 of 1-; 3; the 5-trimethyl-cyclohexane; 1; two (tert-butyl hydroperoxide) cyclohexanes of 1-; 2; two (tert-butyl hydroperoxide) butane of 2-; tert-butyl hydroperoxide; cumyl hydroperoxide (cumene hydroperoxide); the diisopropyl benzene hydrogen peroxide; 2; 5-dimethylhexane-2; 5-diperoxy hydrogen; 1; 1; 3; the 3-tetramethyl butyl hydroperoxide; tert-butyl group cumyl hydroperoxide; dicumyl hydrogen peroxide (dicumylperoxide); 2; 5-dimethyl-2; 5-two (tert-butyl hydroperoxide) hexane; 2; 5-oxygen acyl group (オキサノイ Le) superoxide; succinic acid peroxide; benzoyl peroxide; 2; 4-dichloro-benzoyl superoxide; di-isopropyl peroxydicarbonate; peroxy dicarbonate two-2-Octyl Nitrite; peroxy dicarbonate two-2-ethoxy ethyl ester; peroxidating carbonic acid dimethoxy isopropyl ester; peroxy dicarbonate two (3-methyl-3-methoxyl butyl) ester; peroxide acetic acid butyl ester; the peroxidating neopentanoic acid tert-butyl ester; new peroxide tert-butyl caprate; the peroxidation acid tert-butyl ester; the peroxidating lauric acid tert-butyl ester; 3; 3 '; 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone; 3; 3 '; 4; 4 '-four (uncle's hexyl peroxidating carbonyl) benzophenone; 3; 3 '; 4,4 '-four (p-isopropyl cumyl peroxidating carbonyl) benzophenone; carbonyl two (tert-butyl hydroperoxide dihydro two phthalic esters); carbonyl two (uncle's hexyl peroxidating dihydro two phthalic esters) etc.

As azo-compound, for example can enumerate azo-compound of putting down in writing in the Japanese kokai publication hei 8-108621 communique etc.

As coumarin compound, for example can enumerate 3-methyl-5-amino-((guanamine-yl) amino)-3-phenyl cumarin, 3-chloro-5-diethylamino-((guanamine-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((guanamine-yl) amino)-3-phenyl cumarin etc.

Example as triazo-compound, can be set forth in the organic azide of putting down in writing in No. 2848328 instructions of United States Patent (USP), No. 2852379 instructions of United States Patent (USP) and No. 2940853 instructions of United States Patent (USP), 2, two (4-nitrine the benzal)-4-ethyl cyclohexanones (BAC-E) of 6-etc.

As metallocene compound, can be set forth in Japanese kokai publication sho 59-152396 communique, Japanese kokai publication sho 61-151197 communique, Japanese kokai publication sho 63-41484 communique, Japanese kokai publication hei 2-249 communique, Japanese kokai publication hei 2-4705 communique, various two cyclopentadiene titanium compounds of putting down in writing in the Japanese kokai publication hei 5-83588 communique (titanocene), dicyclopentadienyl-Ti-biphenyl for example, dicyclopentadienyl-Ti-two-2,6-two fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4-two-fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4,6-trifluoro-benzene-1-base, dicyclopentadienyl-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, dicyclopentadienyl-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, two-methyl cyclopentadienyl-Ti-two-2,6-two fluorobenzene-1-base, two-methyl cyclopentadienyl-Ti-two-2,4,6-trifluoro-benzene-1-base, two-methyl cyclopentadienyl-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, two-methyl cyclopentadienyl-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, Japanese kokai publication hei 1-304453 communique, iron-aromatic hydrocarbons of putting down in writing in the Japanese kokai publication hei 1-152109 communique (arene) complex compound etc.

As six aryl united imidazoles, for example can enumerate the special fair 6-29285 communique of Japan, No. the 3479185th, United States Patent (USP), No. the 4311783rd, United States Patent (USP), United States Patent (USP) waits all cpds of putting down in writing in each instructions No. 4622286, specifically can enumerate 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-bromophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (neighbours, right-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (m-methoxyphenyl) bisglyoxaline, 2,2 '-two (o, o '-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (ortho-nitrophenyl base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-methyl-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (adjacent trifluorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline etc.

As the organic boronic salt compound, Japanese kokai publication sho 62-143044 communique is for example arranged, Japanese kokai publication sho 62-150242 communique, Japanese kokai publication hei 9-188685 communique, Japanese kokai publication hei 9-188686 communique, Japanese kokai publication hei 9-188710 communique, TOHKEMY 2000-131837 communique, TOHKEMY 2002-107916 communique, No. 2764769 communique of patent, each communique and Kunz such as TOHKEMY 2002-116539 communique, Martin " RadTech ' 98.Proceeding April 19-22; 1998, Chicago " etc. in the organic borate of record, Japanese kokai publication hei 6-157623 communique, Japanese kokai publication hei 6-175564 communique, organic boron sulfonium complex compound of putting down in writing in the Japanese kokai publication hei 6-175561 communique or organic boron oxygen sulfonium (boron oxosulfonium) complex compound, Japanese kokai publication hei 6-175554 communique, organic boron iodine (boron iodonium) complex compound of putting down in writing in the Japanese kokai publication hei 6-175553 communique, You Ji Peng Phosphonium (boronphosphonium) complex compound of putting down in writing in the Japanese kokai publication hei 9-188710 communique, Japanese kokai publication hei 6-348011 communique, Japanese kokai publication hei 7-128785 communique, Japanese kokai publication hei 7-140589 communique, Japanese kokai publication hei 7-306527 communique, organic boron transition metal coordination complexes of putting down in writing in the Japanese kokai publication hei 7-292014 communique etc. etc.

As the example of two sulphones, can enumerate compound of putting down in writing in Japanese kokai publication sho 61-166544 communique, the TOHKEMY 2002-328465 communique etc.

As oxime ester compound, can be set forth in the compound of putting down in writing in J.C.S.Perkin II (1979) 1653-1660, J.C.S.Perkin II (1979) 156-162, Journal of Photopolymer Science andTechnology (1995) 202-232, the TOHKEMY 2000-66385 communique, the compound of in TOHKEMY 2000-80068 communique, Japanese Unexamined Patent Application Publication 2004-534797 communique, putting down in writing etc.As object lesson, IRGACURE OXE-01, the OXE-02 etc. of preferred Ciba company (Ciba JapanK.K.) system.

As salt compound, for example can be set forth in S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal etc., Polymer, diazonium (diazonium) salt of record in 21,423 (1980), No. 4069055 instructions of United States Patent (USP), the ammonium salt of record in the Japanese kokai publication hei 4-365049 communique etc., No. 4069055 instructions of United States Patent (USP), record De phosphonium salt in each instructions of No. 4069056 instructionss of United States Patent (USP), No. 104143 instructions of European patent, Japanese kokai publication hei 2-150848 communique, the salt compounded of iodine of putting down in writing in each communique of Japanese kokai publication hei 2-296514 communique etc.

The salt compounded of iodine that the present invention can preferably use is a diaryl group iodized salt, from the viewpoint of stability, preferably by electron donating group-substituted such as 2 above alkyl, alkoxy, aryloxy group.

As the sulfonium salt that can use in the present invention, can enumerate No. 370693 instructions of Europe patent, No. 390214 instructionss of European patent, No. 233567 instructionss of European patent, No. 297443 instructionss of European patent, No. 297442 instructionss of European patent, No. 4933377 instructions of United States Patent (USP), No. 4760013 instructionss of United States Patent (USP), No. 4734444 instructionss of United States Patent (USP), No. 2833827 instructionss of United States Patent (USP), No. 2904626 instructions of Deutsche Bundespatent, No. 3604580 instructionss of Deutsche Bundespatent, put down in writing in each instructions of No. 3604581 instructionss of Deutsche Bundespatent sulfonium salt.From the viewpoint of stability and sensitivity, preferably replaced by the electron attractivity group.Hami paricular value of electron attractivity group is preferably greater than 0.As the example of preferred electron attractivity base, can enumerate halogen atom, carboxylic acid etc.

In addition, as other preferred sulfonium salt, can enumerate the sulfonium salt that a substituting group in the triarylsulfonium salt has tonka bean camphor structure or anthraquinone ring and absorption is arranged more than 300nm.As another preferred sulfonium salt, can also enumerate triarylsulfonium salt and have aryloxy group (aryloxy) or arylthio have absorption as substituting group and more than 300nm sulfonium salt.

In addition, as the example of salt compound, can enumerate J.V.Crivello etc., Macromolecules, 10 (6), 1307 (1977), J.V.Crivello etc., J.PolymerSci., PolymerChem.Ed., selenium (selenonium) salt of 17,1047 (1979) middle records and C.S.Wen etc., Teh, Proc.Conf.Rad.Curing ASIA, De Arsenic salt salt such as (arsonium) etc. is put down in writing in p478 Tokyo in October (1988).

As the example of acylphosphanes (oxide) compound, can enumerate IRUGACURE 819, DAROCURE 4265, DAROCURE TPO of Ciba corporate system etc.

Example as Photoepolymerizationinitiater initiater; from the viewpoint of exposure sensitivity, be preferably selected from the trihalomethyl group compound in triazine class; the benzyl dimethyl ketal compound; alpha-hydroxyacetone compounds; the alpha-amido ketonic compound; the acylphosphanes compound; the phosphine oxide compound; metallocene compound; oxime compound; triallyl imidazole dimer (triarylimidazole dimer); salt compound; benzothiazole compound; benzophenone cpd; acetophenone compound and derivant thereof; cyclopentadiene-benzene-iron complex and salt thereof; Lu is for the compound in Jia oxadiazole compound and the 3-aryl substituted cumarin compound.

And then preferred trihalomethyl group triaizine compounds, alpha-amido ketonic compound, acylphosphanes compound, phosphine oxide compound, oxime compound, triallyl imidazole dimer, salt compound, benzophenone cpd, acetophenone compound, the most preferably at least a compound in trihalomethyl group triaizine compounds, alpha-amido ketonic compound, oxime compound, triallyl imidazole dimer, the benzophenone cpd.

The content of Photoepolymerizationinitiater initiater with respect to all solid state composition in the dyed layer, is preferably 0.1 quality %～20 quality %, and more preferably 0.5 quality %～15 quality % are preferably 1 quality %～10 quality % especially.If the content of Photoepolymerizationinitiater initiater in described scope, then can obtain good sensitivity and pattern formation property.

Other composition

In addition, for being used for photosensitive coloring composition of the present invention, except mentioned component, also can use various known adjuvants according to purpose.

Below, above-mentioned adjuvant is described.

Spreading agent

Photosensitive coloring composition among the present invention also can contain macromolecule dispersing agent (macromolecule dispersing agent beyond the macromolecular compound of above-mentioned coverage pigment).Described macromolecule dispersing agent is the resin of weight-average molecular weight in 3000～100000 scopes.And then preferred acid number is 20mgKOH/g～300mgKOH/g.Sometimes above-mentioned specific macromolecule dispersing agent simply is called " dispersion resin ".

Dispersion resin of the present invention is that the dispersing of pigments agent that can enumerate as above-mentioned colorant or the black matrix of aftermentioned form the compound that the spreading agent with the opacifier in the dark composition of photonasty (black matrix formation pigment) works.

Dispersion resin must have specific acid number, therefore preferably has the macromolecular compound of acidic groups.

Macromolecular scaffold as this macromolecular compound, be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, the urethane polymkeric substance, acylamide polymer, epoxide polymer, silicone (silicone) base polymer and their modifier or multipolymer [for example comprise polyethers/polyurethane copolymer, (random copolymerss such as the multipolymer of polyethers/polymer of vinyl monomer, segmented copolymer, in the graft copolymer any)] at least a kind, further be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, in urethane polymkeric substance and their modifier or the multipolymer at least a kind, special preferred vinyl polymer of monomers or multipolymer.

As the method that in above-mentioned macromolecular scaffold, imports acidic groups, will contain the method for monomer copolymerization of acidic groups or the method for behind the above-mentioned macromolecular scaffold of polymerization, utilizing high molecular weight reactive to import in the time of for example can being set forth in the above-mentioned macromolecular scaffold of polymerization.

As the monomer that contains acidic groups, for example can enumerate (methyl) acrylic acid; butenoic acid (crotonic acid); itaconic acid (itaconic acid); maleic acid (maleic acid); fumaric acid (phmalic acid); cinnamic acid (cinnamic acid); acrylic acid dimer (acrylic aciddimer); vinyl benzoic acid; styrene sulfonic acid; 2-acrylamide-2-methyl propane sulfonic acid; mono phosphoric acid ester (methyl) acryloyl group ethyl ester or 2-hydroxyethyl methacry-late etc. contain reactions such as the monomer of alcohol hydroxyl group and cyclic acid anhydrides such as maleic anhydride or phthalic anhydride and monomer of obtaining etc.

In addition, the macromolecular compound with acidic groups can also be the compound that is formed by the copolymerization of vinyl monomer composition.

As above-mentioned vinyl monomer, there is not particular restriction, the ester class of for example preferred (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol, phenylethylene, (methyl) vinyl cyanide etc.

As above-mentioned " acidic groups ", can preferably enumerate carboxylic acid group, sulfonic group, a sulfate group, phosphate, Monophosphate base, boronate, further optimization acid's base, sulfonic group, a sulfate group, phosphate, Monophosphate base, special optimization acid's base, sulfonic group, phosphate.

In order to improve dispersiveness, macromolecule dispersing agent of the present invention also preferably contains the have basic nitrogen atom group of (basic nitrogen atom).As above-mentioned group, for example can preferably enumerate amino (NH with basic nitrogen atom ₂), substituted imido (NHR ⁸Or-NR ⁹R ¹⁰Here, R ⁸, R ⁹And R ¹⁰Represent independently that respectively carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7), the guanidine radicals (guanidyl) of following chemical formula (a1) expression or the amidino groups (amidinyl) of following chemical formula (a2) expression etc.

In the above-mentioned chemical formula (a1), R ¹¹And R ¹²Represent that independently of one another carbon number is that 1～20 alkyl, carbon number aryl or the carbon number more than 6 is aralkyl more than 7.

In the above-mentioned chemical formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7.

Wherein, amino (NH ₂), substituted imido (NHR ⁸Or-NR ⁹R ¹⁰Here, R ⁸, R ⁹And R ¹⁰Represent independently that respectively carbon number is 1～10 alkyl, phenyl or benzyl), the guanidine radicals shown in the above-mentioned chemical formula (a1) [in the chemical formula (a1), R ¹¹And R ¹²Represent independently that respectively carbon number is 1～10 alkyl, phenyl or benzyl], the amidino groups of above-mentioned chemical formula (a2) expression [in the chemical formula (a2), R ¹³And R ¹⁴Represent independently that respectively carbon number is 1～10 alkyl, phenyl or benzyl] etc. also contain by 1～200 hydrogen atom and 0～20 group that sulphur atom forms, they can not be substituted, and also can further have substituting group.

Other spreading agent

The photosensitive coloring composition that uses among the present invention also can be also with present known spreading agent (pigment dispersing agent) except using dispersion resin.

As known spreading agent (pigment dispersing agent), can enumerate macromolecule dispersing agent (for example daiamid and salt thereof, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic copolymer) and polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.

Macromolecule dispersing agent can be further divided into straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule (graft polymer), block type polymer (blockpolymer) on its structure.

Macromolecule dispersing agent is adsorbed in the surface of pigment, works to prevent aggegation again.Therefore, as preferred construction, can enumerate terminal-modified type macromolecule, graft type macromolecule, the block type polymer at grappling (anchor) position that has at surface of pigments.On the other hand, pigment derivative has by surface of pigments being carried out the effect that modification promotes that macromolecule dispersing agent adsorbs.

As the concrete example that can be used in known spreading agent of the present invention (pigment dispersing agent), can enumerate Bi Ke chemistry corporate system " Disperbyk-107 (carboxylate); 130 (polyamide); 161; 162; 163; 164,165,166,170 (high-molecular copolymers) "; EFKA corporate system " EFKA4047,4050,4010,4165 (polyurethane series), EFKA4330,4340 (segmented copolymers), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivates), 6750 (AZO pigments derivants) "; (the Ajinomoto Fine-Techno Co.; Inc.) system " AJISPER (アジスパ one) PB821 of aginomoto fine chemistry company, PB822 "; (the Kyoeisha Chemical Co.; Ltd.) system " FLOWLEN (Off ロ one レ Application) TG-710 (urethane ester homopolymer) "; " POLYFLOW (Port リ Off ロ one) No.50E of chemical company of common prosperity society, No.300 (acrylic acid series copolymer) "; nanmu originally changes into system " DISPARLON (DISPARLON) #7004 (polyether ester) of company (Kusumoto Chemicals Ltd.), DA-703-50, DA-705, DA-725 "; the system " EMULGEN (エマ Le ゲ Application) 920 of KAO. Corp. SA (KAO Corporation), 930,935,985 (polyoxyethylene nonylplenyl ethers) "; " ACETAMIN (アセタミ Application) 86 (octadecane amine acetic acid esters) "; the system " SOLSPERSE5000 (phthalocyanine derivates) of Japanese Lubrizol Corp. (The Lubizol Corporation), 22000 (AZO pigments derivants), 13240 (polyesteramines), 3000,17000,27000 (terminal part has the macromolecule of function portion), 24000,28000,32000,38500 (graft type macromolecules) "; day Optical Chemical Company (Nikko ChemicalsCo., Ltd.) system " NIKKOL (ニ Star コ one Le) T106 (Tween-81), MYS-IEX (polyoxyl 40 stearate) " etc.

Above-mentioned known spreading agent can be as required with respect to dispersion resin be the i.e. uses in the scope of 1/10～1/1 (equivalent) of 10 quality %～100 quality %.

Surfactant

If pigment concentration increases, then the thixotropy of coating fluid (thixotropy) generally can become greatly, therefore is prone to the thickness inequality after coating or transfer printing photosensitive coloring composition form dyed layer (dyed layer is filmed) on the substrate.When particularly forming dyed layer (dyed layer is filmed) by slot coated method (slit coating), it is very important that dyed layer formation forms filming of homogeneous thickness with coating fluid levelling before dry.Therefore, preferably in above-mentioned photosensitive coloring composition, contain suitable surfactant.As above-mentioned surfactant, can preferably enumerate disclosed surfactant in TOHKEMY 2003-337424 communique, the Japanese kokai publication hei 11-133600 communique.

As the surfactant that is used to improve coating, can enumerate non-ionics, fluorine class surfactant, silicone surfactant etc.

As non-ionics, non-ionics such as for example preferred polyoxyethylene glycols, polyoxypropylene glycol class, polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, polyoxypropylene alkyl ether, polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitol anhydride alkyl esters, a glycerine alkyl esters.

As the concrete example of non-ionics, can enumerate polyoxyalkylene diols classes such as polyoxyethylene glycol, polyoxypropylene glycol; Polyoxyalkylene alkyl classes such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polyoxyethylene polystyrene ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyrene ether, polyoxyethylene nonylplenyl ether; Polyoxyalkylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate; Non-ionics such as sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester class.

As their object lesson, can enumerate ADEKA PLURONIC series, ADEKANOL series, TETRONIC series (above is Ai Deke Co., Ltd. system), EMULGEN series, RHEODOL series (above is Kao Corp's system), ELEMINOL series, NONIPOL series, OCTAPOL series, DODECAPOL series, NEWPOL series (above is Sanyo Chemical Industries Co., Ltd.'s system), PIONIN series (above is Zhu Ben's Oil Corporation's system), NISSAN NONION series (above is NOF Corp's system) etc.Can suitably use their commercially available product.Preferred HLB value (Hydrophile-Lipophile Balance) is 8～20, more preferably 10～17.

As fluorine class surfactant, the compound that can preferably use endways, the arbitrary at least position in main chain and the side chain has fluoro-alkyl or fluoro alkylidene.

As concrete commercially available product, for example can enumerate, MEGAFAC (メガ Off ア Star Network) F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F183, MEGAFAC 780, MEGAFAC 781, MEGAFAC R30, MEGAFAC R08 (big Japanese ink (Co., Ltd.) (DICCorporation) is made), FLUORAD (FLUORAD) FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (Sumitomo 3M (Co., Ltd.) (Sumitomo 3M Limited) system), SURFLON (サ one Off ロ Application) S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLONS-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (Asahi Glass (Co., Ltd.) (Asahi Glass Co., Ltd.) system), EFTOP (エ Off ト Star プ) EF351, EFTOP EF 352, EFTOP EF 801, EFTOP EF802 (JEMCO (Co., Ltd.) (JEMCO Inc.) system) etc.

As the silicone-based surfactant, for example can enumerate, Toray Silicone (ト one レシリコ one Application) DC3PA, Toray SiliconeDC7PA, Toray SiliconeSH11PA, ToraySiliconeSH21PA, Toray SiliconeSH28PA, Toray SiliconeSH29PA, ToraySiliconeSH30PA, Toray SiliconeSH-190, Toray SiliconeSH-193, ToraySiliconeSZ-6032, Toray SiliconeSF-8428, Toray SiliconeDC-57, Toray SiliconeDC-190 (more than, east (the DoW Corning Toray Silicone Co. of beautiful DOW CORNING organosilicon Co., Ltd. (Co., Ltd.), Ltd.) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (more than, Momentive Performance Materials Japan system) etc.

The consumption of these surfactants is for to be preferably below 5 mass parts with respect to coating fluid 100 mass parts that are used to form dyed layer, more preferably below 2 mass parts.When the amount of surfactant was following above 5 mass parts, coating caused rough surface, the easy variation of flatness easily when dry.

For the development of the alkali dissolution that promotes uncured portion, can add organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000 with further raising light thermosetting composition.Particularly, for example can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid (enanthic acid), aliphatics monocarboxylic acid such as sad; Oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid (pimelic acid), suberic acid (suberic acid), azelaic acid (azelaic acid), decanedioic acid (sebacic acid), brassylic acid (brasylic acid), methylmalonic acid (methylmalonic acid), ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid aliphatic dicarboxylic acids such as (citraconic acid); The third three acid (tricarballylic acid), aconitic acid (aconitic acid), camphoronic acid aliphatics tricarboxylic acids such as (camphoronic acid); Benzoic acid, toluic acid (toluicacid), cumfrey (cuminic acid), 2,3-mesitylenic acid (hemellitic acid), sym-trimethyl benzene acid aromatic series monocarboxylic acids such as (trimellitic acid); Phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid (trimesic acid), mellophanic acid (mellophanic acid), Pyromellitic Acid aromatic series polybasic carboxylic acids such as (pyromellitic acid); Phenylacetic acid, phenoxyacetic acid, methoxybenzene ethoxyacetic acid, hydratropic acid (hydratropicacid), hydrocinnamic acid (hydrocinnamic acid), mandelic acid (mandelic acid), phenyl succinic acid, atropic acid (atropic acid), cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetate (cinnamylidene acetate), coumaric acid (cumaric acid), umbellic acid (umbellic acid) wait other carboxylic acids.

Alkoxy silane (alkoxysilane) compound

Be used for photosensitive coloring composition of the present invention,, also can contain siloxy silane compound, more preferably silane coupling agent from the viewpoint of raising with the adaptation of substrate.

Silane coupling agent preferably have alkoxysilyl as can with the chemically combined hydrolization group of inorganic material; preferably can interact or become key and show (methyl) acryloyl group, phenyl, sulfydryl, the epoxy radicals silicone hydride of compatibility with organic resin; wherein, more preferably (methyl) acryloyl group propyl trimethoxy silicane.

Addition when using silane coupling agent is preferably the scope of 0.2～5.0 quality % in the total solid state component in the dyed layer that the present invention uses, more preferably 0.5～3.0 quality %.

Be total to sensitizer

The photosensitive coloring composition that the present invention uses also preferably contains common sensitizer as required.Altogether sensitizer of the present invention has further raising sensitizing coloring matter and/or initiating agent to the sensitivity of active radioactive ray or suppress the effects such as polymerization inhibition of oxygen to polymerizable compound.

Example as this common sensitizer; can enumerate for example 3173 pages (1972) of work such as M.R.Sander " Journal of Polymer Society " the 10th volume of amine; Japanese Patent Publication 44-20189 communique; Japanese kokai publication sho 51-82102 communique; Japanese kokai publication sho 52-134692 communique; Japanese kokai publication sho 59-138205 communique; Japanese kokai publication sho 60-84305 communique; Japanese kokai publication sho 62-18537 communique; Japanese kokai publication sho 64-33104 communique; the compound of record etc. among No. 33825, the Research Disclosure specifically can be enumerated triethanolamine; the ESCAROL 507 ethyl ester; to the formoxyl xylidin; to methyl sulfo-xylidin etc.

As other examples that are total to sensitizer, can enumerate mercaptan and thioether class, for example the mercaptan compound of putting down in writing in Japanese kokai publication sho 53-702 communique, Japanese Patent Publication 55-500806 communique, the Japanese kokai publication hei 5-142772 communique, the disulfide compound of Japanese kokai publication sho 56-75643 communique etc. specifically can be enumerated 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc.

As other examples of sensitizer altogether, can enumerate the sulphur compound put down in writing in the hydrogen donor put down in writing in the organometallics put down in writing in amino-acid compound (for example N-phenylglycine etc.), the Japanese Patent Publication 48-42965 communique (for example tributyltin acetate (tributyl tin acetate) etc.), the Japanese Patent Publication 55-34414 communique, the Japanese kokai publication hei 6-308727 communique (for example trithiane etc.) etc.

Viewpoint from the curing rate that improves polymerization growth rate and chain transfer balance, the content of these common sensitizers is preferably the scope of 0.1～30 quality % of quality of total solid state component of solidification compound, the more preferably scope of 0.1 quality %～25 quality %, the more preferably scope of 0.5～20 quality 5%.

(polymerization inhibitor)

Among the present invention, in the manufacturing of photosensitive coloring composition or in preserving,, preferably add a spot of thermal polymerization inhibitor in order to stop the unnecessary thermal polymerization of compound with olefinic unsaturated double-bond that can polymerization.

The example of the thermal polymerization inhibitor that can use as the present invention, can enumerate quinhydrones (hydroquinone), p methoxy phenol, BHT, pyrogallol (pyrogallol), tert-butyl catechol (t-butyl catechol), benzoquinones (benzoquinone), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), the inferior cerium salt of N-nitroso-phenyl azanol, phenoxazine, phenothiazine etc.

The addition of thermal polymerization inhibitor is preferably with respect to the quality in the dyed layer and is about 0.01 quality %～about 5 quality %.In addition, the advanced higher fatty acid derivative etc. that can also add docosanoic acid or docosane acid amides and so on as required is used for preventing that the polymerization that is caused by oxygen from suppressing, and concentrates on the surface of photographic layer in also can the dry run after coating.The addition of advanced higher fatty acid derivative is preferably about 0.5 quality %～about 10 quality % of total composition.

(plastifier)

Among the present invention,, can add inorganic filler or plastifier, wall, can add sense fat agent etc. for the black liquid that improves the photographic layer surface in order to improve the rerum natura of dyed layer.

As plastifier, for example can enumerate dioctyl phthalate, phthalic acid two (dodecyl) ester, triethylene glycol dieaprylate, dimethyl glycol phthalic ester, tricresyl phosphate (tricresyl phosphate), dioctyl adipate, dibutyl sebacate, glyceryl triacetate etc.Using under the situation of bonding agent, can add gross mass with respect to compound with olefinic unsaturated double-bond and bonding agent and be the plastifier below the 10 quality %.

By using mentioned component, photosensitive coloring composition of the present invention is good with high sensitivity curing and storage stability.In addition, also show high adaptation to substrate.Therefore, the photosensitive coloring composition that contains above-mentioned various compositions can be preferred for color filter.

The dark composition of photonasty

Then, the dark composition of the photonasty that is preferred for color filter of the present invention and manufacture method thereof is described.

The dark composition of described photonasty preferably contains opacifier, bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater and solvent, also can contain other adjuvant such as spreading agent or surfactant as required.

Opacifier

As described opacifier, except above-mentioned described colorant, can also enumerate the particulate of carbon black (carbon black), titanium black (titanium black), metal particle, metal oxide, sulfide etc.As long as the optical concentration (OD value) that makes the black matrix of color filter of the present invention more than 3.5, then without limits, wherein especially preferably makes optical concentration (OD value) more than 3.5, the carbon black that the balance of light-proofness and cost is good easily.

They can use or make up multiple use as required separately.For example, carbon black uses separately, or mixes with organic pigment, and carbon black and organic pigment share etc.

As the shading material, all the time, the pigment that share shielding visible region more than at least 2 kinds is as black colorant.As these pigment, can enumerate the pigment of record in TOHKEMY 2005-17716 communique [0038]～[0040], TOHKEMY 2005-17521 communique [0080]～[0088], about using these pigment to form the method for light shield layers, in Japanese kokai publication hei 7-271020 etc., have open.

In order further to strengthen shaded effect, in TOHKEMY 2000-147240, TOHKEMY 2000-143985, TOHKEMY 2005-338328, TOHKEMY 2006-154849 etc., developed carbon black, titanium is black or desirable light screening material such as graphite.In the present invention, from the viewpoint of light-proofness and cost, carbon black is one of preferred light screening material.

As the example of carbon black, preferred pigments is deceived (Pigment Black) 7 (carbon black).As carbon black, for example can enumerate, #2400 is deceived in Mitsubishi Chemical society (Mitsubishi Chemical Corporation) charcoal processing, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4010, #55, #52, #50, #47, #45, #44, #40, #33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, DIABLACK (DIABLACK) A, DIABLACK N220M, DIABLACK N234, DIABLACK I, DIABLACK LI, DIABLACK II, DIABLACK N339, DIABLACK SH, DIABLACK SHA, DIABLACKLH, DIABLACK H, DIABLACK HA, DIABLACK SF, DIABLACKN550M, DIABLACK E, DIABLACK G, DIABLACK R, DIABLACKN760M, DIABLACK LP; Carbon black Color Black FW200, Color Black FW2, Color Black FW1, Color BlackFW18, Color Black S170, Color BlackS160, Special Black6, SpecialBlack5, Special Black4, Special Black4A, PrintexU, PrintexV, Printex 140U, Printex 140V, the Printex35 of De Kusai company (Evonik Degussa Japan) system; Carbon black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, the BLACKPEARLS1400 of Cabot company (Cabot Corporation) system; Rising sun carbon company (Asahi Carbon Co., Ltd.) Zhi carbon black SUNBLACK900, SUNBLACK910, SUNBLACK930, SUNBLACK960, SUNBLACK970 etc.In addition, in order to increase resistance, in order to increase resistance, the above-mentioned carbon black after preferably covering with macromolecular compound.The size of the preferred single-particle of these carbon blacks is 10～100nm, more preferably 10～50nm.

Polymerizable compound

Polymerizable compound as the dark composition of photonasty of deceiving matrix formation usefulness preferably is set forth in the polymerizable compound that uses in the above-mentioned photosensitive coloring composition, preferred especially following compound.

As the polymerizable compound in the dark composition of photonasty, preferably have 2 above olefinic unsaturated double-bonds and the monomer or the homopolymer of addition polymerization under the irradiation of light.As this type of monomer and homopolymer, but can enumerate the ethene unsaturated group that in molecule, has at least 1 addition polymerization, and at boiling point under the normal pressure at the compound more than 100 ℃.As its example, can enumerate monofunctional acrylate or simple function methacrylates such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) isocyanuric acid ester, glycerine three (methyl) acrylate; (methyl) acroleic acid esterification after polyfunctional alcohol such as trimethylolpropane or glycerine and oxirane or the epoxypropane addition polyfunctional acrylic ester or multifunctional methacrylates such as compound.

Acid multifunctional smooth solidity compound also is preferred compound.As the multifunctional smooth solidity compound of acidity, can use (1) by having hydroxyl with dibasic acid anhydride and 3 monomer or oligomer modifications with glazing solidity functional group import the compound that carboxyl obtains, (2) have hydroxyl and 3 with the monomer or the oligomer of glazing solidity functional group and have glycidyl or the additions such as compound of isocyanate group and COOH base import compound that carboxyl obtains or (3) and import compound that sulfonic group obtains etc. by will have 3 aromatics modifications with glazing solidity functional group with the concentrated sulphuric acid or oleum by making.In addition, as the multifunctional smooth solidity compound of acidity, can also use the monomer that will contain acid multifunctional smooth solidity compound itself oligomer as repetitive.

As the example of the multifunctional smooth solidity compound of acidity, the compound that preferred following general formula (i), general formula are (ii) represented.In addition, general formula (i) and general formula (ii) in, when T or G were oxyalkylene group, the end of carbon atom side combined with R, X and W.

In the general formula (i), R represents (methyl) acryloxy, X represents-the COOH base or-OPO ₃H ₂Base.T represents oxyalkylene group, and here, the carbon number of alkylidene is 1～4.N is 0～20.

General formula (ii) in, W represent with general formula (i) in R or the identical implication of X, have the W more than 3 to have identical implication among 6 W with R.T synonym in G and the general formula (i).Z represents-O-or-OC=ONH (CH ₂) _qNHCOO-.P is 0～20, and q is 1～8.R, T, G, the W of a plurality of existence can be identical respectively in a part, also can be different.

The commercially available product of the acid multifunctional smooth solidity compound of (ii) representing as general formula (i) and general formula, (TOAGOSEI Co., Ltd.) system contains carboxyl 3 functional acrylate TO-756 and contains carboxyl 5 functional acrylate TO-1382 etc. for example can to enumerate Toagosei Co., Ltd.

Can also enumerate the urethanes esters of acrylic acid of putting down in writing in Japanese Patent Publication 48-41708 communique, Japanese Patent Publication 50-6034 communique and the Japanese kokai publication sho 51-37193 communique; The polyester acrylate class of putting down in writing in Japanese kokai publication sho 48-64183 communique, Japanese Patent Publication 49-43191 communique and the Japanese Patent Publication 52-30490 communique; Polyfunctional acrylic ester or methacrylate as the epoxy acrylate class of epoxy resin and (methyl) acrylic acid reaction product etc.Wherein, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, above-mentioned carboxylic 5 functional acrylates etc.In addition, can also preferably enumerate " the polymerizable compound B " that puts down in writing in the Japanese kokai publication hei 11-133600 communique.

Form content as black matrix, be preferably 5～50 quality % in total solid state component of the dark composition layer of photonasty, more preferably 7～40 quality %, more preferably 10～35 quality % with the polymerizable compound in the dark composition of photonasty.

Identical in the photosensitive coloring composition of the bonding agent that the dark composition of photonasty uses, polymerization initiator, solvent, other adjuvants etc. and the invention described above, preferred content is also identical.

Color filter and manufacture method thereof

The manufacture method of color filter of the present invention comprises: resin black matrix forms operation, forms resin black matrix on substrate; Colored pattern forms operation, being formed with the described photosensitive coloring composition formation dyed layer of the present invention of coating on the substrate of described resin black matrix, formed dyed layer is carried out pattern exposure, and the dyed layer with pattern exposure develops again, forms colored pattern.

In the manufacture method of color filter of the present invention, in order to use photosensitive coloring composition of the present invention to form colored pattern, under the situation of not appending operations such as grinding or finishing coat are provided with, make following color filter with low-cost and simple method, in the described color filter in overlapping projection that reduces colored pattern of resin black matrix and colored pattern.

In addition, color filter of the present invention is that manufacture method manufacturing by the color filter of the invention described above forms.Therefore, can reduce the projection of colored pattern of the overlapping portion of resin black matrix and colored pattern, when being used for liquid crystal indicator, can suppress the orientation confusion of liquid crystal, improve contrast.

Below, at first resin black matrix is formed operation and describe, then, colored pattern formation operation, substrate and other be describeds.

Resin black matrix forms operation

It is the operation that forms resin black matrix on substrate that described resin black matrix forms operation.

Resin black matrix

Among the present invention, " resin black matrix " is meant the black matrix that is formed by the material that contains resin.

Resin black matrix for example can be formed on the clathrate pattern that is divided into a plurality of pixel regions on the substrate.

There is no particular limitation for the optical concentration of resin black matrix of the present invention (OD (optical density) value), is preferably more than 2.0 below 8.0, more preferably more than 3.0 below 8.0, more preferably more than 4.0 below 6.0.If, then can suppressing the demonstration of degradation display device under the contrast more than 2.0, reduces optical concentration.

Illustrated that optical concentration described here is meant that ISOVisual sees through optical concentration.Measure the analyzer that ISOVisual sees through optical concentration as can be used in, for example can enumerate slope field index Engineering Co., Ltd (SAKATA INX ENG.Co., X-Rite361T Ltd.) (V).

Guarantee the viewpoint of brightness from high apertureization, the live width of resin black matrix of the present invention is preferably 5 μ m～30 μ m.

The thickness of resin black matrix as mentioned above, is preferably 0.5 μ m～2.0 μ m, more preferably 0.8～1.5 μ m.

If this thickness is more than the 0.5 μ m, then the OD value is easier uprises, and can improve light-proofness more.In addition, if this thickness is below 2.0 μ m, the inclination on the chromatograph surface during then stacked chromatograph is precipitous, the bad and light leak that causes of the orientation that can more effectively suppress liquid crystal.

In addition, among the present invention, with being parallel to Width and cutting in the formed cut surface of described resin black matrix perpendicular to the plane of real estate, the shape of the end of described resin black matrix is the shape (the present invention, this shape be called " taper ") of thickness from the distolateral attenuation gradually of the described resin black matrix of described resin black matrix central portion side direction.The above-mentioned shape of doing then can further reduce the angle height of colored pattern.

Fig. 2 illustrates with being parallel to Width and cross section during perpendicular to the plane cutting resin black matrix of orientation substrate.

As shown in Figure 2, in the end of resin black matrix 12, from described resin black matrix center side distolateral towards described resin black matrix, thickness is attenuation gradually.That is, the end of resin black matrix 12 forms described preferred shape, i.e. taper.

Among Fig. 2, the point that the thickness of resin black matrix 12 is begun attenuation is expressed as P, the resin black matrix end is expressed as a Q, the maximal value of the thickness of resin black matrix 12 is expressed as maximum film thickness t, the length on the direction that is parallel to substrate 10 surfaces of described end (that is, from a P to putting the distance of Q on the direction that is parallel to substrate 10 surfaces) is expressed as length L.

Usually, the described length L of resin black matrix or ratio (L/t) are big more, and the angle height of colored pattern has the tendency of reduction more.On the contrary, if length L or ratio (L/t) are little, when then using resin black matrix, the angle height of colored pattern has the tendency that uprises.

In the manufacture method of color filter of the present invention, owing to use the photosensitive coloring composition of the present invention of the angle height can reduce colored pattern, thereby especially effectively (find that the effect that the angle height reduces is effective especially) when using the little resin black matrix of length L or ratio (L/t).

Particularly, from for manifest more reduce the angle height the viewpoint of effect, preferred length L is below the 3.0 μ m, more preferably below the 2.0 μ m.From same viewpoint, preferred ratio (L/t) is below 3.0, and more preferably ratio (L/t) is below 2.0.

Resin black matrix forms in the operation and preferably comprises at least: dark layer forms operation, and the dark composition of usability photosensitiveness forms dark layer on substrate; Exposure process is with described dark layer exposure; And developing procedure, the described dark layer development after the described exposure is formed black matrix pattern.

Resin black matrix forms in the operation, except above-mentioned each operation, also can roasting procedure (prebake conditions operation, back roasting procedure) be set according to other needs and wait other operation.

Illustrated, in the following description, sometimes " resin black matrix " is called simply " black matrix ".

Dark layer forms operation

In this operation, the dark composition of usability photosensitiveness forms dark layer on substrate.For substrate, as mentioned above.

On substrate, form the method for dark layer, for example have, wait by coating and on substrate, give photonasty dark method for compositions.

As on substrate, giving photonasty dark method for compositions, can suitably use slot coated (below, be also referred to as the slot coated method), various adding methods such as ink-jet method, rotary coating (below, be also referred to as " spin-coating method "), curtain coating coating, roller coat cloth, silk screen print method.Wherein, from the viewpoint of precision and speed, preferred slot coated.From improving the viewpoint of coating, preferably before carrying out above-mentioned coating, use ultraviolet ray or various detergent remover cleaning base plates.

In addition, preferably will on interim supporter, give filming of forming in advance, be transferred to the method on the substrate by above-mentioned adding method.

About printing transferring method, preferably use the method for making of record in paragraph [0096]～[0108] of paragraph [0023], [0036]～[0051] or TOHKEMY 2006-47592 communique of TOHKEMY 2006-23696 communique in the present invention.

As the stacked machine (laminator) that uses in the transfer printing, can preferably use the stacked machine of putting down in writing in the stacked machine of large-scale double applying (Japanese original text: Er Ding Stickers ラミネ one タ) put down in writing among Figure 24 of WO2006-4225 or the international application no JP2007/069132 communique.Use these stacked functions to obtain high productivity.

Thickness (for example coating thickness) when giving the dark composition of photonasty on the substrate can be done suitable adjustment according to the design load of the thickness of formed black matrix, generally is preferably 0.5 μ m～2.0 μ m, more preferably 0.8 μ m～1.5 μ m.

Exposure process

In exposure process, will form the dark layer that forms in the operation at above-mentioned dark layer and expose across the mask pattern (mask pattern) of regulation, form pattern (patterning) (during minus, only making by light-struck coated film partly solidified).As the radioactive ray that can in exposure, use, especially preferably use ultraviolet rays such as g line, h line, i line.Exposure is preferably 5～500mJ/cm ², 10～300mJ/cm more preferably ², most preferably be 10～200mJ/cm ²

Exposure machine can adopt proximity (proximity) exposure machine, also can adopt mirror surface projection formula (mirror projection) exposure machine or step-by-step movement (stepper) exposure machine.

Developing procedure

Then, by carrying out the alkali development treatment, for example when the dark composition of photonasty is minus, can make in the above-mentioned exposure light not illuminated portion be dissolved in aqueous alkali, the residual light part of solidifying only.

As developer solution, adopt organic base developer solution or inorganic base developer solution or its mixed solution.

As the alkaline agent that uses in the developer solution, can enumerate for example NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline (choline), pyrroles (pyrrole), piperidines (piperidine) and 1,8-diazabicyclo-[5,4,0]-7-undecylene (1,8-diazabicyclo-[5,4,0]-7-undecene) waits organic basic compound, preferably these alkaline agents are diluted to 0.001～10 quality % with pure water, being preferably the alkaline aqueous solution that 0.01～1 quality % obtains uses as developer solution.In addition, when using this developer solution that forms by alkaline aqueous solution, general usefulness pure water rinsing (rinse) after development.

The section shape of the end behind the roasting procedure is the viewpoint of taper, the present invention before roasting procedure described later, preferred so that in the above-mentioned dark layer lower end form black matrix pattern with respect to the mode that upper end is positioned at the position of-3.0～+ 3.0 μ m.

Here, after " lower end is positioned at the position of-3.0～+ 3.0 μ m with respect to upper end in the dark layer " is meant that the black matrix pattern that will form is with Width that is parallel to this pattern and the face cutting perpendicular to substrate surface, the following state in the cross section of an end of this pattern.

Promptly, upper end (for example, the some P among Fig. 6) with this pattern is a benchmark, make this pattern center side for negative, this pattern outside (side that departs from above-mentioned central portion) is timing, and the position of the lower end of the black matrix pattern on the direction parallel with substrate surface (for example, Fig. 6 mid point Q) is positioned at the scope of-3.0～+ 3.0 μ m.

The definition of " top " " bottom " of dark layer or black matrix pattern as described later.

The cross sectional shape of cross sectional shape, the particularly end of black matrix pattern can utilize each condition of exposure, development and prebake conditions described later to control.Once more, at first the cross sectional shape of the black matrix pattern end behind the developing procedure is elaborated.

In the formation operation of black matrix, when the dark layer after the exposure is developed, when the surface of dark layer (is referred to not the face with substrate contacts; Below in black matrix address too) and from this surface to thickness (dark layer is along the length of substrate normal direction) 1/3rd inner (hereinafter referred to as " dark layer top " with interior layer.Similarly will be in black matrix from the surface of black matrix to thickness 1/3rd with interior being called " black matrix top ") develop and the back side to dark layer (refers to the face with substrate contacts; Below black matrix is called " back side of black matrix " similarly) and 2/3rds inner (hereinafter referred to as " dark layer bottom " with interior layer from this back side to respect to the thickness of dark layer.Being also referred to as " black matrix bottom " at black matrix) when developing for equal extent, the cross sectional shape of dark layer for example is an approximately perpendicular shape (approximate rectangular shape) shown in Figure 3.

Relative therewith, compare with the development that carry out on dark layer top with surface dark layer, too much sometimes or not enough to the development that the back side of dark layer and the dark composition of photonasty carry out.When development was too much, the dark layer bottom was etat lacunaire, and when cutting along the Width of deceiving matrix as if the substrate that will be formed with dark layer (black matrix), the cross sectional shape of dark layer for example is a undercut (back taper (reverse taper)) shown in Figure 4.On the other hand, when underdevelop, the dark layer bottom is outstanding state, and when cutting along the Width of deceiving matrix as if the substrate that will be formed with dark layer (black matrix), the cross sectional shape of dark layer for example is taper (just taper) shown in Figure 5.

In addition, behind this developing procedure, before the roasting procedure described later, when back draught shown in Figure 4 was big, in developing procedure, the teat on top was easily damaged, was easy to generate black matrix plane shape defect.Therefore, the size of back draught is preferably below the 3 μ m, and promptly with respect to the upper end in the dark layer, lower end is preferably placed at the position of-3.0～0 μ m.In addition, when positive tapering shown in Figure 5 is big, because underdevelop, easily the part that should remove dark layer residual residue, therefore, the size of positive tapering is preferably below the 3 μ m, promptly with respect to the upper end in the dark layer, lower end is preferably placed at the position of 0～3.0 μ m.Therefore, most preferred shape is that the end of above-mentioned dark layer shown in Figure 3 is approximately perpendicular shape.Preferably, after development, be approximately perpendicular shape as mentioned above, carry out back baking then and produce the heat limit (Hot ダレ) of collapsing, form circular-arc cross sectional shape.

In fact, there is change in what owing to the unequal of operation, be positioned at the cross sectional shape of position of-3.0～+ 3.0 μ m with respect to upper end just no problem for the lower end that is shaped as of the dark layer after as long as develop, and more preferably lower end is positioned at the cross sectional shape of the position of-2.0～+ 2.0 μ m with respect to upper end.

In order to make the end of above-mentioned dark layer behind this developing procedure, before the aftermentioned roasting procedure is vertical cross-section shape shown in Figure 3, and it is very important suitably to regulate development conditions, by changing development conditions, can regulate cross sectional shape.Roughly,, be back taper, otherwise when under slightly weak condition, developing, be positive taper comparing with development conditions commonly used when developing under the slightly strong condition.

Stronger condition is meant higher temperature, longer time, more flow, higher spray pressure etc., otherwise, more weak condition is meant lower temperature, shorter time, flow still less, lower spray pressure etc., and wherein, the adjusting of temperature and time is particularly important.

Particularly, from regulating the viewpoint of cross sectional shape with good precision, development temperature is preferably 20～35 ℃, more preferably 20～30 ℃.Development time is preferably 20～120 seconds, more preferably 30～70 seconds.

Wherein, as the preferred compositions of development temperature and development time, for example can be set forth in 23 ℃ of developments 40～70 seconds down of temperature, develop 30～60 seconds down for 25 ℃ in temperature.

Press about spray,, be preferably 0.01～0.5MPa, more preferably 0.05～0.3MPa, more preferably 0.1～0.3MPa from preventing the black damaged viewpoint of matrix.

In order to regulate cross sectional shape more subtly, preferably form in the operation and append prebake conditions operation described later at black matrix.

Back roasting procedure

Then, black matrix pattern is implemented to be referred to as the heat treated of back baking.Back baking is in order to make the heat treated after the completely crued development of the dark composition of photonasty, to carry out 150～260 ℃ heat curing usually and handle.

Back baking temperature is preferably 150～260 ℃, more preferably 180～260 ℃, most preferably is 200～240 ℃.Back stoving time is preferably 10～150 minutes, and further preferred 20～120 minutes, most preferably 30～90 minutes.

Behind above-mentioned developing procedure, to the end of the end of above-mentioned dark layer vertical cross-section shape approximate shown in Figure 3, in above-mentioned condition and range, toast, cross sectional shape can be adjusted to approximate shown in Figure 7 circular-arc.This be because, by baking processing the dark composition of the photonasty after developing is heated, before the dark composition full solidification of photonasty, be in low viscosity state, so edge part takes place to curl temporarily under capillary effect, be cured again, thereby form above-mentioned shape.

The curling easiness at the edge that causes by the heating after this development (below be sometimes referred to as " heat collapse limit ") can with the dark composition of photonasty form and prebake conditions condition, conditions of exposure or development conditions change.Usually, in the ratio of components of the dark composition of photonasty, compare with binder polymer described later, the concentration of opacifier is low more, the easy more heat limit of collapsing, and the concentration of opacifier is high more, the difficult more heat limit of collapsing.For example, the thickness after baking is when being 1.4 μ m, and can preferably use OD (optical concentration of black matrix) is 4.1 opacifier concentration.In contrast to this, the thickness after baking is when being 1.0 μ m, is under 4.1 the opacifier concentration at OD, is difficult for taking place the heat limit of collapsing.

Additive method as producing the hot limit of collapsing can be set forth in the method for working hard on the composition of monomer.For example TOHKEMY 2004-163917 communique is described like that, as monomer, and monomer that can be preferably that 3 officials energy is above and the mixed use of 2 functional monomers.

The prebake conditions temperature is low more, the time is short more, the easy more heat limit of collapsing, and temperature is high more, the time is long more, the difficult more heat limit of collapsing, the weak more easy more heat of the exposure intensity limit of collapsing, the limit and strong more difficult more heat is collapsed, development conditions is weak more, the easy more heat limit of collapsing, the limit and strong more difficult more heat is collapsed.When back lower slightly and time of baking temperature is long, the heat limit of collapsing easily, temperature height and time are difficult for the heat limit of collapsing in short-term.

Fig. 6 is an example of the cross sectional shape of the black matrix after the expression baking.

Among Fig. 6, will will deceive the clearing end (promptly black matrix lower end) of matrix from the initial point of smooth black matrix surface circular arc (promptly black matrix upper end) as the P point as the Q point.

Distance on the direction that is parallel to substrate surface of ordering from the P point to Q is above-mentioned " awl length ".The preferable range of awl length as mentioned above.

Figure 7 shows that the sectional view when on the substrate of the black matrix that is formed with above-mentioned Fig. 6, forming colored pixels.The projection (being above-mentioned angle height) that so can suppress the overlapping portion of black matrix and colored pixels.

About baking processing, can use heating plate (hot plate), convection oven (convection oven under these conditions; The heated air circulation type dryer), heating arrangement such as high frequency heating machine, with continous way or batch (-type) the dark layer after developing is carried out.

Other operation

Form in the operation at black matrix of the present invention, after above-mentioned dark layer forms operation, before the above-mentioned exposure process, can also add the prebake conditions operation, behind above-mentioned developing procedure, before above-mentioned baking (back baking) operation, can also contain the operation of the black matrix curing that will form as required by exposure.

The prebake conditions operation

As mentioned above,, form the condition of the exposure imaging in the operation the also preferred prebake conditions condition of suitably regulating in order to regulate black matrix display device movie queen's cross sectional shape except regulating black matrix.Form in the operation at black matrix of the present invention, compare,, then form back taper,, then form positive taper if at high temperature carry out if carry out at low temperatures with prebake conditions condition commonly used.

Particularly, when carrying out prebake conditions with heating plate, the prebake conditions temperature is preferably 65 ℃～120 ℃.More than 65 ℃ the time, can prevent that dark layer is peeled off in the developing procedure, below 120 ℃ the time, can make the state of the development of dark layer bottom for progress.More preferably 70 ℃～100 ℃ of prebake conditions temperature most preferably are 75 ℃～90 ℃.In addition, the prebake conditions time is preferably 50～300 seconds, more preferably 90～200 seconds, most preferably is 100～180 seconds.If carry out prebake conditions under these conditions, then be easy to regulate the cross sectional shape after dark layer develops.

In addition, prebake conditions also can be carried out in baking oven, and this moment also can be by suitably setting prebake conditions condition same as described above, regulates the cross sectional shape after the development.

Colored pattern forms operation

Colored pattern of the present invention forms operation and is at least the photosensitive coloring composition formation dyed layer (dyed layer formation operation) that is being coated with the invention described above on the substrate of above-mentioned resin black matrix being formed with, with formed dyed layer prebake conditions (dyed layer prebake conditions operation), again the dyed layer that forms is carried out pattern exposure (dyed layer exposure process), the dyed layer that will carry out pattern exposure develops (dyed layer developing procedure), forms the operation of the colored pattern with overlapping portion on described resin black matrix.

Colored pattern

Colored pattern of the present invention constitutes the colored pixels of color filter.

Shown in for example above-mentioned colored pattern shown in Figure 16 of colored pattern of the present invention, the form with pattern with overlapping O on resin black matrix 4 forms.That is, preferably on resin black matrix 4, form pattern continuously from the zone that does not form resin black matrix (pixel region) on the substrate 2.Under described state, in the colored pattern 6, the part that is formed at pixel region is called colored pixels.

In addition, the shape of the colored pattern during from the observation of substrate normal direction colored pattern formation face side, being the aggregate of the isolated shape pattern (island pattern) that is divided into each pixel, also can be striated pattern (each row of striated pattern also can be crossed over the pixel region group that straight striated is arranged).

The thickness of colored pattern is preferably 1.0 μ m～3.0 μ m.

Here said " thickness of colored pattern " is meant the thickness at the colored pattern of pixel region.

If this thickness is more than 1.0 μ m, then the ladder difference of the pixel periphery that overlaps with black matrix is not serious, can more effectively suppress the demonstration inequality of light leak.

In addition, if this thickness below 3.0 μ m, then can further improve the thickness homogeneity of large-area chromatograph.

And then from the viewpoint of the angle height of further reduction colored pattern, the thickness of colored pattern is preferably 1.5～2.5 μ m.

Dyed layer forms operation

Dyed layer forms in the operation, is being formed with on the substrate of resin black matrix, uses existing photosensitive coloring composition of the present invention to form dyed layer.

As being formed with the method that forms dyed layer on the substrate of resin black matrix, can use and the same method of method that on substrate, forms dark layer, that is, use coating process or printing transferring method.

Wherein, be formed with the method for the substrate front coating photosensitive coloring composition of black matrix at slot coated device etc., preferred from realizing effect of the present invention effectively.

The layer thickness of dyed layer from obtaining sufficient color reproduction zone and sufficient panel luminance aspect, is preferably the scope of 1.0～3.0 μ m, more preferably the scope of 1.5～2.5 μ m.

Dyed layer prebake conditions operation

Dyed layer prebake conditions operation is that described dyed layer is being formed the operation that the dyed layer that forms in the operation carries out prebake conditions (heat treated).By this operation, can make the dyed layer drying.

In this dyed layer prebake conditions operation, because in the dry run of utilizing prebake conditions to carry out, it is poor to reduce the ladder that the dyed layer surface produces, and then can be through overexposure and the angle height when further reducing as colored pattern of developing.

From the viewpoint of further reduction angle height, the prebake conditions temperature is preferably 60～140 ℃, more preferably 80～120 ℃.The prebake conditions time is preferably 30～300 seconds, more preferably 80～200 seconds.

The prebake conditions of dyed layer can similarly be carried out in hot plate or stove with the prebake conditions of above-mentioned dark layer.

Illustrated, formed at dyed layer between the prebake conditions of the coating of operation and dyed layer prebake conditions operation, preferably also comprised vacuum drying operation dyed layer vacuum drying (being also referred to as drying under reduced pressure).There is no particular limitation for the concrete mode of vacuum drying (drying under reduced pressure), can unrestrictedly use the method for records such as TOHKEMY 2000-241623 communique for example, TOHKEMY 2001-235277 communique, TOHKEMY 2006-19472 number, TOHKEMY 2006-19472 communique.

The dyed layer exposure process

In the dyed layer exposure process, described dyed layer is exposed.

The exposure-processed of dyed layer can similarly be carried out with the exposure process of dark layer.When forming the colored pattern of multiple color, across the mask pattern of shades of colour appointment (for example, the aggregate of above-mentioned isolated shape pattern or striated pattern etc.), expose by of all kinds, can be with the dyed layer patterning of all kinds (solidifying during eurymeric) after the rayed.

Spendable radioactive ray during as exposure especially preferably use ultraviolet rays such as g line, h line, i line.Exposure is preferably 5～500mJ/cm ², 10～300mJ/cm more preferably ², most preferably be 10～200mJ/cm ²

Exposure machine can use the exposure machine near (proximity) mode, also can adopt mirror surface projection formula exposure machine or step-by-step exposure machine.

The dyed layer developing procedure

Among the dyed layer development worker, the described dyed layer after the exposure is developed.

The development treatment of the dyed layer after the exposure can adopt and the operation identical operations of being put down in writing in the explanation of the developing procedure of dark layer, preferably uses the developer solution that illustrates in the described developing procedure.

That is,, can use organic base developer solution or inorganic base developer solution or its mixed liquor as developer solution.

As the alkaline agent that is used for developer solution, for example can enumerate NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-organic basic compounds such as 7-hendecene.These bases are diluted with pure water with concentration 0.001～10 quality %, the mode that is preferably 0.01～1 quality %, obtain alkaline aqueous solution, preferably use this alkaline aqueous solution.Illustrated, when using the developer solution that constitutes by this alkaline aqueous solution, after development, washed (rinse) usually with pure water.

As development conditions, for the length (length of the Width of black matrix) of adjusting the overlapping portion between black matrix and the colored pixels and the height at angle, preferably with the development conditions of in the explanation of the developing procedure of described dark layer, the putting down in writing dyed layer that develops.

That is, as development temperature, be preferably 20～35 ℃, more preferably 20～30 ℃.Development time is preferably 20～120 seconds, more preferably 30～70 seconds.

Wherein, as the preferred compositions of development temperature and development time, for example can enumerate, 23 ℃ of temperature are at 40～70 seconds, 25 ℃ of temperature 30～60 seconds down.

In addition, spray is pressed, and from preventing the viewpoint of black matrix disappearance, is preferably 0.01～0.5MPa, more preferably 0.05～0.3MPa, more preferably 0.1～0.3MPa.

Back roasting procedure

Colored pattern formation operation of the present invention preferably behind described dyed layer developing procedure, also comprises the operation (back roasting procedure) of back baking colored pattern.

When the present invention was provided with the back roasting procedure, it is poor that the colored pattern surface in the dry run of back baking produces ladder,, further reduces the angle height that is.

From above viewpoint, the temperature of back baking is preferably 150～260 ℃, more preferably 180～260 ℃, most preferably is 200～240 ℃.The time of back baking is preferably 10～150 fens, more preferably 20～120 minutes, most preferably is 30～90 fens.

And then, from further reducing the viewpoint of angle height, the thickness of the colored pattern of the thickness of the colored pattern after the baking of back before with respect to the back baking, the film slip is preferably below 25%.

At this, the thickness of the colored pattern of film slip before by later baking is that the thickness of the colored pattern after thickness A, the baking later on is thickness B, and utilizes following formula 3 to try to achieve.

Film slip (%)=((thickness A-thickness B)/thickness A) * 100 ... formula 3

From easily the film slip being adjusted into the viewpoint in the above-mentioned scope, preferably baking after being 10 minutes～60 minutes under 200 ℃～250 ℃, more preferably baking after being 20 minutes～40 minutes under 210 ℃～240 ℃.

Illustrated, form RGB (Red, Green, Blue) during the colored pattern of a plurality of form and aspect such as 3 form and aspect, also repeat the circulation of formation, exposure, development and the back baking of dyed layer according to desired form and aspect number, each form and aspect is carried out formation, exposure and the development of dyed layer, and then together whole form and aspect are carried out the back baking.Thus, can make and possess the colored pixels that the form and aspect by black matrix and regulation form.

Substrate

As substrate of the present invention, the photo-electric conversion element substrate that for example can be set forth in alkali-free glass, soda-lime glass, PYREX (registered trademark) glass, quartz glass that uses in the liquid crystal display cells etc. and the above-mentioned glass that adheres to nesa coating and use in solid-state imager etc. is silicon substrate etc. for example.In addition, can also use plastic base.Wherein, from reagent resistance and stable on heating viewpoint, preferred alkali-free glass.On these substrates, at first form black matrix such as clathrate to isolate each pixel, form colored pixels in the vacancy part of grid (below be also referred to as " peristome " or " pixel ") then.

In addition, on these substrates, can also be provided with as required undercoat with improve and upper layer between adaptation, prevent the material diffusion or make the substrate surface planarization.From the viewpoint of further performance effect of the present invention, substrate is preferably large-scale (Yi Bian being about more than the 1m) substrate.

Other operation

The manufacture method of color filter of the present invention forms the operation except above-mentioned resin black matrix forms operation, colored pattern, also can have formation ELD (for example, ITO (Indium TinOxide) film etc.), column separator (spacer), the orientation control operation with projection pattern etc.

But,, finishing coat is set preferably from shortening the viewpoint that manufacturing process and manufacturing cost lower.

At this,, for example,, on colored pattern, has the state of the transparent electrode layer that joins with this colored pattern in the color filter of made as the state that finishing coat is set.The color filter of this type of state is compared with certain color filter of finishing coat, transmissivity high aspect be effective.

The manufacture method of color filter of the present invention uses photosensitive coloring composition of the present invention to form colored pattern, therefore, even be provided with under the state of above-mentioned finishing coat, also can reduce the projection of colored pattern of the overlapping portion of resin black matrix and colored pattern fully.

In addition, from shortening manufacturing process, lower manufacturing cost, prevent the viewpoint that color filter damages that the manufacture method of color filter of the present invention preferably has grinding step.

Under the state of the resulting color filter of manufacture method that does not have grinding step, for example, when observing the surface with 500 times of multiplying powers, the radical of the damage of preferred striated is 3/cm ²Below.The color filter of state is effective suppressing aspect the defective that damage produced of color filter like this.

The manufacture method of color filter of the present invention uses photosensitive coloring composition of the present invention to form colored pattern, therefore, even under the situation that does not have above-mentioned grinding step, also can fully reduce the projection of the colored pattern among resin black matrix and colored pattern overlapping.

In addition, the color of the colored pattern of described color filter (colored pixels) is preferably more than 3 looks.Wherein, be preferably R (red), G (green), this 3 look of B (indigo plant) especially.

Color filter of the present invention can be applicable to televisor, PC, industry with or the display device of various uses such as the carried terminal of medical etc. watch-dog, liquid crystal projection apparatus, game machine, mobile phone etc., digital camera, automobile navigation instrument.

Liquid crystal indicator

Liquid crystal indicator of the present invention is the liquid crystal indicator that possesses color filter of the present invention.Therefore, has high contrast.

Separator can preferably adopt coating method for making and transfer printing method for making.From the simple viewpoint of operation, preferably be coated with method for making.From the good viewpoint of the homogeneity of spacer height, preferred transfer printing method for making.About the transfer printing method for making, the method for putting down in writing among the preferred especially TOHKEMY 2008-146018.

About the definition of display device and the explanation of each display device, for example (on the books in the wooden clear husband's work of assistant assistant, Co., Ltd.'s census of manufacturing meeting (Kogyo Chosakai Publishing, Inc.) nineteen ninety distribution), " display equipment (display デバイス) " (she blows along chapter work, industry books Co., Ltd., puts down into distribution in the first year) etc. at " electronic console device (electronic console デバイス) ".In addition, about liquid crystal indicator, for example on the books in " inferior generation lcd technology (inferior generation LCD Ji Intraoperative) " (Uchida Tatsuo edits, Co., Ltd. census of manufacturing can distribution in 1994).Can use liquid crystal indicator of the present invention not have particular restriction, for example can be used for liquid crystal indicator in the variety of way of above-mentioned " inferior generation lcd technology (inferior generation liquid crystal デイスプレイ Ji Intraoperative) " record.

Wherein, the present invention is effective especially for the liquid crystal indicator of colored TFT (Thin Film Transistor) mode.About the liquid crystal indicator of colored TFT mode, for example (on the books in upright altogether publication Co., Ltd. (KyoritsuShuppan Co., Ltd.) distribution in 1996) in " colored TFT liquid crystal display (カラ one TFT LCD) ".In addition, the present invention can also be applicable to liquid crystal indicator, STN (Super-twisted Nematic), TN (Twisted Nematic), VA (VerticalAlignment), OCS (On Chip Spacer), FFS (Fringe Field Switching) and the R-OCB (Reflective Optically Compensated Bend) etc. that IPS transverse electric field type of drive such as (In-Plane Switching), MVA visual angles such as pixel partitioning scheme such as (Multi-domainVertical Alignment) enlarge.About these modes, for example on the books in the 43rd page of " the up-to-date trend in EL, PDP, LCD demonstration-technology and market (EL, PDP, the up-to-date Move of LCD display-Ji Intraoperative と city Games to-) " (eastern beautiful research centre investigation (TorayResearch Center Inc.) research department calendar year 2001 distribution).

Liquid crystal indicator also ensures various parts formations such as film by electrode base board, polarizing coating, phase retardation film, backlight (backlight), separator, visual angle except that color filter.Band photomask substrate of the present invention goes for the liquid crystal indicator with these known parts formations.

About these parts, for example (on the books in the island Itou Kentaro, the MC of Co., Ltd. C (CMC Publishing Co., Ltd.) distribution in 1994), " present situation of 2003 liquid crystal relevant markets and vision of the future (the brilliant Seki Even of 2003 liquid city Games Now shape と looks forward in the future) (last volume) " (good lucky, the Fuji of Co., Ltd. of table always grinds (Fuji Chimera Research InstituteInc.) and issued in 2003) at " market (' the 94 LCD periphery material ケミカ Le Block city Games of 94 liquid crystal display periphery material chemistry) ".

About backlight, on the books in 25～30 pages (Yagi spark gap is grand bright) in 18～24 pages (the island health is abundant) in SID meeting Digest 1380 (2005) (A.Konno etc.), display monthly magazine (monthly magazine デイスプレイ) in Dec, 2005 number, display monthly magazine in Dec, 2005 number etc.

When the three-wavelength pipe of color filter of the present invention and present known cold-cathode tube makes up, can realize high-contrast, led light source (RGB-LED) by using red, green, blue can provide the high Color reproduction of brightness height and excitation good liquid crystal indicator as backlight.

On the other hand, the desired performance of liquid crystal indicator is the raising of image response speed.In order to improve response speed, the speed of orientation of liquid crystal is improved.On the other hand, the structural plane of (cell) is considered from the unit, wants to reduce cost to reduce the thickness of liquid crystal layer.Reducing another required technology of thickness of liquid crystal layer is to reduce the liquid crystal aligning confusion of the boundary member of colored pixels and black matrix.Therefore, make every effort to reduce projection (angle) at the boundary member of colored pixels and black matrix.

Use in the color filter of color filter manufacture method manufacturing of the present invention,, therefore when being used for liquid crystal indicator, can suppressing the orientation confusion of liquid crystal, thereby can improve contrast owing near the ladder difference of the colored pattern overlapping the O is little.

As mentioned above, color filter of the present invention can reduce the liquid crystal aligning confusion of above-mentioned overlapping portion, and the visuognosis of image when showing also is improved.For liquid crystal indicator of the present invention, the color filter of the application of the invention, can make the overlapping portion flattening of each colored pixels and black matrix, because flatness is good, make the liquid crystal layer attenuation, before laying transparency electrode ITO, need not to grind or give planarization layer, thereby help rationalization and the cost decline and the batch process of operation.

[embodiment]

Below, enumerate embodiment and be described more specifically the present invention.Material shown in the following embodiment, reagent, ratio, instrument, operation etc. are only otherwise depart from the scope of the present invention all and can do suitable change.Therefore, scope of the present invention is not limited to following object lesson.Need to prove, in following embodiment, under the prerequisite of no specified otherwise, " % " and " part " expression " quality % " and " mass parts ", molecular weight is represented weight-average molecular weight.In addition, " wt% " expression " quality % ".

Embodiment 1

1. the dark preparation of compositions of photonasty

The preparation of carbon black dispersion liquid (K-1)

Prepare carbon black dispersion liquid (K-1) with following prescription.

Carbon black (De Kusai corporate system COLOR BLACK FW2) ... 26.7 portion

3.3 ones of spreading agents (nanmu originally changes into system DISPARLON DA7500 acid number 26 amine values 40)

Benzyl methacrylate/methacrylic acid (=72/28[mol ratio]) multipolymer (50 quality % solution of molecular weight 30000, propylene glycol methyl ether acetate) ... 10 ones

Propylene glycol methyl ether acetate ... 60 ones

Use homogenizer above-mentioned each composition to be stirred 1 hour with the condition of 3000rpm.Use has utilized the pearl dispersion machine (trade name: DESPERMAT (デイスパ one マ Star ト), GETZMANN company (VMA-GETZMANN GMBH) system) of 0.3mm zirconium oxide bead, the mixed solution that obtains is implemented 8 hours diffusing processing of differential, obtain carbon black dispersion liquid (K-1).

Use resulting carbon black dispersion liquid (K-1), with the prescription of following table 1, the dark composition CK-1 of preparation photonasty.Numeric representation mass ratio in the table 1.

[table 1]

The details of each composition in the table 1 is as described below.

Resin solution C-2: benzyl methacrylate/methacrylic acid (=85/15 mol ratio) multipolymer, (50 quality % solution of Mw10000, propylene glycol methyl ether acetate)

UV curable resin C-3: trade name CYCLOMER PACA-250 Daicel chemical industry (Co., Ltd.) system " side chain have alicyclic ring, COOH base and acryloxy acrylic acid series copolymer, propylene glycol methyl ether acetate solution (solid state component: 50 quality %) "

Polymerizable compound C-5: the potpourri of Japanese chemical drug (Co., Ltd.) system KAYARADDPHA and Japanese chemical drug (Co., Ltd.) system KAYARADR-684 60 to 40 (mass ratioes)

Initiating agent C-7: trade name " OXE-02 " Ciba corporate system

Surfactant C-8: big Japanese ink chemical industry (Co., Ltd.) system of trade name " MEGAFAC R30 "

Solvent: PGMEA=propylene glycol methyl ether acetate

EEP=3-ethoxyethyl group propionic ester

2. the formation of resin black matrix

The dark composition layer of photonasty forms operation

Use the dark composition CK-1 of resulting photonasty, on glass substrate, form the resin black matrix of clathrate pattern in the following way.

At first, use slit coater (slit coater) (model HC6000, Hirata Spinning Ltd. (Hirata Corporation) system), regulate spacing between slit and the glass substrate and spray volume so that the thickness after the baking of back is 1.1 μ m, and with coating speed 120mm/ second the glass substrate (MILLENIUM of Corning corporate system, thick 0.7mm) after cleaning go up the dark composition CK-1 of the above-mentioned photonasty of coating.

Then, (coated film (dark layer) vacuum drying 30 seconds that chemical industry society (Tokyo OhkaKogyo Co., Ltd.) system) obtains coating is answered in Tokyo to use Minton dryer VCD.

Prebake conditions operation and exposure process

Then, to the coated film after the vacuum drying (dark layer), use hot plate under 80 ℃, to carry out heating (prebake conditions processing) in 120 seconds, use then near mode exposure machine (type kind LE5565A, Hitachi High Tech. Corp.'s corporate system (Hitachi High-TechnologiesCorporation) system) with 60mJ/cm ²Carry out pattern exposure.

Developing procedure

Then, transporting the type developing apparatus with level develops.Promptly, adopt potassium hydroxide class developer solution CDK-1 ((the FUJIFILM ElectronicMaterials Co. of Fujiphoto Electronics Materials Co., Ltd, Ltd.) the 1.0% developer solution (dilution that contains 1 mass parts CDK-1 and 99 mass parts pure water system), 24 ℃), set the spray pressure and be 0.15MPa, developed 37 seconds, and cleaned, the black matrix pattern after obtaining developing with pure water.

Back roasting procedure

Then, in 220 ℃ cleaning ovens (clean oven), carry out 40 minutes after baking processing, obtained on substrate, forming the black matrix base plate of band of the black matrix of clathrate pattern.

The peristome as pixel of resulting black matrix is 90 μ m * 200 μ m, and thickness is 1.1 μ m, and the live width of the pattern of the direction parallel with the length direction of pixel is 25 μ m.

Use X-Rite 361T (V) (SAKATA INX ENG.Co., Ltd. system) to measure the optical concentration (OD) of the black matrix that makes, the result is 4.2.

3. the preparation of photosensitive coloring composition

3-1. red (R) uses the preparation of photosensitive coloring composition CR-1

Synthesizing of polymkeric substance 1 (side chain has the macromolecular compound of heterocycle)

M-11 (following structure) 27.0g, methyl methacrylate 126.0g, methacrylic acid 27.0g and 1-methoxyl-2-propyl alcohol 420.0g are directed into by in the there-necked flask after the nitrogen displacement, use stirring machine (new eastern science (Co., Ltd.) (Shinto Scientific Co., Ltd.): スリ one ワ Application モ, one タ (Three-One Motor)) stir, when flowing into nitrogen in the flask, heat, be warming up to 90 ℃.To wherein adding 1.69g 2,2-azo two (2, the 4-methyl pentane nitrile) (with the pure medicine of light (Co., Ltd.) (Wako Pure Chemical IndustriesLtd.) system V-65) was 90 ℃ of following heated and stirred 2 hours.After 2 hours, add 1.69gV-65 again, stir after 3 hours, obtain 30 quality % solution of polymkeric substance 1 (side chain has the macromolecular compound of heterocycle).In order to polystyrene is the weight-average molecular weight of the resulting macromolecular compound of gel permeation chromatography (GPC) mensuration of standard substance, and the result is 2.0 ten thousand.In addition, by using the titration of sodium hydroxid, the acid number that obtains solid state component is 98mgKOH/g.

The preparation of coverage pigment 1

With the solution 20g of pigment (C.I.Pigment Red254 Ciba system CROMOPHTALREDBP) 50g, common salt 500g, above-mentioned polymkeric substance 1 and diglycol 100g 1 gallon of kneader of stainless steel (aboveground making (Inoue Manufacturing Co. of institute that packs into, Ltd.) system), mixing 9 hours.Then, this potpourri is dropped in about 3 liters water,, filter then, wash, remove sodium chloride and solvent, drying, preparation coverage pigment 1 with high-speed mixer (high speed mixer) stir about 1 hour.

The evaluation of the coverage of pigment

Resultant pigment 10g is put among 1-methoxyl-2-propyl alcohol 100mL, use bobbing machine at room temperature to shake 3 hours.Then, use centrifugal separator, spend 8 hours with 80000rpm and make the pigment precipitation.Obtain the solid state component of supernatant part with seasoning.Try to achieve from the amount of the free macromolecular compound of pigment, according to its with handle in the ratio of the macromolecular compound that uses, calculate ionization rate (%).Ionization rate is approximately little, and is high more to the coverage of pigment.

The coverage pigment 1 that obtains in above-mentioned shows the ionization rate that 20 quality % are following, obtains covered pigment as can be known.

The preparation of dispersible pigment dispersion 1

Prepare dispersible pigment dispersion 1 in the following way.That is,, use homogenizer, stir with rotation number 3000r.p.m. and mixed in 3 hours with the described composition of following table 2, the preparation mixed solution, and then, use and utilized (longevity industrial group (Kotobuki Industries Co., Ltd.) system) carries out 8 hours dispersion treatment to the pearl dispersion machine Ultra ApexMill of zirconium oxide bead (ウ Le トラアペ Star Network スミ Le).

[table 2]

The particular content of the composition in the described table 2 is as described below.

·C.I.PigmentRed254

Ciba system CROMOPHTAL RED BP

(R in the described general formula (A) is the pigment of chlorine atom)

·Disperbyk?161

Bi Ke chemistry corporate system

" use 30 quality % solution.Therefore, solid state component is 2.1 parts.”

·PEGMEA

Methyl proxitol acetate

The preparation of photosensitive coloring composition CR-1

The composition of the composition below adding in resulting dispersible pigment dispersion 1 again mixes, preparation photosensitive coloring composition coating fluid CR-1.

Alkali soluble resin: multipolymer weight-average molecular weight=30,000 19.8 of benzyl methacrylate and methacrylic acid (=70/30[mol ratio]) part

Monomer: 20 parts of Japanese chemical drug corporate system DPHA

Polymerization initiator: 2,2 '-two (2-chlorophenyl)-4,4 ', 5,3 ones of 5 '-tetraphenyl bisglyoxalines

Polymerization initiator: 4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,3 parts of 6-two (trichloromethyl)-s-triazine

0.5 part of diethylamino benzophenone

0.5 part of N-phenyl mercaptobenzimidazole

Multi-functional epoxy compound: the big system EPICLON of Japanese ink chemical industry society (エピ Network ロ Application) 695 5 parts

Surfactant: 1.0 parts of surfactant C-8

Solvent (methyl proxitol acetate/3-ethoxyethyl group propionic ester=8/2)

400 parts

For the pigment among the photosensitive coloring composition coating fluid CR-1, with respect to " primary particle size surpasses the pigment of 0.08 μ m " and as described below the trying to achieve of ratio of " pigment of primary particle size less than 0.02 μ m " of all solid state composition of photosensitive coloring composition coating fluid CR-1.

That is, observe the pigment powder with transmission electron microscope (TEM), graphical analysis TEM photo is investigated size distribution, tries to achieve primary particle size.Particularly, the population of calculating all particles number in the observation sample under 100,000 times and less than 0.02 μ m and surpassing the pigment of 0.08 μ m.

For the ratio of the primary particle of primary particle size less than 0.02 μ m, surpass for the ratio of primary particle of 0.08 μ m, by measuring the major diameter of each one-level particle, the ratio (number %) of particle of calculating less than 0.02 μ m and surpassing the pigment of 0.08 μ m.Observe the pigment powder with transmission electron microscope with 30,000 times～100,000 times, take pictures, measure the major diameter of 1000 primary particles, the ratio of calculating less than 0.02 μ m and surpassing the primary particle of 0.08 μ m.Change the position of pigment powder, carry out this operation amounting to 3 positions, calculate average result, result's's " primary particle size surpasses the pigment of 0.08 μ m " ratio is 0.50% (number distribution), and the ratio of " pigment of primary particle size less than 0.02 μ m " is 1.6% (number distribution).

3-2. green (G) uses the preparation of photosensitive coloring composition coating fluid CG-1

Use dispersion liquid (G-1) with following prescription preparation green (G).

Pigment Green36 (mean grain size that SEM observes is 47nm)

11 parts

Pigment Yellow150 (mean grain size that SEM observes is 39nm)

7 parts

Dispersion resin A-3 described later ... 5 parts

Spreading agent (trade name: Disperbyk-161, Bi Ke chemistry corporate system 30% solution)

3 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer

(=85/15[mol ratio] multipolymer, molecular weight 30000, propylene glycol methyl ether acetate solution (solid state component: 50 quality %)) ... 11 parts

Solvent: propylene glycol methyl ether acetate ... 70 ones

Use homogenizer under the condition of 3000rpm, to stir above-mentioned each composition 1 hour.Use has utilized the pearl dispersion machine (trade name: DESPERMAT, GETZMANN corporate system) of 0.3mm zirconium oxide bead, and resulting mixed solution is implemented 8 hours the diffusing processing of differential, obtains green (G) dispersion liquid (G-1).

Use resulting green (G) with dispersion liquid (G-1), with following prescription preparation green (G) photosensitive coloring composition coating fluid CG-1.Observe with SEM once more, mean grain size is 32nm as a result.

Green (G) uses dispersion liquid (G-1) ... 100 parts

Epoxy resin: (trade name EHPE3150 Daicel chemical industrial company system) ... 2 parts

Polymerizable compound: the KAYARADDPHA of Nippon Kayaku K. K ... 8 parts

Polymerizable compound: four (ethoxy propylene acid esters) of pentaerythrite

2 parts

Polymerization initiator: 1, the two trihalomethyl groups of 3--5-benzo tetrahydrofuran triazine

2 parts

Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 ... 1 part

Polymerization initiator: diethyl thioxanthone ... 0.5 part

Polymerization inhibitor: p-metoxyphenol ... 0.001 part

Fluorine is a surfactant (trade name: the big Japanese ink of Megafac R08 chemical industrial company system) ... 0.02 part

Nonionic is a surfactant (trade name: EMULGEN A-60 KAO. Corp. SA system) ... 0.5 part

Solvent: propylene glycol methyl ether acetate ... 120 parts

Solvent: propylene glycol n-propyl ether acetic acid esters ... 30 parts

Mix and stir above-mentioned composition, obtain green (G) photosensitive coloring composition coating fluid CG-1.

3-3. blue (B) uses the preparation of photosensitive coloring composition CB-1

Use dispersion liquid (B-1) with following prescription preparation blue (B).

Pigment Blue15:6 (mean grain size that SEM observes is 55nm)

14 parts

Pigment Violet23 (mean grain size that SEM observes is 61nm)

1 part

Dispersion resin A-3 described later ... 5 parts

3 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer

(=80/20[mol ratio] multipolymer, molecular weight 30000, propylene glycol methyl ether acetate solution (solid state component: 50 quality %)) ... 4 parts

Solvent: propylene glycol methyl ether acetate ... 73 parts

Use homogenizer, stirred above-mentioned each composition 1 hour with the condition of 3000rpm.The differential that use has utilized the pearl dispersion machine (trade name: DESPERMAT, GETZMANN corporate system) of 0.3mm zirconium oxide bead that resulting mixed solution was implemented 4 hours looses and handles, and obtains blueness (B) dispersion liquid (B-1).Once more, observe with SEM, mean grain size is 39nm as a result.

Use resulting blueness (B) with dispersion liquid (B-1), use photosensitive coloring composition CB-1 with following prescription preparation blue (B).

Blue (B) uses dispersion liquid (B-1) ... 100 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer (=80/20[mol ratio] multipolymer, molecular weight 30000), propylene glycol methyl ether acetate solution (solid state component: 50 quality %)) ... 7 parts

Epoxy resin: (trade name CELLOXIDE 2080 Daicel chemical industrial company systems) ... 2 parts

UV curable resin: (trade name CYCLOMERP ACA-250 Daicel chemical industrial company system)

(side chain has certain acrylic acid series copolymer, the propylene glycol methyl ether acetate solution (solid state component: 50 quality %) of alicyclic ring, COOH base and acryloyl group ... 4 parts

Polymerizable compound: the KAYARAD DPHA12 of Nippon Kayaku K. K part

Polymerization initiator: 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazyl-3-yl)-1-(o-acetyl oxime) ethyl ketone ... 3 parts

Polymerization inhibitor: p-metoxyphenol ... 0.001 part

Fluorine is a surfactant (trade name: the big Japanese ink of Megafac R08 chemical industrial company system)

0.02 part

Nonionic is a surfactant (trade name: EMULGEN A-60 KAO. Corp. SA system) ... 1.0 part

Solvent: 3-ethoxyl ethyl propionate ... 20 parts

Solvent: propylene glycol methyl ether acetate ... 150 parts

Mix and stir mentioned component, obtain blueness (B) and use photosensitive coloring composition CB-1.

4. dispersion resin A-3's is synthetic

1. chain-transferring agent A3's is synthetic

With dipentaerythritol six (3-mercaptopropionic acid ester) (DPMP; Sakai chemical industry (Co., Ltd.) (Sakai Chemical Industry Co., Ltd.) system) (following compound (33)) 7.83 parts and 4.55 parts of following compounds (m-6) having adsorption site and have a carbon-to-carbon double bond are dissolved in 28.90 parts of the propylene glycol monomethyl ethers, flow down at nitrogen and are heated to 70 ℃.To wherein adding 2,0.04 part of 2 '-azo two (2, the 4-methyl pentane nitrile) (the pure pharmaceutical worker's industry of V-65 and light (Co., Ltd.) system) heated 3 hours.The V-65 that adds 0.04 part again is nitrogen stream, 70 ℃ of following reactions 3 hours.Be cooled to room temperature, obtain 30% solution of mercaptan compound shown below (chain-transferring agent A3).

2. dispersion resin A-3's is synthetic

Mixed solution with 19.0 parts of 4.99 parts of 30% solution, the methyl methacrylates of the above-mentioned chain-transferring agent A3 that obtains and 1.0 parts of methacrylic acids, 4.66 parts of propylene glycol monomethyl ethers flows down at nitrogen, is heated to 90 ℃.Spent 205 hours to splash into 2 when stirring this mixed solution, the mixed solution that 0.139 part of the two isobutyric acid dimethyl ester of 2 '-azo (the pure pharmaceutical worker's industry of V-601 and light (Co., Ltd.) system), 5.36 parts of propylene glycol monomethyl ethers and propylene glycol methyl ether acetate are 9.40 parts.After splashing into termination, after making it to react 2.5 hours under 90 ℃, drop into 2, the mixed solution of 0.046 part of the two isobutyric acid dimethyl ester of 2 '-azo, 4.00 parts of propylene glycol methyl ether acetates makes it to react 2 hours again.In reactant liquor, add 1.52 parts of propylene glycol monomethyl ethers, 21.7 parts of propylene glycol methyl ether acetates, be cooled to room temperature, obtain the solution (specific dispersion resin 30 quality %, propylene glycol monomethyl ether 21 quality %, propylene glycol methyl ether acetate 49 quality %) of dispersion resin A-3 (mean molecular weight 24000 of polystyrene conversion) thus.

The acid number of this dispersion resin A-3 is 48mg/g.The structure of dispersion resin A-3 is as follows.

5. the making of color filter

Dyed layer forms

At first, the above-mentioned redness that obtains (R) is formed the face side with the black matrix that photosensitive coloring composition CR-1 coats described black matrix base plate.Particularly, same with the situation that dark layer forms, use slot coated device (model HC6000, formula commercial firm of Hirata Spinning Ltd. system), the bed thickness of the dyed layer after toasting later on is that the mode of 2.0 μ m is regulated interval and the spray volume between slit and the black matrix base plate, is coated with second for 120mm/ with the coating speed.

Then, use Minton dryer VCD (the chemical industry corporate system is answered in Tokyo), the dyed layer vacuum drying that described coating is obtained 30 seconds.

Dyed layer prebake conditions operation and dyed layer exposure process

Then,, use hot plate, under 100 ℃, heated (prebake conditions processing) 120 seconds the dyed layer after the described vacuum drying.

Then, the dyed layer to after the prebake conditions processing uses proximity printing machine (Hitachi's high-tech company system, LE5565A), forms across red pattern and uses mask, with exposure 90mJ/cm ²Carry out pattern exposure.

In addition, the mode that is 8.0 μ m with overlapping (the exposure lap) of exposing patterns and black matrix is set mask pattern and exposure machine.

Roasting procedure behind dyed layer developing procedure and the dyed layer

Then, use developing apparatus (Hitachi's high-tech company system), with potassium hydroxide is 1.0% developer solution (be 1 Quality Mgmt Dept, be the dilution, 25 ℃ of 99 mass parts with pure water with CDK-1) of developer solution CDK-1 (Fujiphoto electronic material (Co., Ltd.) system), pressing with spray is 0.2MPa, developed 45 seconds, clean with pure water, obtain red pattern (red pixel).

Then, resulting red pattern (red pixel) is carried out baking processing after 30 minutes, obtain the red pixel after the thermal treatment with 220 ℃ cleaning ovens.

Then, after above-mentioned dyed layer forms operation, dyed layer prebake conditions operation, dyed layer exposure process, dyed layer developing procedure and dyed layer in the roasting procedure, redness (R) is used photosensitive coloring composition CG-1 with photosensitive coloring composition CR-1 instead of green (G), in addition, similarly form green pattern.But, in the pattern exposure that this green pattern forms, do not use red pattern to form and use mask, use green pattern to form and use mask.

And then, then redness (R) is replaced with blueness (B) with photosensitive coloring composition CR-1 and use photosensitive coloring composition CB-1, similarly form blue pattern in addition, obtain color filter.But, in the pattern exposure that this blueness pattern forms, do not use red pattern to form and use mask, use blue pattern to form and use mask.

The making of liquid crystal indicator

On the R of the above-mentioned color filter that obtains pixel, G pixel and B pixel and black matrix, further form ITO (Indium Tin Oxide: transparency electrode tin indium oxide) by sputter.At this moment, under the situation that finishing coat is not set, on R pixel, G pixel and B pixel and black matrix, directly form ito transparent electrode.

Then, be equivalent on the above-mentioned ito transparent electrode black matrix above part column photoinduction separator is set.At this moment, do not carry out the milled processed of color filter.When observing the color filter surface with optical microscope (500 times of multiplying powers), the radical of the damage of striated is 0/cm ²

Then, on ito transparent electrode that is provided with color filter and column photoinduction separator, the alignment films that is formed by polyimide is set again.

In addition, the active-matrix substrate of preparing to have TFT (thin film transistor (TFT)) forms the face side at TFT the alignment films that is formed by polyimide is set as counter substrate.

Then, on the position that is equivalent to surround the black matrix housing that is provided with around the colored pixels group of color filter, utilize the sealant of allocation scheme coating ultraviolet curable resin, drip TN pattern liquid crystal, under vacuum state, fit with counter substrate.After the substrate of fitting carried out the UV irradiation, heat-treat and make sealant cures.Obtain liquid crystal cells in the manner described above.Paste the polarization plates HLC2-2518 that SANRITZ Corporation makes on the two sides of this liquid crystal cells, then, at the backlight that constitutes cold-cathode tube and be arranged at the back side one side of the liquid crystal cells that is provided with above-mentioned polarization plates, make liquid crystal indicator.

Measure and estimate

For photosensitive coloring composition, color filter and liquid crystal indicator, carry out following mensuration and evaluation.With the table 3 that the results are shown in of measuring and estimating.

The mensuration of black matrix

For the substrate of giving above-mentioned resin black matrix, with the Width that is parallel to resin black matrix and have the substrate of resin black matrix perpendicular to the cutting of the face of substrate, use scanning electron microscope, take section SEM photo (5000 times of multiplying powers) with above-mentioned composition shown in Figure 2.

According to resulting SEM photo, the length L of the maximum film thickness t of mensuration resin black matrix and the end of resin black matrix.

Facing of photosensitive coloring composition is coated with the preceding viscosity (25 ℃) and the mensuration of solid state component amount

In the formation of dyed layer, according to following facing of method mensuration photosensitive coloring composition CR-1 being coated with preceding solid component concentration and viscosity (25 ℃).

The assay method of solid component concentration

At first, reclaim the photosensitive coloring composition CR-1 (15mL) that faces before being coated with, quality measurement (as quality 1) with spoon.

Then, with the photosensitive coloring composition CR-1 that reclaims in vacuum drying oven under the room temperature dry 3 hours again, measure dry mass (as quality 2).

From quality 1 and quality 2, measure the solid component concentration that faces the preceding photosensitive coloring composition CR-1 of coating according to following formula 2.

Illustrated, above be determined at before the coating 0.5 hour and carry out with interior.

Face preceding solid component concentration (quality %)=(quality 2/ quality 1) * 100 of coating ... formula 2

The assay method of viscosity (25 ℃)

At first, reclaim the photosensitive coloring composition CR-1 that faces before being coated with spoon, use the determination of viscoelasticity device STRESSTECH of REOLOGICA InstrumentsAB system, under the condition of 25 ℃ of dyed layer (photosensitive coloring composition) temperature, frequency 1Hz, measure viscosity.

The mensuration of solid state component 70% viscosity (25 ℃) of photosensitive coloring composition

For the above-mentioned photosensitive coloring composition CR-1 that obtains,, measure " solid state component 70% viscosity (25 ℃) " (viscosity under 25 ℃ when being concentrated into solid component concentration and being 70 quality %) according to following method.

Solid component concentration is measured

At first, reclaim the photosensitive coloring composition CR-1 (15mL) face before the coating, in vacuum drying oven under the room temperature dry 3 hours, measure dry mass (as quality 2) with spoon.

Reclaim the photosensitive coloring composition CR-1 (15mL) that faces before being coated with separately with spoon,, in the time of near the solid component concentration shown in the following formula 1 (quality %) becomes 60 quality %, take out, as sample 1 with hot plate limit heating edge quality measurement (quality X).Measure quality X accurately once more for the sample 1 that takes out, and, obtain solid component concentration (quality %) accurately according to following formula 1.

Reclaim the photosensitive coloring composition CR-1 (15mL) that faces before being coated with separately with spoon,, in the time of near solid component concentration becomes 70 quality %, take out, as sample 2 with hot plate limit heating edge quality measurement (quality X).Measure quality X accurately once more for the sample 2 that takes out, obtain solid component concentration (quality %) accurately according to following formula 1.

Reclaim the photosensitive coloring composition CR-1 (15mL) that faces before being coated with separately with spoon, limit hot plate heating edge quality measurement (quality X), take out in the time of near solid component concentration becomes 80 quality %,, obtain solid component concentration (quality %) accurately for the sample 3 that takes out as sample 3.

Viscosimetric analysis

To sample 1, sample 2 and the sample 3 of above-mentioned taking-up, use the determination of viscoelasticity device STRESSTECH of REOLOGICAInstrumentsAB system respectively, under the condition of 25 ℃ of specimen temperatures, frequency 1Hz, measure viscosity.

Illustrated that after the taking-up 0.5 hour of being determined at of above viscosity is carried out with interior.

Solid component concentration and viscosity by the above-mentioned sample that records 1, sample 2 and sample 3 are obtained the typical curve that shows the relation between solid component concentration and the viscosity, try to achieve solid state component 70% viscosity (25 ℃) from the typical curve that makes.

Toast the mensuration of the film slip that causes by the back

In the making of above-mentioned color filter, measure the thickness (as thickness A) of development and washing back and the preceding red pattern of back baking, measure the thickness (as thickness B) of the identical red pattern in baking back, back.

Use the thickness A and the thickness B of gained, obtain the film slip according to following formula 3.

Film slip (%)=((thickness A-thickness B)/thickness A) * 100 ... formula 3

The mensuration of above-mentioned film slip is undertaken by 10 positions in real estate, the film slip that the mean value of 10 positions is caused as the back baking that utilizes color filter.Illustrated that the mensuration of thickness utilizes contact surfaceness meter P-10 (KLA Tencor Co., Ltd. system) to carry out.

The angle height of colored pattern

At first, in the making of above-mentioned color filter, prepare the test sample till the formation of finishing red pixel (back baking).

Adopt contact surface roughometer P-10 (KLA Tencor Co., Ltd. system), be determined at said determination with " the angle height " of 100 red pixels of selection at random in the sample, with arithmetic mean as the average angle height.

The mensuration of angle height is near the central authorities of red pixel long side, carries out at the Width of pixel (that is the Width of black matrix) moving hand.

In addition, the angle height with from the central portion of colored pixels (with the non-overlapped portion of black matrix; The form of the height till tabular surface pixel region) and the position the highest in overlapping of the black matrix of colored pixels is tried to achieve.

The contrast of LCD degree is estimated

To the above-mentioned liquid crystal indicator energising that obtains, brightness and full brightness of deceiving when showing when in the darkroom, using chroma-luminance meter (opening up general health corporate system BM-5A) to measure white full the demonstration respectively.Arbitrary brightness is all measured at the display frame central portion of liquid crystal indicator.

With ratio (brightness during complete white demonstration the/full brightness during black the demonstration) degree as a comparison, estimate contrast according to following evaluation criterion.

Metewand

A ... contrast is more than 800.

B ... contrast is more than 500 and less than 800.

C ... contrast is more than 250 and less than 500.

D ... contrast less than 250.

Embodiment 2

Among the embodiment 1, except photosensitive coloring composition CR-1 being changed to synthetic in the following way photosensitive coloring composition CR-2, make color filter and liquid crystal indicator similarly to Example 1, carry out similarly to Example 1 mensuration and evaluation.Evaluation result is shown in following table 3.

Red (R) uses the preparation of photosensitive coloring composition CR-2

The time change that utilizes homogenizer to stir except will prepare dispersible pigment dispersion the time is 4 hours, and is same with the preparation of photosensitive coloring composition CR-1 with red (R), and photosensitive coloring composition CR-2 is used in preparation red (R).

Embodiment 3

Among the embodiment 1, in the making of color filter, except photosensitive coloring composition CR-1 being changed to synthetic in the following way photosensitive coloring composition CR-3, make color filter and liquid crystal indicator similarly to Example 1, carry out similarly to Example 1 mensuration and evaluation.Evaluation result is shown in following table 3.

Red (R) uses the preparation of photosensitive coloring composition CR-3

The time change that utilizes homogenizer to stir except will prepare dispersible pigment dispersion the time is 5 hours, similarly prepares redness (R) with red (R) with the preparation of photosensitive coloring composition CR-1 and uses photosensitive coloring composition CR-3.

Embodiment 4 and embodiment 5

In the resin black matrix of embodiment 1 forms, by making development time elongated, the length L of the end of described resin black matrix is changed according to the mode shown in the table 3, in addition, make resin black matrix, color filter and liquid crystal indicator similarly to Example 1, carry out mensuration and the evaluation identical with embodiment 1.Evaluation result is shown in following table 3.

Comparative example 1

Among the embodiment 1, in the process of making color filter, except photosensitive coloring composition CR-1 being changed in the following way synthetic relatively using the photosensitive coloring composition (relatively using composition R1), similarly to Example 1, make color filter and liquid crystal indicator, carry out mensuration and the evaluation identical with embodiment 1.Evaluation result is shown in following table 3.

Relatively use photosensitive coloring composition (relatively using composition R1)

The time change that utilizes homogenizer to stir except will prepare dispersible pigment dispersion the time is 7 hours, and same with the preparation of photosensitive coloring composition CR-1 with red (R), photosensitive coloring composition (relatively using R1) is relatively used in preparation.

Comparative example 2

Among the embodiment 1, in the process of making color filter, except photosensitive coloring composition CR-1 being changed to synthetic in the following way relatively using the photosensitive coloring composition (relatively using composition R2), similarly to Example 1, make color filter and liquid crystal indicator, carry out similarly to Example 1 mensuration and evaluation.Evaluation result is shown in following table 3.

The photosensitive coloring composition of usefulness (relatively using composition R2) relatively

The time change that utilizes homogenizer to stir except will prepare dispersible pigment dispersion the time is 9 hours, and red (R) is same with photosensitive coloring composition CR-1 with preparation, and photosensitive coloring composition (relatively using R2) is relatively used in preparation.

As shown in table 3, use solid state component 70% viscosity (25 ℃) can reduce the angle height as the color filter that the photosensitive coloring composition below the 50Pas forms, use this color filter and the contrast of LCD degree made is good.

In above embodiment, main in the formation of red pixel, to use solid state component 70% viscosity (25 ℃) to describe as example as the photosensitive coloring composition below the 50Pas, also can obtain same effect certainly by the formation of carrying out green pixel, blue pixel.

Claims

1. photosensitive coloring composition, it contains colorant, polymerizable compound, bonding agent and solvent, and to be concentrated into solid component concentration be that viscosity behind the 70 quality % is below the 50Pas in the time of 25 ℃.

2. photosensitive coloring composition according to claim 1, wherein, described colorant is by the covered pigment of macromolecular compound.

3. photosensitive coloring composition according to claim 2, wherein, described pigment is red pigment,

Described macromolecular compound is the polymkeric substance that contains following polymerized unit, and described polymerized unit is from the monomer shown in the following general formula (1),

4. photosensitive coloring composition according to claim 3, wherein, in the described general formula (1), R ¹Shown alkyl is that carbon number is 1～12 alkyl, R ²Shown divalent links group for replacing or unsubstituted alkylidene; The carbon number of the nitrogen heterocyclic ring structure shown in the Z is 6～12.

5. photosensitive coloring composition according to claim 3, wherein, the nitrogen heterocyclic ring structure shown in the Z is phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure or cyclic imide structure.

6. the manufacture method of a color filter, it has:

Resin black matrix forms operation, forms resin black matrix on substrate;

Colored pattern forms operation, the described photosensitive coloring composition of coating claim 1 forms dyed layer on the substrate of described resin black matrix being formed with, the formed dyed layer of prebake conditions, dyed layer after the prebake conditions is carried out pattern exposure, the dyed layer behind the pattern exposure is developed, formation has the colored pattern that is overlapped in the overlapping portion on the described resin black matrix again.

7. the manufacture method of color filter according to claim 6 wherein, between described coating and described prebake conditions, has the dyed layer by described coating formation is carried out vacuum drying operation.

8. the manufacture method of color filter according to claim 6, wherein, described colored pattern forms operation and also has the operation of the described colored pattern that forms being carried out the back baking.

9. the manufacture method of color filter according to claim 8, wherein, the film slip of the caused colored pattern of described back baking is below 25%.

10. the manufacture method of color filter according to claim 6, wherein, be parallel to Width and perpendicular to the cut surface after the described resin black matrix of the plane cutting of real estate in,

Be t at maximum film thickness with described resin black matrix, when being L with the length on the direction that is parallel to substrate surface of described end, ratio L/t is below 3.0.

11. the color filter that the manufacture method by each described color filter in the claim 6～10 makes.

12. color filter according to claim 11 wherein, has the transparent electrode layer that joins with described colored pattern on described colored pattern.

13. color filter according to claim 11, wherein, when observing the surface with 500 times multiplying powers, the radical of striated damage is 3/cm ²Below.

14. liquid crystal indicator that possesses the described color filter of claim 11.