WO2007077751A1

WO2007077751A1 - Ink-jet ink composition for color filter, color filter, process for producing the same, and liquid-crystal display

Info

Publication number: WO2007077751A1
Application number: PCT/JP2006/325495
Authority: WO
Inventors: Hideaki Ito
Original assignee: Fujifilm Corporation
Priority date: 2005-12-28
Filing date: 2006-12-21
Publication date: 2007-07-12
Also published as: CN101346647A; JPWO2007077751A1; TW200728416A; KR20080084842A

Abstract

An ink composition which has suitability for general-purpose use and is effective in forming a colored region having improved flatness (in particular, flatness around partition walls for deep-color separation) through droplet impartation by the ink-jet method. The ink-jet ink composition for color filters, which is for use in forming a colored region through droplet impartation by the ink-jet method, comprises a colorant and a fluorochemical surfactant (copolymer) comprising at least one structural unit (a) derived from a monomer represented by the following general formula (a) and at least one structural unit (b) derived from a monomer represented by the following general formula (b), the proportion of the structural unit (a) to the structural unit (b), (a/b), being from 20/80 to 60/40 by mass [R1 to R3 each is H or methyl; R4 is H or C1-5 alkyl; m is 2-14; n is 1-18; and p and q each is 0-18 (provided that p=q≠0)].

Description

Specification

Ink composition for inkjet color filter, color filter, method for producing the same, and liquid crystal display device

Technical field

[0001] The present invention relates to an ink composition for an inkjet color filter that is suitable for forming colored pixels by applying droplets by an inkjet method, a color filter in which colored pixels are applied by droplets by an inkjet method, and the same The present invention relates to a manufacturing method and a liquid crystal display device.

Background art

[0002] A color filter for a display device is provided in a dot shape, for example, by arranging dot-like images such as red (R), green (G), and blue (B) in a matrix on a substrate such as glass. It has a structure in which images are separated from each other by a dark color separation wall such as a black matrix.

[0003] Conventionally, color filters have been colored by (1) dyeing method, (2) printing method, (3) application of colored photosensitive resin solution, exposure, and development. Method for forming a pattern image (colored resist method; see, for example, Patent Documents 1 to 3), (4) Method for sequentially transferring a pattern image formed on a temporary support onto a final or temporary substrate (See, for example, Patent Documents 4 to 6), (5) A photosensitive colored layer is formed by applying a colored photosensitive resin solution on a temporary support in advance, and the photosensitive colored layer is finally or A method (transfer method) for forming a colored pattern image by directly transferring, exposing and developing on a temporary substrate is known (for example, see Patent Document 7). A method using an ink jet method is also known (see, for example, Patent Document 8).

Among these methods, the colored resist method can produce a color filter with high positional accuracy. However, the colored resist method is not advantageous in terms of cost due to a large loss in the application of the photosensitive layer resin solution. Further, only by the ink jet method, there is a tendency that it is difficult to obtain a pixel with good force position accuracy that is less costly and less costly.

[0005] Corresponding to the above, a method has been proposed in which a black matrix is formed by a colored resist method, and then a colored pattern (pixel) such as RGB is formed by using an inkjet method. However, when a colored ink (R, G, B, etc.) is deposited on a recess (colored layer forming region) surrounded by a partition such as a black matrix to produce a color filter, When the solid content concentration is low, a desired thickness cannot be obtained after drying unless the amount of droplet ejection is sufficient. Therefore, it is necessary to deposit colored ink over the volume of the recess surrounded by the partition walls. However, as the solvent evaporates, irregularities occur in the vicinity of the partition walls in the colored layer (pixels), which causes display unevenness when a display device (panel) is formed.

[0007] In this connection, a technique for improving the flatness of the colored layer surface by adjusting the surface energy and boiling point of the solvent used is known. This technology requires the use of special solvents. Therefore, further studies including versatility were considered essential.

On the other hand, it is known to use a composition containing a specific surfactant for the production of a color filter (see, for example, Patent Document 9). According to this, it is said that it is possible to prevent the coated surface from being damaged due to the influence in the manufacturing process after coating the substrate.

[0009] Further, it is disclosed that a fluorosurfactant can be used as an additive in a resin composition for producing a color filter as required (see, for example, Patent Document 10) Patent Document 1 : JP-A 63-298304

Patent Document 2: Japanese Patent Laid-Open No. 63-309916

Patent Document 3: JP-A-1 152449

Patent Document 4: JP-A 61-99103

Patent Document 5: Japanese Patent Laid-Open No. 61-233704

Patent Document 6: JP-A 61-279802

Patent Document 7: JP-A-61-99102

Patent Document 8: JP-A-8-227012

Patent Document 9: Japanese Patent Laid-Open No. 2003-337424

Patent Document 10: Japanese Unexamined Patent Publication No. 2000-310706

Disclosure of the invention

Problems to be solved by the invention

[0010] As described above, an inkjet method is used between partition walls (dark color separation walls) formed in advance on a substrate. Various studies have been made on techniques for forming pixel patterns by ejecting more liquid ink. However, after drying the ink due to solvent volatilization, etc., the surface of the colored area that becomes the pixel has an uneven shape, and immediately after the solvent is dried, simply containing a fluorine-based surfactant or the like. It is difficult to form a colored layer (pixel pattern) with good flatness.

[0011] The present invention has been made in view of the above circumstances, and is excellent in flatness of a colored region (particularly in the vicinity of a dark color separation wall) formed by applying droplets by an inkjet method having high versatility. An ink composition for an inkjet color filter capable of obtaining a color filter (including colored pixels constituting the color filter) is provided. In addition, the present invention has no display unevenness and high display quality.

V, a color filter, a manufacturing method thereof, and a liquid crystal display device are provided.

Means for solving the problem

[0012] Specific means for achieving the above object are as follows.

<1> An ink jet color filter ink composition used for forming a colored region formed by applying droplets by an inkjet method, comprising a colorant and a fluorosurfactant, wherein the fluorosurfactant comprises A structural unit derived from a monomer represented by the following general formula (a) and at least one structural unit b derived from a monomer represented by the following general formula (b): An ink composition for an inkjet color filter, which is a copolymer that is a copolymer having a mass ratio (aZb) of a to the structural unit b of 20Z80 to 60Z40.

[0013] [Chemical 1]

In the general formula (a) or (b), and R are each independently a hydrogen atom or a Represents a til group. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 2 to 14, and n represents an integer of 1 to 18. p and q each independently represent an integer of 0 to 18, and p and q do not represent 0 at the same time.

<2> Content power of the fluorosurfactant Inkjet color filter as described in <1> above, which is 0.01 to 0.2% by mass of the total mass of the ink yarn and the composition. It is an ink composition.

<3> At least one of the structural units a is such that R ¹ is a hydrogen atom and a CF force m 2m + l

-C F, wherein n is a unit derived from a monomer of 2,

6 13

> Or <2> The ink composition for an inkjet color filter according to <2>.

<4> At least one of the structural units b is as follows: R ² is a hydrogen atom, R ³ force methyl group, R ⁴ is a hydrogen atom, p is 7, and q is 0 The ink composition for an inkjet color filter according to any one of 1) to <3>, wherein the ink composition is derived from a monomer that is

<5> At least one of the structural units b is as follows: R ² is a hydrogen atom, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, p is 0, and q is 7. The ink composition for an ink jet color filter according to any one of the above items 1> to <4>, wherein the ink composition is a unit derived from a monomer of 7.

<6> A binary or ternary or higher copolymer containing 20 to 60% by mass of the structural unit a and 80 to 40% by mass of the structural unit b. The ink composition for ink-jet color filters according to any one of the above items 1> to <5>.

<7> The proportion of the structural unit a is 25 to 60 wt%, the ink jet color filter according to the rather 6> the proportion of the structural unit b is characterized in that it is a 60 to 40 weight ^_0/0 Ink composition.

<8> The content of the fluorine-based surfactant, for ink jet color filter according to <2>, which is a 0.05 to 0.15 weight ^_0/0 of the total weight of the ink composition Ink composition.

<9> The above-described <1>, further comprising a polymerizable compound and a polymerization initiator 8> The ink composition for inkjet color filters according to any one of 8>.

<10> A method for producing a color filter having a pixel group of two or more colors having different hues on a substrate and a light-shielding dark color separation wall that separates the pixels constituting the pixel group from each other. Thus, a colored region is formed by applying the ink composition for an inkjet color filter according to any one of <1> to <9> to the recesses separated by the dark color separation wall by an inkjet method. A method of manufacturing a color filter having a step of:

<11> The method for producing a color filter according to <10>, wherein the dark color separation wall has a height in the normal direction of the substrate of 1.0 to 6. O / zm.

<12> The above <10> or <10>, wherein the variation range of the thickness in the normal direction of the colored region within 0.5 m in the direction parallel to the substrate surface from the edge of the dark color separation wall is 0.5 μm or less <11> The method for producing a color filter according to <11>.

<13> The above <10>, further comprising a first curing step of irradiating at least one colored region formed in the step of forming the colored region with an actinic ray to cure. ~ <12> !, the deviation is one of the methods for producing a color filter.

<14> After the first curing step, the method further includes a second curing step in which all the colored regions having a desired hue including red (R), green (G), and blue (B) are cured by heat. The method for producing a color filter as described in 13> above.

[0019] <15> A color filter produced by the method for producing a color filter according to any one of <10> to <14>.

<16> A liquid crystal display device comprising the color filter according to <15>.

The invention's effect

[0020] According to the present invention, a color filter excellent in flatness of a colored region (particularly in the vicinity of a dark color separation wall) formed by applying droplets by an inkjet method having high versatility (constitutes this) Ink composition for ink-jet color filter can be provided which can provide colored pixels.

In addition, according to the present invention, it is possible to provide a color filter having no display unevenness and high display quality, a manufacturing method thereof, and a liquid crystal display device.

BEST MODE FOR CARRYING OUT THE INVENTION [0021] Hereinafter, the ink yarn composition for an inkjet color filter of the present invention will be described in detail. Details of the color filter using this ink composition, a method for producing the same, and a liquid crystal display device are also described.

[0022] Ink Composition for Inkjet Color Filter>

The ink composition for ink-jet color filters of the present invention (hereinafter sometimes referred to as “the ink composition of the present invention”) contains at least a colorant and the following fluorosurfactant according to the present invention. The ink composition of the present invention is used to form a colored region formed by applying droplets to a recess surrounded by a dark color separation wall by an inkjet method. In addition, the ink composition of the present invention can be constituted by using a polymerizable compound, a polymerization initiator, a solvent, and other components as required.

[0023] The ink composition of the present invention provides a surface of a colored region to which droplets have been applied when droplets are applied between dark color separation walls by an inkjet method to form a colored region that constitutes a color filter. It can be formed with good flatness, display non-uniformity, and high-quality image display with display quality.

[0024] In the present invention, flatness means from the end of the dark color separation wall of the colored region (colored layer that becomes R pixel, G pixel, B pixel, etc.) constituting the color filter. Thickness variation within 10 / zm in the direction parallel to the substrate surface. The fluctuation range is preferably less than 0. This fluctuation range is measured using a stylus type film thickness meter (P10, manufactured by KLA-Tencor Corporation).

[0025] Hereinafter, each component constituting the ink composition of the present invention will be described in detail.

(Coloring agent)

The ink composition of the present invention can be constituted using a known colorant (dye, pigment). Among known colorants, when a pigment is used, it is desirable that the pigment is uniformly dispersed in the colored liquid composition. Accordingly, the particle diameter of the pigment is preferably 0.1 m or less, particularly preferably 0.08 m or less.

[0026] Known dyes or pigments include, for example, Victoria 'Pure One Blue BO (CI 425 95), Auramin (CI 41000), Huaz-Black HB (CI 26150), CI Pigment, Yellow 1, CI Pigment 'Yellow 3, CI Pigment''Yellow 12, CI Pigme Yellow, 13, CI pigment 'Yellow 14, CI pigment' Yellow 5, CI pigment 'Yellow 16, CI pigment' Yellow 17, CI pigment 'Yellow 20, CI pigment' Yellow 24, CI pigment 'Yellow 31, CI pigment 'Yellow 55, CI Pigment' Yellow 60, CI Pigment 'Yellow 61, CI Pigment' Yellow 65, CI Pigment 'Yellow 71, CI Pigment' Yellow 73, CI Pigment 'Yellow 74, CI Pigment' Yellow 81, CI Pigment 'Yellow 83, CI Pigment; Yellow 93, CI Pigment' Yellow 95, CI Pigment 'Yellow 97, CI Pigment' Yellow 98, CI Pigment 'Yellow 100, CI Pigment' Yellow 101, CI Pigment 'Yellow 104, CI Pigment 'Yellow 106, CI Big Pigment''Yellow 108, CI Big Bear Yellow 109, CI Pigment Yellow 110, CI Pigment 卜. Yellow 113, CI Big Men 卜 'Yellow 114, CI Big Men 卜' Yellow 116, C. I. Big Men 卜 'Yellow 117, CI Pigment 卜' Yellow 119, CI Pigment 卜 Yellow 120, CI Pigment 'Yellow 126, CI Pigment' Yellow 127, CI Pigment Yellow 128, CI Pigment 'Yellow 129, CI Pigment' Yellow 138, C. I. Pigment 'Yellow 139, CI Pigment' Yellow 150, CI Pigment 'Yellow 1 51, CI Pigment' Yellow 152, CI Pigment 'Yellow 153, CI Pigment-Yellow 154, CI Pigment 卜' Yellow 155, CI Pigment 卜 'Yellow 156, CI Pigment' Yellow 166, CI Pigment 'Yellow 168, CI Pigment' Yellow 17 '5, CI Pigment' Yellow 180, CI Pigment 'Yellow 185 ;

CI Pigment 'Orange 1, CI Pigment' Orange 5, CI Pigment 'Orange 13, CI Pigment' Orange 14, CI Pigment 'Orange 16, CI Pigment' Orange 17, CI Pigment 'Orange 24, CI Pigment' Orange 34, CI CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment 'Orange 40, CI Pigment 卜' Orange 43, CI Pigment ビ Orange 46, CI Pigment 卜 Orange 49, CI Pigment 'Orange 51, CI Pigment' Orange 61 CI Pigment 'Orange 63, CI Pigment' Orange 64, CI Pigment 'Orange 71, CI Pigment' Orange 73; CI Pigment Noy: GI Pigment No .: LI Pigment No .: Let 19, No. 23 CI Pigment No. 23, CI Pigment Nonot 29, CI Pigment Nonot 32, CI Pigment Nore 36, CI Pigment 38;

CI Pigment 'Red 1, CI Pigment' Red 2, CI Pigment 'Red 3, CI Pigment' Red 4, CI Pigment 'Red 5, CI Pigment' Red 6, CI Pigment Red 7, CI Pigment 'Red. 8, CI Pigment 'Red 9, CI Pigment' Let 10, CI Pigment 'Red 11, CI Pigment' Red 12, CI Pigment 'Red 14, CI Pigment' Red 15, CI Pigment 'Red 16, CI Pigment' Red 16 , CI Pigment 'Red 18, CI Pigment' Red 19, CI Pigment 'Red 21, CI Pigment.Red 22, CI Pigment.Red 23, CI Pigment.Red 30, CI Pigment.Red 31, CI Pigment.Red 32 CI Pigment Red 37, CI Pigment Red 38, CI Pigment 'Le , CI Pigment 'Red 41, CI Pigment' Red 42, CI Pigment 'Red 48: 1, CI Pigment' Red 48: 2, CI Pigment 'Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment-Red 49: 2, CI Pigment 'Red 50: 1, CI Pigment' Red 52: 1, CI Pigment 'Red 53: 1, CI Pigment' Red 57, CI Pigment 'Red 57: 1, CI Pigment 'Red 57: 2, CI Pigment' Red 58: 2, CI Pigment 'Red 58: 4, CI Pigment' Red 60: 1, CI Pigment 'Red 63: 1, CI Pigment' Red 63 : 2, C.I. pigment 'Red 64: 1, CI pigment' Red 81: 1, CI pigment 'Red 83,

C. I. Pigment 'Red 88, C. I Pigment' Red 90: 1, C. I. Pigment. Red 97, C

I. Pigment Red 101, C. I. Pigment Red 102, C. I. Pigment Red 104, C

I. Pigment Red 105, C. I. Pigment Red 106, C. I. Pigment Red 108, C

I. Pigment Red 112, C. I. Pigment Red 113, C. I. Pigment Red 114, C

I. Pigment Red 122, C. I. Pigment Red 123, C. I. Pigment Red 144, C

I. Pigment Red 146, C. I. Pigment Red 149, C. I. Pigment Red 150, C

I. Pigment Red 151, C. I. Pigment Red 166, C. I. Pigment Red 168, C

I. Pigment Red 170, C. I. Pigment Red 171, C. I. Pigment Red 172, C

I. Pigment Red 174, C. I. Pigment Red 175, C. I. Pigment Red 176, C

I. Pigment Red 177, C. I. Pigment Red 178, C. I. Pigment Red 179, C

I. Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, C I. Pigment '' Red 188, CI Pigment '' Red 190, CI Pigment. Red 193, C

I. Pigment '' Red 194, C. I. Pigment '' Red 202, C. I. Pigment 'Red 206, C

I. Pigment '' Red 207, C. I. Pigment '' Red 208, C. I. Pigment '' Red 209, C

I. Pigment '' Red 215, C. I. Pigment '' Red 216, C. I. Pigment '' Red 220, C

I. Pigment '' Red 224, C. I. Pigment '' Red 226, C. I. Pigment '' Red 242, C

I. Pigment '' Red 243, C. I. Pigment '' Red 245, C. I. Pigment 'Red 254, C

I. Pigment '' Red 255, C. I. Pigment '' Red 264, C. I. Pigment '' Red 265;

[0029] C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 1

5: 4, C.I. pigment 'blue 15: 6, C.I. pigment' blue 60;

[0030] C. I. Pigment 'Green 7, C. I. Pigment' Green 36;

C. I. Pigment 'Brown 23, C. I. Pigment' Brown 25;

C. I. Pigment 'Black 1, C. I. Pigment' Black 7;

, Etc.

[0031] Among the colorants, (i) CI pigment 'Red 25 4 is preferred for the R (red) ink composition, and (ii) CI pigment' green 36 for the G (green) ink composition. Force S is preferred, and (iii) CI pigment 'Blue 15: 6 is preferred in the ink composition of B (Blue).

Further, the pigments may be used in combination.

[0032] When pigments are used in combination, the preferred pigment combinations are CI Pigment 'Red 254, CI Pigment Red 177, CI Pigment Red 224, CI Pigment' Yellow 139, or CI Pigment ' In combination with Violet 23, CI Pigment 'Green 36, CI Pigment' Yellow 150, CI Pigment 'Yellow 139, CI Pigment' Yellow 185, CI Pigment 'Yellow 13 8, or CI Pigment' Yellow 180 ' In the CI Pigment 'Blue 15: 6, a combination with CI Pigment' Violet 23 or CI Pigment 'Blu 60 is mentioned.

[0033] When the pigment is used in combination, the CI pigment 'Red 254, CI pigment' Dalene 36, or CI pigment 'Blue 15: 6 in the pigment contains the CI pigment' In Red 254, 80% by mass or more is preferable, particularly 90% by mass or more is preferable. In the C.I. Pigment 'Green 36, 50% by mass or more is preferable, and 60% by mass or more is particularly preferable. Also, in the CI pigment 'Blue 15: 6, 80% by mass or more is preferable, particularly 90% by mass or more is preferable.

[0034] The pigment is preferably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant to a polymerizable compound (or vehicle or solvent) described later. There are no particular restrictions on the disperser used when dispersing the pigment. For example, the aider, roll mill, and the like described in “Encyclopedia of Pigments” (Asakura Kunizo, 1st edition, Asakura Shoten, 2000, p. 438) Well-known dispersers such as Atrider, Super Mill, Dissolver, Homomixer, and Sand Mill can be used. Further, the material may be finely pulverized using frictional force by mechanical grinding described on page 310 of “Encyclopedia of Pigments”.

The particle diameter of the colorant (pigment) is preferably 0.001 to 0.1 μm in terms of number average particle diameter, and more preferably 0.01 to 0.08 μm. When the number average particle diameter is within the above range, the particle surface energy is lowered, aggregation is suppressed, and pigment dispersion can be performed satisfactorily. In addition, the dispersion state can be kept more stable and good contrast can be obtained.

“Particle size” refers to the diameter when particles in an electron micrograph image are represented by a circle having the same area. “Number average particle size” means an average value obtained by calculating the particle size of particles and taking the average of 100 particles.

[0036] The contrast of the colored region can be improved by reducing the particle size of the dispersed pigment. Reducing the particle size can be achieved by adjusting the dispersion time of the pigment dispersion. For the dispersion, the known disperser can be used.

The dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is within the above range, a good contrast with a small pigment particle size can be obtained. In addition, an increase in the viscosity of the dispersion can be suppressed, and ink jet head force can be discharged well.

Also, the difference in contrast between two or more colored areas is preferably within 600. In order to adjust within 600, it is desirable to adjust the pigment particle size. [0037] The contrast of each colored region constituting the color filter is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast is within the above range, an easy-to-see image with a whitish impression can be obtained when an image of a liquid crystal display device including a color filter is observed. The difference in contrast between the colored regions is preferably 600 or less, more preferably 410 or less, still more preferably 350 or less, and most preferably 200 or less. If the difference in contrast is within 600, the amount of light leakage from each colored area at the time of black display does not differ greatly, and the color balance of black display is good.

The “contrast of the colored region” means a contrast that is individually evaluated for each color of R, G, and B constituting the color filter. Contrast can be measured as follows. In other words, the brightness of light passing through the other polarizing plate with the backlight applied from the side of one polarizing plate with the polarizing plates overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates made parallel to each other Measure Y1. Further, with the polarizing plates orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. Y1ZY2 is calculated using the measured values obtained.

Note that the polarizing plate used for contrast measurement is the same as the polarizing plate used for a liquid crystal display device using a color filter.

[0039] The amount of the colorant in the ink composition is a force that can be appropriately selected in order to obtain a desired hue and density, and is preferably 3.0% by mass or more based on the total mass of the ink composition. More preferably, it is 5.0% by mass or more.

[0040] (Fluorosurfactant)

The ink composition of the present invention is derived from at least one of structural units a derived from a monomer represented by the following general formula (a) and a monomer represented by the following general formula (b) as a fluorine-based surfactant. And at least one copolymer (hereinafter referred to as “surface activity according to the present invention”) having a mass ratio (a / h) of structural unit a to structural unit b of 20Z80 to 60Z40. "Sometimes referred to as an agent"). This fluorosurfactant is a fluorine-containing polymer. This fluorosurfactant is an ink surface formed by ink-jetting ink into a recess that is finely partitioned by a dark color separation wall and surrounded by the separation wall. That is, the surface of the colored region can be flattened.

[0041] [Chemical 2]

[0042] The monomer represented by the general formula (a) (hereinafter, also referred to as monomer a) will be described.

In the general formula (a), R ¹ represents a hydrogen atom or a methyl group. In general formula (a), —CF may be linear or branched! /. m represents an integer of 2 to 14, preferably 4 to 1 m 2m + l

It is an integer of 2. n represents an integer of 1 to 18, preferably 2 to 10.

[0043] Examples of C F include C F, C F, and C F.

m 2m + l 4 9 6 13 12 25

[0044] The proportion of -C F is preferably 20 to 70% by mass with respect to the total mass of the monomer a m 2m + l

Particularly preferred is 40 to 60% by mass.

[0045] Among the monomers a, R ¹ is a hydrogen atom, -CF is CF, n is 2 and m 2m + l 6 13

Certain compounds are particularly preferred.

[0046] The monomer represented by the general formula (b) (hereinafter, also referred to as monomer b) will be described.

In the general formula (b), R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each independently represent an integer of 0 to 18, and p and q do not represent 0 (zero) at the same time. p and q are preferably 2-8.

[0047] The alkyl group having 1 to 5 carbon atoms represented by R ⁴ is preferably a methyl group or an ethyl group.

[0048] Among the monomers b, a compound wherein R ² is a hydrogen atom, an R ³ force methyl group, R ⁴ is a hydrogen atom, p is 7, and q is 0 Or a compound in which R ² is a hydrogen atom, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, p is 0, and q is 7. preferable.

[0049] As the monomer a contained in one molecule of the surfactant according to the present invention, only one type having the same structure may be used, or a plurality of types having different structures may be used. The same applies to monomer b.

[0050] The weight average molecular weight Mw of the surfactant according to the present invention is preferably 1000 to 40000 force S, more preferably 5 000 to 30000 force! / ヽ.

[0051] As described above, the surfactant according to the present invention is a copolymer obtained by copolymerizing at least the monomer a and the monomer b, and the ratio of the monomer aZ monomer b in the copolymer is as follows. The (mass ratio) is 20Z80-60Z40. When the copolymerization ratio is within the above range, the ink is applied and dried so as to rise above the wall height of the separation wall in the concave portion that is finely divided by the dark separation wall and surrounded by the separation wall. In this case, the upper surface of the ink, that is, the surface of the colored region to be a colored pixel can be flattened, and this is particularly effective for improving the flatness near the dark color separation wall.

[0052] The surfactant according to the present invention is also preferably a copolymer obtained by copolymerizing the above-mentioned monomers a and b with other optional monomers. In this case, other optional monomers that can be copolymerized in addition to monomers a and b include, for example, styrene, butyltoluene, α-methylstyrene, 2-methylstyrene, chlorostyrene, butylbenzoic acid, and sodium benzenebenzene sulfonate. Styrene such as aminostyrene and derivatives thereof, substituted products, gens such as butadiene and isoprene, acrylonitrile, butyl ethers, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, Styrene sulfonic anhydride Maleic acid, kain cinnamate, vinyl chloride, vinyl acetate, etc.

[0053] For example, when the surfactant according to the present invention is 100 parts by mass, a copolymer of a binary or ternary or monomer having a force of 20 to 60 parts by mass of monomer a and 80 to 40 parts by mass of monomer b, monomer A ternary or higher copolymer consisting of a20 to 60 parts by mass, monomers b80 to 40 parts by mass, and other optional monomers (remaining mass) is preferred.

Furthermore, a binary or ternary or higher copolymer consisting of 25 to 60 parts by weight of monomer a and 60 to 40 parts by weight of monomer b, 25 to 60 parts by weight of monomer a, 60 to 40 parts by weight of monomer b, A ternary or higher copolymer consisting of other optional monomers (remaining mass) is preferred.

[0054] The surfactant according to the present invention is a copolymer obtained by copolymerizing at least the monomer a and the monomer b, and regular random block copolymerization, for example, block copolymerization is not particularly limited. Even if the graft copolymer is out of alignment! /.

[0055] As the surfactant according to the present invention, two or more surfactants having different molecular structures and different Z or monomer compositions can be used.

[0056] Specific examples of the surfactants according to the present invention (exemplary compounds Νο.1 to Νο.16) are shown below. However, the present invention is not limited to these.

[0057] [Chemical 3] Fluorosurfactant

Monomer a Monomer b ¹ Monomer b ²

Common ratio Mass average

= a: b ¹ : b ² Molecular weight

No. R ¹ mn ³ R ⁴ P q R ^{2 3} R ⁴ P q

1 H 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000

2 H 6 2 H CH ₃ H 7 0 HHH 0 7 40:40:20 30000

3 H 6 2 H CH ₃ H 7 0 One 40: 60: 0 30000

4 H 6 2 H CH ₃ H 7 0 HHH 0 7 25:60:15 30000

5 H 6 2 H CH ₃ H 7 0 HHH 0 7 60:25:15 30000

6 H 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 5000

7 H 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000

8 H 6 2 H CH ₃ H 6 1-40: 60: 0 30000

9 H 6 2 H CH ₃ H 1 6 ― 40: 60: 0 30000

10 CH ₃ 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000

11 H 6 2 H CH ₃ CH ₃ 0 HH CH ₃ 0 7 40: 55: 5 30000

12 H 6 2 CH ₃ CH ₃ H F 0 CH ₃ HH 0 7 40: 55: 5 30000

13 H 12 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000

14 H 4 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000

15 H 6 2 H CH ₃ H 14 0 HHH 0 7 40: 55: 5 30000

16 H 6 2 H CH ₃ H 7 0 HHH 0 14 40: 55: 5 30000 [0058] The content of the surfactant according to the present invention in the ink composition for an inkjet color filter is preferably 0.01 to 0.2% by mass of the total mass of the ink. % Is more preferable. When the content is within the above range, it is possible to improve the flatness of the pattern surface when an ink jet is applied between the dark color separation walls to form a colored pattern.

As a result, it is possible to prevent display unevenness in the image when the image is displayed.

[0059] (Polymerizable compound)

As the polymerizable compound, a radical polymerizable compound that is cured by a polymerization reaction with a radical active species and a cationic polymerizable compound that is cured by a cationic polymerization reaction with a cationic active species can be used.

The ink composition of the present invention can be formed into a radical polymerizable composition when the radical polymerizable compound is used. The ink composition of the present invention can be formed into a cationically polymerizable composition when a cationically polymerizable compound is used. Any of these configurations is suitable.

[0060] Radical polymerizable compound

Specific examples of the radical polymerizable compound include, but are not limited to, the following compounds. The radical polymerizable compound includes a monofunctional monomer, a bifunctional or higher monomer, and an oligomer.

[0061] The monofunctional monomer has one ethylenically unsaturated double bond. For example, butanediol monoacrylate, N, N dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-methoxyethyl acrylate N-Bull Force Prolatatam, N Vinylpyrrolidone, Ataliloyl Morpholine, N-Burformamide, Cyclohexyl Atalylate, Cyclic Hexinoremetatalylate, Dicyclopenta-Nolemetatalylate, Glycidyl Atalylate Rate, isodecyl acrylate, phenoxymetatalylate, stearyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxychetyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate Butyl Atari rate, t- butyl Atari rate, isobutyl O Chi le Atari rate, Isoboru - Le Atari rate, methoxy triethylene glycol Atari rate, 2-ethoxy E chill Atari rate, tetrahydropyran Acquisition of full Ril attalylate, 3-methoxybutyl acrylate, benzyl acrylate, ethoxyethyl cetyl acrylate, butoxy catechol acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methyl phenoxy acetyl acrylate Examples include dipropylene glycol acrylate.

[0062] Examples of the bifunctional or higher functional monomers and oligomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 6 hexanediol di (Meth) acrylate, ethoxylated 1,6 hexanediol ditalate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) attaly , Tripropylene glycol di (meth) acrylate, polypropylene glycol diathalate, 1,4 butanediol di (meth) acrylate, 1,9-nonandi dialate, tetraethylene glycol dialate —Butyl 2— Thirul 1,3 propanediol ditalylate, dimethylol-tricyclodecane diacrylate, hydroxypivalic acid neopentylglycol ditalylate, 1,3 butylene glycol di (meth) atalylate, ethoxylated bisphenol A di ( (Meth) acrylate, propoxylated bisphenol A di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, dimethylol dicyclopentane diathalate, trimethylol propane triacrylate, ethoxylated trimethylol Propane tritalylate, propoxylated trimethylol Propane tritalylate,

[0063] pentaerythritol triatalylate, tetramethylolpropane tritalylate, tetramethylol methane tritalylate, pentaerythritol tetratalylate, force prolatatone modified trimethylolpropane tritalylate, ethoxylated isocyanuric acid triatalylate, tri ( 2-Hydroxyethylisocyanurate) triatareyl, propoxylate glyceryl riatalylate, tetramethylol methane tetraatarylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraatalylate, ethoxylated pentaerythritol tetraatalylate Hexaatalylate, Neopentyl glycolo Rigoatarylate, 1, 4 Butanediol oligoattaryl DOO, 1, 6 hexane diol oligo Atari rate, trimethylolpropane oligo Atari rate, pentaerythritol cage Examples include goat acrylate, urethane acrylate, epoxy acrylate, and polyester acrylate.

These compounds may be used alone or in combination of two or more as required.

[0064] One force thione polymerizable compound

The cationically polymerizable compound is a compound that cures by causing a polymerization reaction by the cationic active species generated from the photopolymerization initiator.

Examples of the cationically polymerizable compound include various known cationically polymerizable monomers known as photopower thione polymerizable monomers. For example, JP-A-6-9714, JP-A-2001-31892, 2001-40068, 2001-55507, 2001-310938, 2001-310937, 2001-220526, etc. And bule ether compounds, oxetane compounds, oxsilani compounds and the like.

[0065] Examples of the cationically polymerizable compound having a bull ether as a functional group include urethane bull ether (bull ether urethane) and ester bull ether. These oligomers can be used alone or in combination.

[0066] Further, as specific examples of the aromatic epoxy resin, polyvalent phenol having at least one aromatic ring, or polyglycidyl ether of alkylene oxide-attached product thereof, such as bisphenol A, bisphenol F, Further, glycidyl ether, epoxy novolac resin, bisphenol A novolak diglycidyl ether, bisphenol F novolac diglycidyl ether, and the like, which are further carotenated with alkylene oxide, can be mentioned.

As a specific example of alicyclic epoxy resin, polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring or cyclohexene, cyclopentene ring-containing compound is epoxidized with an oxidizing agent. The resulting cyclohexene oxide structure-containing compound, cyclopentene oxide structure-containing compound, or vinyl cyclohexane structure-containing compound obtained by epoxidizing a compound having a vinylcyclohexane structure with an oxidizing agent. Things. For example, hydrogenated bisphenol nore A diglycidinoreethenole, 3, 4 epoxycyclohexenoremethinolere 3, 4-epoxy cyclohexyl carboxylate, 3, 4 epoxy 1-methylcyclohexyl luo 3, 4 Epoxy 1-Methylcyclohexanecarboxylate, 6-Methyl-3,4 Epoxycyclohexylmethyl-6-Methyl-3,4-Epoxycyclohexanecarboxylate, 3, 4 Epoxy-3-Methylcyclohexylmethyl-3,4-Epoxy-3— Methylcyclohexanecarboxylate, 3, 4 Epoxy 5—Methylcyclohexylmethylol 3,4 Epoxy 5-—Methylenocyclohexyl hexanolate, 2- (3,4-epoxycyclohexylene 5,5-spiro 3,4-epoxy) Cyclohexane metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, butylcyclohexene dioxide, 4 vinyl epoxycyclohexane, bis (3,4-epoxy 6-methylcyclohexylmethyl) adipate, 3, 4 Epoxy 6-methylcyclohexyl Ruruboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene oxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and the like.

As specific examples of aliphatic epoxy resin, polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polybasic acid, and aliphatic long-chain unsaturated hydrocarbon are oxidized with an oxidizing agent. Examples thereof include epoxy-containing compounds, glycidyl acrylate or homopolymer of glycidyl methacrylate, copolymers of glycidyl acrylate or glycidyl methacrylate. Representative compounds include 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglyceride. Polyglycol glycidyl ethers such as glycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycolanol diglycidinole ether, polypropylene glycolanol diglycidyl ether, and aliphatics such as propylene glycol and glycerin Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to polyhydric alcohol, aliphatic long-chain dibasic Like diglycidyl ester of. In addition, aliphatic Monoglycidyl ethers of higher alcohols, phenol, cresol, butylphenol, polyether alcohol monoglycidyl ethers obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxy soybean oil, epoxy stagyl stearate, epoxy Examples thereof include butyl stearate and epoxidized rubber oil.

[0068] The amount of the polymerizable compound in the ink composition is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the ink composition. When the polymerizable compound is within the above range, the curability can be satisfied with the intensity of a general active energy ray, and it is not necessary to lengthen the irradiation time.

[0069] (Polymerization initiator)

The polymerization initiator used in the present invention generates radically active species upon irradiation with active energy rays, and generates a radical polymerization initiator that initiates polymerization of a radical polymerizable compound, and a cationically active species. Any cationic polymerization initiator that initiates polymerization of the cationic polymerizable compound can be used in accordance with the polymerizable compound.

[0070] Radical polymerization initiator

Examples of the radical polymerization initiator include the following. For example, the benzophenone series includes benzophenone, benzoylbenzoic acid, 4-phenol-penzophenone, 4,4-jetylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-benzoyl 4'-methyldiphen- Rusulfide etc. are mentioned. Examples of thixanthone include thixanthone, 2 chloroxanthone, 2, 4 jetylthioxanthone, 1 chloro-4 propoxythixanthone, isopropyl xanthone, and the like. As the acetophenone system, 2-methyl-1-mono (4-methylthio) phenol- 2-morpholinopropane 1-one, 2-benzyl-1-2-dimethylamino-1-(4-morpholinophenol) -butanone 1, 2 —Hydroxy-2-methyl 1-phenolpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4 -Phenoxydichloroacetophenone, diethylacetophenone, 1-hydroxycyclohexyl phenol ketone and the like. As benzoin series, benzoin methyl ether, benzoin isobutyl ether, benzine And rumethyl ketal. Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6 trimethylbenzoyl) acylphosphine oxide, and the like.

[0071] One force thione polymerization initiator

As the cationic polymerization initiator, for example, a diazonium salt, an iodine salt, a sulfonium salt, an iron arene complex, and an organic polyhalogen compound are preferable. Examples of diazo-um salt, monodonium salt, and sulfo-um salt are JP-B 54-14277, JP-B 54-14278, JP-A 51-56885, US Pat. 70, 296 specification, 3,853, 002 specification etc. are mentioned.

Examples of the light-power thione polymerization initiator include aromatic diazo-um salt, aromatic sulfo-um salt, aromatic ododonium salt, meta-oxycene compound, and key compound Z aluminum complex. It is done.

[0072] The amount of the polymerization initiator in the ink composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass with respect to the polymerizable compound (mass). When the polymerization initiator is within the above range, the curability can be satisfied with the intensity of a general active energy ray, and it is not necessary to lengthen the irradiation time.

[0073] (Solvent)

The ink composition of the present invention can be constituted using a solvent in addition to the above components. When a solvent is contained, an appropriate fluidity can be imparted for droplet ejection by the ink jet method, and it is effective for the formation of flatness by the surfactant according to the present invention described above. The amount of the solvent can be appropriately selected within a range that does not impair the effects of the present invention.

The solvent in the present invention assists the dissolution or dispersion of functional materials such as a colorant, a polymerizable monomer, an additive, and a polymer contained in the ink composition of the present invention. This solvent functions to enhance the fluidity of the ink composition of the present invention to facilitate droplet ejection and the like, and after droplet ejection of the ink composition and predetermined drying or heat treatment, Most of them (approximately 90% or more) have properties that are removed by 1S evaporation. For example, the polymerizable monomer is also in a liquid state, but when the solvent is added thereto, the fluidity is further increased and droplet ejection is facilitated.

[0075] As the solvent, an organic solvent having a boiling point of 100 ° C or lower is usually used. Ink dry For the purpose of preventing dryness and clogging of the head, a high boiling point solvent having a boiling point of 200 ° C or lower, and sometimes higher, is used.

[0076] Examples of the solvent include those described in "New Edition Solvent Pocket Book" (edited by Organic Synthetic Science Association, published by Ohm) and "Solvent Handbook" (edited by Shozo Asahara et al., Kodansha, 1976). Specific examples include ion-exchanged water, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethylol ether, diethylene glycol monomethenole etherenole; diethylene glycol Diethylene glycol monoalkyl ether acetates such as mono-n-butyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol noremonomethinoatenoreacetate and propyleneglycolenoethylenoleatenoreacetate; diethylene glycol dimethyl ether Other ethers such as: cyclohexanone, 2 heptanone, 3 heptanone, methyl ethyl keto , Ketones such as methyl isobutyl ketone and acetone; lactic acid alkyl esters such as 2-hydroxypropionate ethyl; 3-methyl-3-methoxybutyropionate, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxy Echiru propionic acid, acetic acid n- butyl, isobutyl acetate, formic acid n- Amiru acetate Isoamiru, n- butyl propionate, butyrate Echiru, isopropyl butyrate n- butyl, other esters such as pyruvic acid Echiru; _Y Buchirorataton etc. These high boiling solvents can be used.

[0077] The ink composition for an inkjet color filter of the present invention preferably has a solid content of 15% by mass or more, more preferably 50% by mass or more. Here, the solid content is a component other than the solvent, and the solvent is as described above.

In addition, the ink composition for an inkjet color filter of the present invention preferably has a viscosity of 2 to 30 mPa's, more preferably 5 to 20111? & '5, and a surface tension of 10 to 50 dyneZ cm. 20-40 dyneZcm is more preferable.

The color filter according to the present invention includes, on a substrate, a pixel group of two or more colors having different hues and a light-shielding dark color separation wall that separates the pixels constituting the pixel group from each other. is there. This color filter is configured by forming a pixel pattern by providing a colored region (colored layer) by a inkjet method in a recess surrounded by a dark color separation wall.

[0079] The method for producing a color filter of the present invention includes the above-described ink composition for an ink-jet color filter according to the present invention applied to the concave portions partitioned and separated by a dark color separation wall by an ink-jet method. (Hereinafter, sometimes referred to as a “colored region forming step”). The method for producing a color filter of the present invention preferably further comprises a curing step in which at least one colored region formed is cured by irradiation with actinic rays, or after all colored regions having a desired hue are formed. It has a hardening process which hardens by. In addition, the color filter manufacturing method of the present invention can be configured by providing other processes such as a beta process and an ink repellent process as needed.

Note that the dark color separation wall is formed on the substrate in advance before the colored region forming step, and details of the method of forming the dark color separation wall will be described later.

[0080] One colored region forming step

The colored region forming step includes an inkjet color filter ink containing a colorant (including R, G, or B) together with the surfactant according to the present invention in the recesses between the dark color separation walls as described above. A droplet of the composition is applied by an inkjet method to form a colored region. This colored region is a color pixel of red (R), green (G), blue (B), etc. constituting the color filter.

[0081] The colored region is formed by a coloring liquid for forming colored pixels (for example, RGB three-color pixel pattern) in the recesses surrounded by the dark color separation wall formed on the substrate as described above. As the body composition, the ink composition for an inkjet color filter of the present invention can be penetrated to form a plurality of pixels of two or more colors.

[0082] Inkjet methods are known such as a method of thermally curing ink, a method of photocuring ink, and a method of ejecting ink after forming a transparent image-receiving layer on a substrate in advance. This method can be used.

[0083] In this step, the discharge amount discharged to the recess surrounded by the dark color separation wall can be appropriately selected in order to obtain a desired hue and density. Preferably, the size of one droplet is preferably 0.1 to 100 pl (picoliter), more preferably 1 to 50 pl. [0084] The shape of the color filter pattern is not particularly limited, and may be a general stripe shape as a black matrix shape, a lattice shape, or a delta arrangement.

[0085] As an ink jet method, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and an ink is heated and intermittently utilized by using its foaming. Various methods such as a spraying method can be adopted.

[0086] As the ink ejection conditions, it is preferable from the viewpoint of ejection stability that the ink is heated to 40 to 70 ° C to lower the ink viscosity. Since the colored liquid composition is generally higher in viscosity than the water-based ink, the viscosity fluctuation range due to temperature fluctuation is large. It is important to keep the ink temperature as constant as possible because viscosity fluctuations directly affect the droplet size and droplet ejection speed, and easily cause image quality degradation.

As the ink jet head (hereinafter also simply referred to as a head), a known one can be applied, and a continuous type or a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operating valve as described in JP-A-9323420 for discharging. As the piezo head, for example, the heads described in European Patent A277, 703, European Patent A278, 590, etc. can be used. The head should have a temperature control function so that the ink temperature can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa's, and to control the ink temperature so that the fluctuation range of the viscosity is within 5%. The driving frequency is preferably 1 to 500 kHz.

[0088] The color filter according to the present invention preferably has a configuration constituted by a group of three colored regions (colored layers) by spraying RGB three colors of ink.

[0089] Curing process

Next, steps that can be provided other than the colored region forming step will be described below.

《First curing process》

A step (first curing step) in which at least one colored region formed in the colored region forming step is cured by irradiation with an actinic ray can be provided. In the first curing process, red A cured colored region can be formed by curing the curable ink of the present invention of each color including color (R), green (G), and blue (B). Curing may be performed every time a colored region of one color is formed, or may be performed after forming colored regions of a plurality of colors.

[0090] Curing of the curable ink according to the present invention, such as R, G, B, etc., involves an exposure process that promotes polymerization and curing using an energy source that emits active energy rays in a wavelength region corresponding to the photosensitive wavelength of the ink. It can be done by applying.

[0091] Examples of the energy source include ultraviolet rays of 400 to 200 nm, far ultraviolet rays, g-line, h-line, i-line, KrF excimer laser beam, ArF excimer laser beam, electron beam, X-ray, molecular beam, or ion. A beam, such as a beam, to which the above-described polymerization initiator is sensitive can be appropriately selected and used. Specifically, a light source emitting active light belonging to a wavelength region of 250 to 450 nm, preferably 365 ± 20 nm, for example, LD, LED (light emitting diode), fluorescent lamp, low pressure mercury lamp, high pressure mercury lamp, metal nitride lamp, carbon An arc lamp, a xenon lamp, a chemical lamp, or the like can be preferably used. Preferred light sources include LEDs, high pressure mercury lamps, and metal halide lamps.

[0092] The irradiation time of the active energy ray can be appropriately set according to the combination of the polymerizable compound and the polymerization initiator. For example, when exposure is performed at an illuminance of 20 mWZcm ² , 1 to 750 Can be seconds.

[0093] << Second curing step >>

In the method for producing a color filter of the present invention, a step (second curing step) of curing all the colored regions of a desired hue including red (R), green (G), and blue (B) by heat. Further, it can be provided. As described above, by providing the first curing step and the second curing step, it is possible to achieve both the production efficiency of the color filter and the display characteristics.

In this step, a colored region having a desired hue and a dark color separation wall are formed, and after performing the first curing step, a heat treatment (so-called beta treatment) is further performed to cure by heat. . That is, a substrate on which a colored region photopolymerized by light irradiation and a dark color separation wall are formed is heated in an electric furnace, a dryer, or an infrared lamp is irradiated. Shoot and heat.

[0095] As the size of the colored region (colored layer; that is, pixel) formed by the method for producing a color filter of the present invention, the length of one side of the pixel is preferably 50 to 300 / ζ πι. Particularly preferred is 111 to 100-300 m. Further, it may be a stripe shape in which pixels of the same color are arranged in a vertical shape.

[0096] The heating temperature and heating time at this time depend on the composition of the colored liquid composition and the thickness of the colored region. In general, from the viewpoint of ensuring sufficient solvent resistance, alkali resistance, and ultraviolet absorbance, the heating temperature and heating time are preferably about 120 ° C. to about 250 ° C. for about 10 minutes to about 120 minutes.

[0097] The surface roughness (Ra value) of the colored region (colored layer) formed by applying the ink composition for an inkjet color filter of the present invention to an inkjet is preferably 5 nm or less, more preferably. 4 nm or less. This Ra value is measured by a contact film thickness meter (a stylus type surface roughness meter P10 manufactured by Tencor).

[0098] Partition formation process

Before performing the colored region forming step and the curing step described above, a partition wall forming step for forming a dark color separation wall can be provided, and this partition wall forming step is performed using a dark color composition. Form a wall.

[0099] The dark color composition is preferably a composition having a high optical density, and the preferred optical density is 2.0 to 2.0 when a photosensitive resin composition layer having a thickness equivalent to a dark color separation wall is formed. 10. Optical density at 0. The more preferable optical density is 2.5 to 6.0, and particularly preferably 3.0 to 5.0. Further, as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important for the photosensitive resin layer and the dark color composition, preferably when cured with a photoinitiating system. The optical density value is preferably 2.0 to 10.0 force S, more preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. When the optical density is within the above range, the polymerization and curing becomes good, and a dark color separation wall having a desired shape can be formed. The dark color property can be imparted by using various coloring materials such as dyes and pigments described later, carbon in various forms, or materials having a combination of these, and black is the most common.

[0100] The dark color composition is composed of at least a colorant, a polymerization initiation system, and a polymerizable compound. As the polymerization initiation system, a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are generally mentioned, but it is preferable to be composed of a photoinitiation system.

[0101] In the case of using the photoinitiating system, the formation of the dark color separation wall constituting the color filter in the present invention is performed, for example, on at least one of the substrates before the colored region forming step and the curing step described above are performed. A photosensitive resin layer is formed using the dark color composition, and the formed photosensitive resin layer can be suitably exposed by patterning (preferably under poor oxygen conditions) and developing. . As described above, the dark color separation wall is a partition wall pattern that separates colored areas formed by ejecting droplets of the curable ink (colored liquid composition) of the present invention by an ink jet method. . In addition, after forming and exposing at least the photosensitive resin layer in the partition wall forming step, other steps such as a beta treatment or an ink repellent treatment can be provided as necessary.

Hereinafter, the case where it is configured using a photoinitiation system as a polymerization initiation system will be mainly described.

[0102] [Formation of photosensitive resin layer]

The photosensitive resin layer can be constituted by using a dark color composition containing a coloring material, a polymerizable compound, and a photoinitiating system, and if necessary, further a binder, a known additive such as a plasticizer, Other components such as a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, and an adhesion promoter can be used.

Specifically, the photosensitive resin layer is a method of applying a dark color composition (for example, containing at least a polymerizable monomer, a photopolymerization initiator, a binder, and a coloring material) onto a substrate (preferably a dark color composition). Or a method of transferring a photosensitive resin layer onto a substrate using a photosensitive transfer material having a photosensitive resin layer using a dark color composition (transfer method). Can do. Details of the dark color composition and the photosensitive transfer material will be described later.

[0103] In the case of applying a photosensitive resin layer by coating (coating method), the coating is preferably performed using a slit-shaped nozzle or slit coater having a slit-shaped hole in a portion for discharging the liquid.

Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002- No. 79163, slit-shaped nose described in JP 2001-310147 A, etc. And a slit coater can be suitably used. As another example, a spinner of all, Howaira ^one to "ゝthe mouth ¹ ~"'~^"co-1to"data' ~ "ゝforce. ~" Te, Noyu ~ "data '~"ゝNaifuko ^one to "data' ~ It is possible to use an applicator such as “ゝ Wire ¹ ~” “No ¹ ” ~ “Co ¹ ~” or an Etrustruder.

[0104] In the case of the coating method, a step of coating and forming a photosensitive resin layer using a dark color composition on a substrate is provided, and as described later, the coated and coated photosensitive resin layer [preferably Is exposed to an oxygen condition (for example, an oxygen barrier layer is further formed on the photosensitive resin layer and formed through the oxygen barrier layer, or an inert gas atmosphere or a reduced pressure condition). By darkening, a dark color separation wall is formed. The oxygen blocking layer can be formed in the same manner as the oxygen blocking layer in the photosensitive transfer material described later.

Details of exposure and development will be described later.

[0105] In the case of the transfer method, a photosensitive transfer material described later is used, and the photosensitive resin layer formed in a film shape on the temporary support is pressure-bonded with a roller or a flat plate heated and Z or pressed on the substrate surface. Alternatively, pasting by thermocompression bonding (laminate), leaving the temporary support (under anoxic conditions), remove the photosensitive resin layer, or further remove the temporary support to remove the photosensitive resin layer. The photosensitive resin layer that has been transferred and transferred is exposed (preferably under poor oxygen conditions (for example, through an oxygen barrier layer provided on the photosensitive resin layer)), developed, and patterned. A deep color separation wall is formed by Jung. Details of exposure and development will be described later.

Specifically, the laminating can be performed by a laminator and a laminating method described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. The Details regarding the photosensitive transfer material and transfer by a transfer method will be described later.

[0106] The layer thickness of the photosensitive resin layer is not particularly limited and depends on the solid content of the dark color composition and the height of the dark color separation wall to be formed. ~: LO / zm is preferred 1.8-8. Force is more preferred, 2. 2-5.0 m force ^ More preferred! / ,.

[0107] ~ Dark color composition, photosensitive resin layer ~

Hereinafter, the dark color composition for forming the dark color separation wall and the components of the photosensitive resin layer using the same will be described in detail.

[0108] Monopolymeric compound It is preferable that the photosensitive resin layer or the dark color composition for forming the dark color separation wall contains at least one polymerizable compound. It can be cured by the action of active species from the photoinitiating system described later to form noturn.

[0109] Examples of the polymerizable compound include monofunctional or polyfunctional monomers, and polyfunctional monomers are preferred. The polyfunctional monomer is a polymerizable monomer having two or more polymerizable groups, and can be used alone or in combination with other monomers.

[0110] Specific examples of the monofunctional or polyfunctional monomer include t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol. Di (meth) acrylate, trimethylol propane tri (meth) acrylate, 2-ethyl-2-propane diol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta erythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxyethyl trimethylol propane tri (meth) acrylate, tris (2- (meth) acryloyloxie Chill) isocyanurate, 1,4-diisopropyl Robert benzene, 1,4-dihydroxybenzene di (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitic acid, lauryl (meth) acrylate, ( And (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

In addition, compounds having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate

And reaction products with diisocyanates such as hexamethylene diisocyanate, toluene diisocyanate, and xylene diisocyanate.

[0111] Among the above, pentaerythritol tetraatalylate, dipentaerythritol hexaatalylate, dipentaerythritol pentaatalylate, and tris (2-acryloyloxychetyl) isocyanurate are particularly preferable.

[0112] The content of the polymerizable compound in the photosensitive resin layer or the dark color composition is preferably 5 to 80% by mass with respect to the total solid content (mass) of the layer or composition. -70% by weight is particularly preferred. When the content is within the above range, it is effective to ensure the resistance to the alkali developer after photocuring. [0113] One light start system

It is preferable that the photosensitive resin layer or the dark color composition for forming the dark color separation wall contains at least one photoinitiating system. The photoinitiating system is a compound that generates an active species that initiates polymerization of the polymerizable compound upon irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. It can select suitably from these compounds.

[0114] For example, torino, romethyl group-containing compounds, atalidine compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds Compounds, xanthone compounds, diazo compounds, and the like.

[0115] Specifically, trino, trihalomethyloxazole derivatives or _s -triazine derivatives substituted with a trino or romethyl group described in JP-A-2001-117230, trihalomethyl described in US Pat. No. 4,239,850 — S triazine compounds, trihalomethyl group-containing compounds such as trihalomethyl oxadiazole compounds described in US Pat. No. 4,212,976;

[0116] 9 Phenulacridine, 9 Pyridylatridine, 9 Pyrazuracridine, 1, 2 Bis

(9-Ataridyl) ethane, 1,3 bis (9-Ataridyl) propane, 1,4 bis (9-Ataridyl) butane, 1,5 bis (9-Ataridyl) pentane, 1, 6 Bis (9-Ataridiyl) hexane, 1,7 Bis (9-Ataridiyl) heptane, 1,8 Bis (9-Ataridiyl) octane, 1,9 Bis (9-Ataridiyl) Nonane, 1, 10 Bis (9-Ataridyl) decane, 1, 11-Bis (9-Ataridyl) undecane, 1,12 Bis (9-Ataridyl) dodecane, etc. Attalizyl) alkanes, and other atalidine compounds;

[0117] 6- (p-methoxyphenyl) 2, 4-bis (trichloromethyl) s triazine, 6- [p- (N, N bis (ethoxycarbomethyl) amino) phenol] 1, 2, 4 Bis (trichloromethyl) -triazine compounds such as triazine; 9, 10, dimethylbenzphenazine, Michler's ketone, benzophenone Z Michler's ketone, hexaarylbisimidazole / mercaptobenzimidazole, benzyldimethylketal, Thioxanthone / amine, 2,2'-bis (2,4 dichlorophenol) -1,4 ', 5,5'-tetraphenyl-1,2'bisimidazole, and the like. [0118] Of the above, a trihalomethyl group-containing compound in which at least one selected from trino, romethyl group-containing compounds, atalidine compounds, acetophenone compounds, bisimidazole compounds, and triazine compounds is preferred And at least one selected from the atalidine-based compounds is particularly preferred. Torino, romethyl group-containing compounds, and atalidine compounds are also useful because they are versatile and inexpensive.

[0119] The trihalomethyl group-containing compound is particularly preferably 2 trichloromethyl.

5- (p-styrylstyryl) 1,3,4-oxadiazole, 2- (p-butoxystyryl) 5 trichloromethyl-1,3,4-oxadiazole. -Lucridine, and the triazine compound is 6- [p — (N, N bis (ethoxycarbomethyl) amino) phenol] -2, 4 bis (trichloromethyl) s-triazine, The Benzophenone compound is Michler's ketone, and the biimidazole compound is 2,2′-bis (2,4 dicyclophenyl) —4, 4 ′, 5, 5′-tetraphenyl 1 , 2'-bisimidazole.

[0120] The polymerization initiation system (particularly the photoinitiation system) may be used in combination of two or more in addition to being used alone.

The total amount in the photosensitive resin layer or dark color composition of the polymerization initiation system (especially the photoinitiation system) is 0.1 to 20% by mass relative to the total solid content (mass) of the layer or composition. Preferred is 0.5 to 10% by mass. When the total amount is within the above range, the curing efficiency is high and the curing can be performed in a short time, and the image pattern formed at the time of development is not lost or the pattern surface is not rough.

[0121] The photoinitiating system may be configured with a hydrogen donor. The hydrogen donor is preferably a mercabtan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. Here, the “hydrogen donor” refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

[0122] The mercabtan compound has a benzene ring or a heterocyclic ring as a mother nucleus, and has one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus. (Hereinafter, referred to as “mercabbutane-based hydrogen donor”).

Further, the amine compound has a benzene ring or a heterocyclic ring as a mother nucleus, and is directly connected to the mother nucleus. It is a compound having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups bonded to each other (hereinafter referred to as “aminic hydrogen donor”).

The hydrogen donor may have a mercapto group and an amino group at the same time.

[0123] Specific examples of the mercaptan-based hydrogen donor include 2 mercaptobenzozoazole, 2 mercaptobenzoxazole, 2 mercaptobenzozoimidazole, 2, 5 dimercapto 1, 3, 4-thiadiazole, 2 mercapto 2 , 5 dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable! /.

[0124] Specific examples of the amine-based hydrogen donor include 4, 4 'bis (dimethylamino) benzophenone, 4, 4'-bis (jetylamino) benzophenone, 4-jetylaminoacetophenone, 4- Examples include dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzozotolyl and the like. Of these, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (jetylamino) benzophenone are preferable, and 4,4′-bis (jetylamino) benzophenone is particularly preferable.

[0125] The hydrogen donors can be used singly or in combination of two or more.

A hydrogen donor is one or more mercabtan hydrogen donors and one or more amine hydrogen donors because the formed image is less likely to fall off the substrate during development and can also improve strength and sensitivity. It is preferred to use in combination with the body.

[0126] Specific examples of the combination of the mercabtan based hydrogen donor and the amine based hydrogen donor include 2 mercaptobenzothiazole Z4, 4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole Z4, 4'-bis (Jetylamino) benzophenone, 2 mercaptobenzoxazole Z4,4'-bis (dimethylamino) benzophenone, 2mercaptobenzoxazole Z4,4'-bis (jetylamino) benzophenone, and the like. A more preferred combination is 2 mercaptobenzothiazole / 4,4'-bis (jetylamino) benzophenone, 2mercaptobenzoxazole Z4,4'-bis (jetylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzozothiazole / 4, 4 'Bis (jetylamino) benzophenone.

[0127] Merca when the mercabtan-based hydrogen donor and the amine-based hydrogen donor are combined. The mass ratio (M: A) of the butane-based hydrogen donor (M) to the amine-based hydrogen donor (A) is usually preferably 1: 1 to 1: 4, more preferably 1: 1 to 1: 3. .

The total amount of the hydrogen donor in the photosensitive resin layer or dark composition is preferably 0.1 to 20% by mass relative to the total solid content (mass) of the layer or composition. 5-: LO mass% is particularly preferred.

[0128] One color material

The photosensitive resin layer or dark color composition for forming a dark color separation wall preferably contains at least one colorant. By containing a color material, a visible image having a desired color can be formed.

[0129] Examples of the color material include pigments and dyes described in paragraphs [0038] to [0054] of JP-A-2005-17716, and paragraphs [0068] to [0072] of JP-A-2004-361447. And the colorants described in paragraph numbers [0080] to [0088] of JP-A-2005-17521 can be suitably used.

Of these, organic pigments, inorganic pigments, dyes, and the like are suitable as the color material. Further, when light-shielding properties are required for the photosensitive resin layer or the dark color composition, as a coloring material, metal oxide powder such as carbon black, titanium carbon, titanium oxide, iron tetroxide, metal sulfide powder, A light-shielding agent such as metal powder, and a mixture of pigments such as red, blue, and green can be used. Known colorants (dyes, pigments) can be used. Examples of black color materials include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, and the like.

When a pigment is selected as the color material, it is preferable that the pigment is uniformly dispersed in the photosensitive resin layer or the dark color composition.

[0131] The content of the coloring material in the photosensitive resin layer or the dark color composition is 30 to 70% by mass in terms of shortening the development time with respect to the solid content (mass) of the layer or composition. 40-60% by mass is more preferable 50-55% by mass is more preferable.

[0132] The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle is a paint liquid. The part of the medium in which the pigment is dispersed when in the body state is a liquid part that binds to the above-mentioned pigment and hardens the coating film (binder), and a component that dissolves and dilutes this (organic solvent) ). Examples of the disperser used when dispersing the pigment include, but are not particularly limited to, a kneader described in “Encyclopedia of Pigments” (Asakura Kunizo, 1st edition, page 438, Asakura Shoten (2000)). Well-known dispersers such as Ronore Lenore, Atridor, Super Minore, Dizonoleno, Homomixer, Sand Mill and the like can be mentioned. Further, it may be finely pulverized by using frictional force by mechanical grinding described on page 310 of “Encyclopedia of Pigments”.

[0133] From the viewpoint of dispersion stability, the number average particle diameter of the coloring material (particularly pigment) is 0.001 to 0.1111, preferably 0.01 to 0.08 / zm. Better than power! / ヽ. The “particle diameter” refers to the diameter when the particles are represented by a circle having the same area as the area of the particles in the electron micrograph. “Number average particle size” means an average value of 100 particles of a plurality of particles.

[0134] Binder

The photosensitive resin layer or dark color composition for forming a dark color separation image wall can be constituted using at least one binder.

As the noinder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and As described in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial ester oxalic maleic acid copolymer And the like.

[0135] In addition, cellulose derivatives having a carboxylic acid group in the side chain may also be mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.

Particularly preferred examples include copolymers of benzyl (meth) atalylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylate, and other Mention may be made of multicomponent copolymers with monomers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with an ordinary film-forming polymer!

[0136] The content of the binder in the photosensitive resin layer or the dark color composition includes a layer or a set. 20 to 50% by mass is preferable with respect to the total solid content (mass) of the composition, and 25 to 45% by mass is more preferable.

[0137] One organic solvent

In general, the dark color composition used for producing the dark color separation wall in the present invention can be constituted using an organic solvent in addition to the above components. Examples of the organic solvent include methyl ethinoleketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, and strength prolatatum.

[0138] Other ingredients

In the dark color composition or photosensitive resin layer in the present invention, the following components, for example, surfactant, ultraviolet absorber, and known additives such as plasticizer, filler, stabilizer, thermal polymerization prevention An agent, a solvent, an adhesion promoter and the like can be contained. Furthermore, it is preferred that the dark color composition is a thermoplastic which preferably becomes soft or tacky at a temperature of at least 150 ° C. From this point of view, it can be modified by adding a compatible plasticizer.

[0139] <Surfactant>

When the dark color composition is applied on a substrate or a temporary support of a photosensitive transfer material described later, a uniform film thickness can be controlled by including a surfactant in the dark color composition. Cloth unevenness can be effectively prevented. Preferred examples of the surfactant include surfactants described in JP-A No. 2003-337742 and JP-A No. 11-133600. The content of the surfactant in the dark color composition is generally 0.001 to 1% by mass with respect to the total solid content (mass) of the composition, and 0.01 to 0. 5% by mass is preferred 0.03 to 0.3% by mass is particularly preferred.

[0140] <Ultraviolet absorber>

The dark color composition may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include compounds described in JP-A-5-72724, and compounds such as salicylate, benzophenone, benzotriazole, cyanoacrylate, nickel chelate, and hindered amine. [0141] For example, phenyl salicylate, 4 t-butyl ferric salicylate, 2, 4-ji t-butyl ferrule 3 ', 5'-di-t- 4'-hydroxybenzoate, 4-t-butyl phenol Salicylate, 2,4-Dihydroxybenzophenone, 2 Hydroxy-4-methoxybenzophenone, 2 Hydroxy 4-n-Otoxybenzophenone, 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2 'Hydroxy 3'—t-butyl-5'-methylphenol) 5 Chronobenzobenzolazole, Ethyl 2 Cyan 3,3 Di-di-phthalate, 2, 2' Hydroxy-4-methoxybenzophenone, Nickel dibutyl Dithiocarbamate, bis (2, 2, 6, 6-tetramethyl-4-pyridine) sebacate, 4-t butylphenol salicylate, salicylate, 4-hydroxy 2, 2, 6, 6— Tetramethylpiperidine condensate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -ester, 2— [2 Hydroxy-3,5 bis (α, a- Dimethylbenzyl) phenyl] -2H-benzotriazole, 7- {[4 black mouth 6 (jetylamino) 5 triazine-2-yl] amino} 3 phenol coumarin, and the like.

In the case of using an ultraviolet absorber, the content of the ultraviolet absorber with respect to the total solid content of the dark color composition is generally 0.5 to 15% by mass, and preferably 1 to 12% by mass. ˜10 mass% is particularly preferred.

[0142] <Thermal polymerization inhibitor>

The dark composition preferably contains a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-tert-butyl-ρ-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butyl Phenol), 2,2′-methylenebis (4-methyl 6t-butylphenol), 2 mercaptobenzimidazole, phenothiazine and the like.

In the case of using a thermal polymerization inhibitor, the content relative to the total solids in the dark composition 0. A 01-1 mass ^_0/0 power S- general, from 0.02 to 0.7 mass ^_0/0 Force S is preferable, and 0.05 to 0.5% by mass is particularly preferable.

[0143] In addition to the above components, the dark color composition may contain "adhesion aid" described in JP-A-11-133600, other additives, and the like. [0144] -Photosensitive transfer material-

Next, the photosensitive transfer material used in the transfer method will be described in detail.

The photosensitive transfer material is formed by providing a photosensitive resin layer composed of at least the dark color composition on a temporary support, preferably an oxygen barrier layer and a photosensitive layer on the temporary support side. What was provided and provided with the characteristic rosin layer can be used. When a material having an oxygen blocking layer provided on the photosensitive resin layer is used, the photosensitive resin layer made of the dark color composition is protected by the oxygen blocking layer in the atmosphere. It automatically becomes an anoxic condition. Therefore, there is an advantage that the current process which does not need to be performed under an inert gas or under reduced pressure can be used as it is. It is also effective in that a dark color separation wall can be formed easily and at low cost.

[0145] The photosensitive transfer material can be further provided with a thermoplastic resin layer, a protective film or the like, if necessary.

[0146] Temporary support

The temporary support can be appropriately selected from those that are chemically and thermally stable and made of a flexible material. Specifically, a thin sheet or film such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyester, or a laminate thereof is preferable. Of these, biaxially stretched polyethylene terephthalate film is particularly preferred.

[0147] The thickness of the temporary support is suitably 5 to 300 µm, preferably 20 to 150 µm. When the thickness is within the above range, it is possible to avoid tearing at the time of peeling of the temporary support, and it is possible to avoid a decrease in resolution when exposed through the temporary support.

[0148] Photosensitive resin layer

The photosensitive resin layer is composed of the above-described dark-colored composition, and is similar to the layer formed by the above-described coating method in terms of properties such as shape and formation method. The aspect is also the same.

[0149] Oxygen barrier

It is preferable to further provide an oxygen barrier layer between the temporary support and the photosensitive resin layer or between the thermoplastic resin layer and the photosensitive resin layer. The oxygen barrier layer is 2000cmV (m ^2- dayatm) or less, and the oxygen permeability is preferably 100 cm ³ Z (m ² · day • atm) or less, more preferably 50 cm ³ Z (m ² · dayatm) or less. LV preferred. If the oxygen permeability is higher than 2000 cm ³ Z (m ² · day · atm), oxygen may not be effectively cut off and a dark color separation wall having a desired shape may not be obtained.

[0150] As specific examples of the resin material for forming the oxygen barrier layer, the polybutyl ether Z maleic anhydride polymer described in JP-A-46-2121 and JP-B-56-40824 , Water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polybutyl alcohol, polybulur pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid , Gelatin, ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, copolymers of styrene Z maleic acid, maleate resin, and combinations of two or more thereof.

[0151] As the oxygen barrier layer, a layer mainly composed of polyethylene, polyvinyl chloride, polyvinyl alcohol (PV A), etc. (especially PVA as a main component) is preferred. A combination of polybulal alcohol and polypyrrole pyrrolidone, which may be added with a polymer such as acrylamide, is particularly preferred. PVA having an oxidation rate of 80% or more is preferable. The content of polyvinylpyrrolidone is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, more preferably 1 to 75% by mass of the total solid content of the oxygen barrier layer. The content of PVA in the oxygen barrier layer is particularly preferably 50 to 80% by mass, more preferably 50 to 90% by mass, and more preferably 50 to 90% by mass.

The amount of the above-mentioned resin material added is 1 to 40% by mass, more preferably 10 to 35% by mass, based on the entire layer. If the amount of polyvinyl pyrrolidone added is too large, oxygen barrier properties may be insufficient.

[0152] Thermoplastic resin layer

A thermoplastic resin layer can be provided between the temporary support and the photosensitive resin layer as required. Providing a thermoplastic resin layer is effective in improving the adhesion to the substrate on which the dark color separation wall is formed.

[0153] The thermoplastic resin layer should contain at least a resin component and be alkali-soluble. Is preferred. As the resin component, a thermoplastic resin that is alkali-soluble and has a substantially soft softness point of 80 ° C or less is preferable.

Examples of alkali-soluble thermoplastic resins having a soft softness point of 80 ° C or lower include saponified products of ethylene and acrylate copolymers, and saponified products of styrene and (meth) acrylate copolymers. , Kento compound of butyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate Keny's food, etc.

[0154] In addition to the above, there is a soft score in the “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). Among organic polymers of about 80 ° C or less, those soluble in an alkaline aqueous solution can be used.

[0155] In addition, an organic polymer substance having a soft spot of 80 ° C or higher can be substantially added by adding various plasticizers compatible with the polymer substance to the organic polymer substance. The soft saddle point can be lowered to 80 ° C or lower.

These organic polymer substances include various polymers, supercooled substances, and adhesion improvers within the range where the effective soft spot does not exceed 80 ° C for the purpose of adjusting the adhesive strength with the temporary support. Alternatively, a surfactant, a release agent, etc. can be added. Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphosphate, biphenyl diphosphate. it can.

[0156] One Protection Finolem

A protective film is preferably provided on the surface of the photosensitive resin layer formed on the temporary support in order to protect it from contamination and damage during storage. It is important that the protective film can be easily separated from the photosensitive resin layer force in that it can be made of the same or similar material as that of the temporary support and can perform transfer well.

As a material constituting the protective film, for example, silicone paper, polyolefin, or polytetrafluoroethylene sheet is suitable. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 m force S, particularly preferably 10 to 25 m. [0157] The photosensitive transfer material can be produced, for example, as follows. For example, a thermoplastic resin layer is provided by applying a coating solution (thermoplastic resin layer coating solution) in which the components of the thermoplastic resin layer are dissolved on a temporary support and drying. On this thermoplastic resin layer, a solution using a solvent that does not dissolve the thermoplastic resin layer is applied and dried to laminate an intermediate layer. Thereafter, a dark color composition prepared as described above is further applied onto the intermediate layer using a solvent that does not dissolve the intermediate layer, and dried to laminate a photosensitive resin layer.

The coating is preferably performed using a coating device (slit coater) using a slit-like nozzle that can be applied by the known coating method described above.

[0158] In addition to the above, the photosensitive transfer material is prepared by preparing a sheet provided with a thermoplastic resin layer and an intermediate layer on a temporary support, and a sheet provided with a photosensitive resin layer on a protective film. In addition, the oxygen blocking layer and the photosensitive resin layer can be bonded to each other, and the sheet having the thermoplastic resin layer on the temporary support and the photosensitive film on the protective film can be used. A sheet having a resin layer and an intermediate layer is prepared, and the sheet is bonded so that the thermoplastic resin layer and the intermediate layer are in contact with each other.

[0159] One board

Examples of the substrate (permanent support) include a metal base material, a base material bonded with metal, glass, ceramic, a synthetic resin film, and the like. Preferred are those that are transparent and have good dimensional stability, especially glass and synthetic resin films.

[0160] [Exposure, development]

Exposure of the photosensitive resin layer formed as described above can be performed by irradiating the photosensitive resin layer with light through a mask using a mask provided with a desired pattern. At this time, the exposure is preferably performed under an anoxic condition. For example, a layer capable of blocking oxygen (for example, an oxygen blocking layer or a temporary support left without being removed at the time of exposure when a photosensitive transfer material is used) is provided on the photosensitive resin layer. Or by using an inert gas atmosphere or a reduced-pressure atmosphere. Among these, exposure is preferably performed under an anoxic condition formed by adjusting to an inert gas atmosphere or a reduced pressure atmosphere.

[0161] Hypoxic conditions include an inert gas atmosphere, a reduced pressure, and a layer that can block oxygen. The

The inert gas is a general gas such as N, H, or CO, or a rare gas such as He, Ne, or Ar.

2 2 2

Gases. Among these, N is preferable in terms of safety, availability, and cost.

2 The reduced pressure refers to a state of 500 hPa or less, preferably lOOhPa or less. Further, as the layer capable of blocking oxygen, the oxygen blocking layer in the above-described photosensitive transfer material and various films can be applied, for example, polyesters including polyethylene terephthalate (PET), nylon and the like. Also suitable are polyamides and ethylene-vinyl acetate copolymers (EVAs). These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm. When producing a dark color separation wall using a light-sensitive transfer material, the hypoxic condition is formed by placing the temporary support and Z or oxygen barrier on the photosensitive resin layer. .

[0162] For the exposure, for example, a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra high pressure mercury lamp can be used. Examples of the light source include medium to ultra high pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

The [0163] intensity, preferably at 300MWZcm ² or more, particularly preferably ^2, OOOmW / cm 2 or more. From the viewpoint of obtaining the effect of the present invention, the upper limit value of illuminance can be increased to a desired illuminance unless there is a particular problem in apparatus and equipment. This illuminance can be adjusted to the above range by methods such as increasing the output of the light source, increasing the number of light sources, and reducing the distance between the light source and the object to be exposed.

[0164] After the exposure, a developing process is performed using a developer to form a pattern image on the photosensitive resin layer. Thereafter, a water washing process is performed as necessary.

[0165] Prior to development, it is preferable that pure water is sprayed onto the photosensitive resin layer with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin layer. A dilute aqueous solution of an alkaline substance is preferably used as the developer used in the development processing, but it may be a solution obtained by adding a small amount of an organic solvent miscible with water.

[0166] Examples of the alkaline substance include alkali metal hydroxides (for example, sodium hydroxide and potassium hydroxide), alkali metal carbonates (for example, sodium carbonate and potassium carbonate), Lucari metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, metasilicate) Potassium), triethanolamine, jetanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of alkaline substances is preferably 0.01 to 30% by mass. The pH is preferably 8 to 14.

[0167] Examples of the "water-miscible organic solvent" include, for example, methanol, ethanol, 2-prononole, 1-propanol, butanol, diacetone-ethanolo, ethyleneglycol-no monomethinoatenore, Ethylene glycol-monoethylenoleatenole, ethylene glycol-monomonone n butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε — force prolataton, γ-butyrolataton, dimethylformamide, dimethylacetamide, hexamethylphospho Preferable examples include luamide, ethyl acetate, methyl lactate, ε-strength prolatatam, and メチル -methylpyrrolidone. The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass.

Furthermore, the concentration of the surfactant to which a known surfactant may be added is preferably 0.01 to 10% by mass.

[0168] The developer may be used as a bath solution or a spray solution.

When removing the uncured portion of the photosensitive resin layer, methods such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. Within this range, a dark color separation wall having a suitable shape can be obtained. In other words, if the development time is too short, the development of the area to be developed and removed may be insufficient, and at the same time, the UV absorbance may be insufficient. Sometimes. It is also possible to put a water washing step after the development processing.

[0169] The height of the dark color separation wall in the present invention is preferably 1.0 to 6. and more preferably 1.5 to 5 in terms of the height in the substrate normal direction. If the height is within the above range, As described above, when ink droplets are formed by the ink jet method, ink spreads and protrudes beyond the dark color separation wall, color mixing between adjacent pixel patterns, and white spots in the pixel pattern. This is effective for forming a color filter with good hue and high display quality.

[0170] The width of the dark color separation wall in the present invention is preferably 5.0 μm or more and 50 μm or less in the direction perpendicular to the normal direction of the substrate. And the variation width of the thickness in the substrate normal direction of the colored region (R pixel, G pixel, B pixel, etc.) within m in the direction parallel to the substrate surface from the edge of the dark color separation wall (for example, the end surface) is 0.5 m or less is preferable. When the fluctuation range is within the above range, it is possible to effectively prevent display unevenness such as color unevenness in an image when the image is displayed in a display device such as a liquid crystal display device. This fluctuation range is preferably not more than 0. It can be adjusted by adding a surfactant to the ink forming the colored pixels.

[0171] Hereinafter, an example of forming a dark color separation image wall will be specifically described.

1) Formation of dark color separation wall by coating with dark color composition

After cleaning the substrate, the substrate is heat treated to stabilize the surface state. Thereafter, the temperature of the substrate is adjusted, and the dark color composition is applied onto the temperature-controlled substrate. After coating, part of the solvent in the coating layer is dried to eliminate the fluidity of the layer, and then the unnecessary coating solution around the substrate is removed with an EBR (edge 'bead' remover) etc. A characteristic rosin layer is obtained. The coating can be performed using a known glass substrate coater (for example, MH-1600 manufactured by FS Asia Co., Ltd.) provided with a slit-like nozzle. The drying can be performed by a known drying apparatus (for example, V CD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)), and the prebeta can be performed by heating at 120 ° C. for 3 minutes, for example. The layer thickness of the photosensitive resin layer is as described above.

Subsequently, with the substrate on which the photosensitive resin layer is formed and a mask having a pattern (for example, a quartz exposure mask) standing vertically, the distance between the mask surface and the photosensitive resin layer is appropriately set ( For example, set to 200 m) and perform exposure in a nitrogen atmosphere by purging with nitrogen and controlling the oxygen partial pressure. The exposure can be performed by, for example, a proximity type exposure machine (for example, manufactured by Hitachi, Ltd., Techtech Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp. Exposure amount is appropriate (for example, 300mJ Zcm ² ) Can be selected. The oxygen partial pressure at this time can be measured using an oximeter (for example, G-102 manufactured by Iijima Electronics Co., Ltd.). After the exposure, development processing is performed with a developer to obtain a pattern image, and washing with water is performed as necessary to obtain a dark color separation image wall.

[0172] 2) Formation of dark color separation wall by transfer method using photosensitive transfer material

First, the protective film of the photosensitive transfer material is peeled and removed, and the exposed surface of the photosensitive resin layer is overlaid on the substrate surface, passed through a laminator or the like, and heated and Z or pressurized to form a laminate. The laminator can be appropriately selected from conventionally known laminators, vacuum laminators, and the like, and an auto-cut laminator can also be used from the viewpoint of increasing productivity. Next, the laminate strength temporary support is peeled off and removed. Subsequently, a desired photomask (for example, Sekihide exposure mask) is placed above the exposed surface (oxygen barrier layer surface) exposed by removing the temporary support, and the pattern is made through the mask under reduced oxygen conditions under reduced pressure. Irradiate ultraviolet rays in the shape, and after the irradiation, develop with a predetermined processing solution to obtain a dark color separation wall. At this time, washing with water is performed as necessary. The developer used for the development process and the light source used for the exposure are the same as the developer and the light source used in the coating method.

[0173] [Other processes]

In the method for producing the color filter of the present invention, the formed deep color separation wall and the colored region are further heated (beta) to be cured (the following heat treatment and post-exposure) or the above-described dark color separation. Other processes such as the process of applying ink repellent treatment to the dark color separation wall on the substrate after the image wall is formed and before the colored area forming process, and the OC process for forming the overcoat (OC) layer are provided. May be.

[0174] ~ Heat treatment ~

By applying heat treatment (also referred to as post-beta), it is possible to react the monomer or the crosslinking agent contained in the dark color composition or the photosensitive resin layer to ensure the hardness of the dark color separation wall.

The heat treatment temperature is preferably in the range of 150 to 250 ° C. When the temperature is within the above range, good hardness is obtained, and the color purity is good without coloring the resin. The heat treatment time is preferably 10 to 150 minutes. When the time is within the above range, good hardness can be obtained, the resin is not colored, and the color purity is good. The heat treatment may be changed depending on the color. Also before After all colors are formed by the ink jet method described above, the final heat treatment may be further performed to stabilize the hardness. In that case, it is preferable in terms of hardness to carry out at a higher temperature (for example, 240 ° C).

[0175] ~ Post exposure ~

Post-exposure (also referred to as re-exposure) can be performed between development and heat treatment. When post exposure is performed, control of the cross-sectional shape of the dark color separation wall, control of the hardness of the dark color separation wall, control of surface unevenness of the dark color separation wall, and control of film reduction of the dark color separation wall It is preferable from the viewpoints. Examples of the light source used for the post-exposure include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp described in paragraph No. [0074] of JP-A-2005-3861. In the post-exposure, it is preferable from the viewpoint of simplification of equipment and power saving that the substrate is directly irradiated with light having a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask. If necessary, carry out from both sides of the substrate. In this case, the exposure dose can be appropriately adjusted in the range of 100 to 2000 mjZcm ² on the upper surface side and 100 to 2000 mj / cm ² on the lower surface side according to the control purpose.

[0176] Regarding the ink repellent treatment, for example, (1) a method of kneading an ink repellent substance on a dark color separation wall (for example, see JP-A-2005-36160), (2) a new ink repellent layer (3) A method for imparting ink repellency by plasma treatment (for example, see JP-A-2002-62420), (4) Dark color separation wall A method of applying an ink repellent material to the upper surface of the wall (see, for example, JP-A-10-123500), and in particular, (3) ink repellent by plasma on a dark color separation wall formed on a substrate. A method of applying a crystallization treatment is preferable.

[0177] After the colored region (colored pixel) and the dark color separation wall are formed as described above and the color filter is formed, the entire surface of the colored region and the dark color separation wall is formed for the purpose of improving the durability. An overcoat layer can be formed so as to cover.

[0178] The overcoat layer can protect the colored areas such as R, G, and B and the dark-colored / high-color separation wall, and can also flatten the surface. However, it is preferable not to set up because the number of processes increases.

The overcoat layer can be formed using a resin _(oc agent). As rosin (OC agent) Examples thereof include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters usually has an acrylic resin as the main component, and since it has excellent adhesion, the acrylic resin A composition is desirable. Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A-2003-28 7618, and as an overcoat agent commercial product, Optomer 1 SS6699G manufactured by JSR Corporation may be mentioned. .

[0179] The color filter of the present invention is produced by the above-described method for producing the color filter of the present invention. For example, the color filter of the present invention is a portable terminal such as a television, a personal computer, a liquid crystal projector, a game machine, or a cellular phone. It can be suitably applied to applications such as digital cameras and car navigation systems without particular limitation.

Example

[0180] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. Unless otherwise specified, “part” and “%” are based on mass.

[0181] Preparation of ink composition

Compounds in the composition shown in Table 1 below were mixed to prepare an ink composition having red ink composition R, green ink composition G, and blue ink composition B.

[0182] [Table 1]

Ink composition R Ink composition G Ink composition B Pigment 'let' 254 100-- Gemen! 《■ Gelene 36-100-Pigmen 卜-Bull-1 5: 6--100

Nobenzyl methacrylate copolymer

(Copolymerization weight ratio = 28/72, weight average molecular weight = 3 50 50 50

(0, 000)

Dipentaerythri! ~ One Rupentaacrylate 50 50 50

2, 2'—Bis (2-phenyl) 1, 4, 4 ', 5, 5'

—Tetrakis (4 ethoxycarbonyl phenyl) 1 10 10 10

1, 2'-biimidazole

4, 4 'Onebis (Jetylamino) benzophenone 10 10 10

Tetraethylene glycol dimethyl ether 1700 1700 1700 Total 1920 1920 1920

Unit: part

[0183] Subsequently, 100 parts of each of the obtained ink compositions R, G, and B was added with or without 0.1 part of a fluorosurfactant shown in Table 2 below. L～16, ink No.LO 0-101 was prepared (添力卩量is 0.1 mass ^_0/0). Note that ink Nos. 1 to 16 and inks N o.100 to 101 include inks of R, G, and B colors, respectively.

[0184] [Table 2]

Fluorosurfactant

Monomer a Monomer b ¹ b ² Copolymerization ratio Poor average Remarks

= a: b ': b ² molecular weight

R ¹ mn R ² R ³ R ⁴ P q R ^z R ³ R ⁴ P q

Ink o

No. 1 H 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000 Example 1

No. 2 H 6 2 H CH ₃ H 7 0 HHH 0 7 40:40:20 30000 Example 2

No. 3 H 6 2 H CH ₃ H 7 0 ― 40: 60: 0 30000 Example 3

No. 4 H 6 2 H CH ₃ H 7 0 HHH 0 7 25:60:15 30000 Example 4

No. 5 H 6 2 H CH ₃ H 7 0 HHH 0 7 60:25:15 30000 Example 5

No. 6 H 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 5000 Example 6

No. 7 H 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000 Example 7

No. 8 H 6 2 H CH ₃ H 6 1-40: 60: 0 3D000 Example 8

No. 9 H 6 2 H CH ₃ H 1 6 ― 40: 60: 0 30000 Example 9

No. 10 CH ₃ 6 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000 Example 10

No. 11 H 6 2 H CH ₃ CH ₃ 7 0 HH CH ₃ 0 7 40: 55: 5 30000 Example 11

_{No. 12 H 6 2 CH 3 CH} 3 H 7 0 CH 3 HH 0 7 40: 55: 5 30000 Example 12

H 12 2 H CH ₃ H 7 0 HHH 0 7 40: 55: 5 30000 Example 13

_{No. 14 H 4 2 H CH 3} H 7 0 HHH 0 7 40: 55: 5 30000 Example 14

No. 15 H 6 2 H CH ₃ H 14 0 HHH 0 7 40: 55: 5 30000 Example 15

No, 16 H 6 2 H CH ₃ H 7 0 HHH 0 14 40: 55: 5 30000 Example 16 No addition Comparative Example 1

No. 101 H 6 2 I H J H H 7 0 I H I H I H 0 7 115: 60: 25 30000 Comparative Example 2

[0185] Preparation of dark color composition K1

First, K pigment dispersion 1 and propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd., MMPGAC) in the amounts shown in Table 3 below are removed and heated at a temperature of 24 ° C (± 2 ° C). Mix and stir at 150 rpm for 10 minutes, then methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2, 4 bis (trichloromethylolene) — 6— [4'— (N, N Diethoxycarbonylmethylamino) —3′-bromophenyl] —s Triazine and Surfactant 1 are weighed out and added in this order at a temperature of 25 ° C (± 2 ° C) and a temperature of 40 ° C (± 2 ° In C), a dark color composition K1 was prepared by stirring at 150 rpm for 30 minutes.

[0186] [Table 3] Amber composition K1 K2

K Pigment Dispersion 1 (Strong-Honflac) 25 30 Propylene glycol monomethyl ether acetate 8.0 7.3 Methyl ethyl ketone 53 34 Cyclohexanone 0 8.6 Binder 1 9.1 14

DPHA solution 4.2 5.8

2, 4-bis (trichloromethyl) mono 6- [4 'mono (N, N-je

Toxicarbonylmethyl) amino-1 3'-bromophenyl] 1 0.22 0.22 s- 卜 lyazine

Hydroquinone monomethyl ether 0.002 0 Phenothiazine 0 0.006 Surfactant 1 0.044 0.058

(Mass)

[0187] Details of each component in Table 3 are shown below.

* K pigment dispersion 1

'Carbon black (Nipex35, Degussa)… 13. 1%

'The following dispersant: … 0. 65%

'Polymer (benzyl metatalate Z methacrylic acid = 72 28 molar ratio random copolymer, molecular weight 37,000)… 6. 72%

'Propylene glycol monomethyl ether acetate… 79. 53%

[0188] [Chemical 4]

[0189] * Binder 1

'Random copolymer of polymer (benzyl metatalylate Z methacrylic acid (= 78Z22 [molar ratio]), molecular weight 38,000)… 27%

'Propylene glycol monomethyl ether acetate… 73%

[0190] Water DPHA solution

'Dipentaerythritol Hexaatalylate… 76%

(KAYARAD DPHA, polymerization inhibitor MEHQ 500ppm contained, Nippon Kayaku Co., Ltd.)

'Propylene glycol monomethyl ether acetate ... 24%

[0191] * Surfactant 1

• The following structures 1-30%

• Methyl ethyl ketone… 70%

[0192] [Chemical 5] Structure 1

(n = 6, x-55, y = 5 »

w = 33940, w / Mn = 2.55

(PO: propylene oxide, EO: ethylene oxide)

[0193] Production of dark photosensitive transfer material K1

Using a slit-like nozzle on a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), apply a thermoplastic resin coating solution consisting of the following formulation HI, and dry it to make the thermoplastic A resin layer was formed. Next, an intermediate layer coating solution having the following formulation P1 was further applied onto this thermoplastic resin layer and dried to laminate the intermediate layer. Subsequently, the dark color composition K1 obtained above was applied onto the intermediate layer and dried to further laminate a black dark color photosensitive layer.

[0194] As described above, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1, and a dark photosensitive layer having a dry film thickness of m are formed on the PET temporary support. A protective film (polypropylene film with a thickness of 12 m) was pressure-bonded to the surface of the dark photosensitive layer. In this manner, a dark color photosensitive transfer material having a laminated structure of a temporary support Z, a thermoplastic resin layer, a Z intermediate layer, and a Z dark color photosensitive layer was produced. Hereinafter, this is referred to as dark color photosensitive transfer material K1.

[0195] <Prescription of coating solution for thermoplastic resin layer Hl>

• Methanol '·. _Η .1 part

'Propylene glycol monomethyl ether acetate ... 6.36 parts

• Methyl ethyl ketone ".52.4 parts

'Methyl methacrylate // 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer… 5.83 parts

(Copolymerization ratio [molar ratio] = 55Zll.7 / 4.5 / 28.8, molecular weight = 100,000, Tg 70 ° C) • Styrene Z acrylic acid copolymer ··· 13.6 parts (Copolymerization ratio [molar ratio] = 63Z37, average molecular weight = 10,000, Tg = 100 ° C)

• 2, 2 Bis [4— (Methacryloxypolyethoxy) phenol] propane (manufactured by Shin-Nakamura Engineering Co., Ltd.)… 9. 1 part

• Mega Fuck F780F (Dainippon Ink Chemical Co., Ltd.) ... 0. 54 parts

Shizuru

• C F CH CH OCOCH = CH (40 parts) and H (OCH (CH) CH) OCOCH = C

6 13 2 2 2 3 2 7

Copolymer of H (55 parts) and H (OCH CH) OCOCH = CH (5 parts) (mass average molecular weight

2 2 2 7 2

30, 000)

• Methyl ethyl ketone… 70 parts

[0196] Prescription of coating solution for intermediate layer Pl>

• PVA- 205… 32. 2 copies

[Manufactured by Kuraray Co., Ltd., acidity = 88%, polymerization degree 550; polybulu alcohol]

'Polybylpyrrolidone… 14. 9 parts

(ISPI, Japan, K-30)

'Distilled water 524 parts

• Methanore · '· 429 咅

[0197] Formation of dark color separation wall (transfer method)

An alkali-free glass substrate (hereinafter, simply referred to as “glass substrate”) was cleaned with a rotating brush having nylon hair while spraying a glass cleaning solution adjusted to 25 ° C. for 20 seconds by a shower. Further, after washing with pure water shower, a silane coupling solution (N-β (aminoethyl) _Ύ- aminopropyltrimethoxysilane _0.3 % aqueous solution; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is showered. Sprayed for 2 seconds and washed with pure water shower. Thereafter, this substrate was heated at 100 ° C. for 2 minutes using a substrate preheating apparatus.

[0198] The protective film was peeled and removed from the dark photosensitive transfer material K1 obtained above on the glass substrate after the silane coupling treatment. After superposition so that the surface of the dark photosensitive layer exposed by removal and the surface of the glass substrate are in contact with each other, a laminator Lamic II type (manufactured by Hitachi Industries Ltd.) is used, with a rubber roller temperature of 130 ° C. and a line. Lamination was performed under conditions of a pressure of 100 NZcm and a conveyance speed of 2. 2 mZ. Subsequently, the PET temporary support was peeled off at the interface between the PET temporary support and the thermoplastic resin layer, and the temporary support was removed and transferred. After peeling the temporary support, use a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra high pressure mercury lamp, and vertically stand the substrate and mask (quartz exposure mask with image pattern) With the distance between the mask surface and the dark photosensitive layer set to 200 m, pattern exposure was performed at an exposure of 70 mi / cm ² .

[0199] Next, KOH-based developer (KOH, containing non-ionic surfactant, CDK-1 (trade name; manufactured by Fuji Film Elect Kokuku Materials Co., Ltd.)) 100 times with pure water In the diluted solution), spray development is performed at 23 ° C for 80 seconds and with a flat nozzle at a pressure of 0.04 MPa, and shower development is performed. The plastic rosin layer was removed. In this way, a black pattern was obtained on the glass substrate. Subsequently, the entire surface of the glass substrate was post-exposed with 2, OOOmiZcm ² from the side of the glass substrate where the black pattern was formed using an aligner in the atmosphere, and a dark color separation with an optical density (D) of 4.0. A wall was formed (hereinafter referred to as a dark color separation wall-mounted substrate). O

[0200] (Example 1)

Formation of one colored pixel part

Using the substrate with the dark color separation wall obtained as described above, the inks of R, G, and B of ink No. 1 shown in Table 2 were ejected on the dark color separation wall at an ejection speed of 7 mZ seconds by the inkjet method. After discharging to the enclosed recess and discharging until the height of the applied ink surface rises higher than the height of the dark color separation wall, place it on a hot plate for 2 minutes at 200 ° C Post-beta was performed to evaporate the solvent. At this time, the rise of the ink was flat. Furthermore, it was cured by post-beta in a 200 ° C oven for 1 hour. In this way, a color filter in which colored pixel portions of three colors of R pixel, G pixel, and B pixel were arranged on the substrate was obtained (hereinafter referred to as a color filter substrate).

[0201] Fabrication of liquid crystal display device

Next, an ITO (Indium Tin Oxide) film was further formed on the R pixel, G pixel, B pixel, and dark color separation wall constituting the obtained color filter substrate by sputtering to form a transparent electrode. Separately, prepare a glass substrate as the counter substrate, and apply an etching resist for PVA mode on the transparent electrode of the color filter substrate and on the counter substrate, respectively. And patterned.

[0202] Next, a photospacer is provided on the transparent electrode (ITO film) of the color filter substrate above the dark color separation wall, and an alignment film made of polyimide is further formed thereon. Was provided. After that, a sealant of epoxy resin is printed on the outer peripheral wall of the partition wall so as to surround the entire color pixel portion of the RGB color of the color filter substrate, and a PVA mode liquid crystal is dropped on the opposite substrate. After bonding, the bonded substrates were heat-treated to cure the sealing agent, and a liquid crystal cell was produced.

Further, a polarizing plate HLC2-2518 manufactured by Sanritz Co., Ltd. was attached to the substrate surfaces on both sides of the produced liquid crystal cell. Next, a cold cathode tube was used to form a backlight, and this knock light was placed on the side of the liquid crystal cell on which the polarizing plate was provided to provide a liquid crystal display device.

[0203] (Examples 2 to 16)

In Example 1, except that the ink No. 1 was replaced with each of the ink Nos. 2 to 16 shown in Table 2 above, a color filter substrate was prepared and a liquid crystal display device was prepared in the same manner as in Example 1. Produced.

[0204] (Example 17)

In Example 1, a color filter substrate was produced and a liquid crystal display device was produced in the same manner as in Example 1, except that the dark color separation wall was formed by the transfer method by the coating method shown below. did.

[0205] Formation of dark color separation wall (coating method)

An alkali-free glass substrate (hereinafter referred to as a unit “glass substrate”) was cleaned with a UV cleaning device, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. Thereafter, the glass substrate was heat treated at 120 ° C for 3 minutes to stabilize the surface state.

[0206] After cooling the glass substrate, the temperature was adjusted to 23 ° C, and the glass substrate coater with a slit-like nozzle, MH-1600 (manufactured by F'AS Asia Co., Ltd.), was obtained from the above. Color composition K1 was applied. Subsequently, using a VCD (vacuum dryer, manufactured by Tokyo Ohka Kogyo Co., Ltd.), part of the solvent is dried for 30 seconds to eliminate the fluidity of the coating layer, and then pre-beta for 3 minutes at 120 ° C.

A dark photosensitive layer K1 having a thickness of 2 m was formed. [0207] Using a proximity-type exposure machine equipped with an ultra-high-pressure mercury lamp (manufactured by Hitachi, Ltd., Techtech Engineering Co., Ltd.), a glass substrate and mask (quartz with an image pattern) on which a dark photosensitive layer K1 is formed With the exposure mask standing vertically and the distance between the mask surface and the dark photosensitive layer K1 set to 200 / zm, pattern exposure was performed at a dose of 300 miZcm ² in a nitrogen atmosphere.

[0208] Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark photosensitive layer K1, and then a KOH developer (KOH, containing a nonionic surfactant, CDK-1) (Product name: Fujifilm Elect Mouth-X Materials Co., Ltd.) diluted 100 times with pure water) and sprayed at 23 ° C for 80 seconds with a flat nozzle at a pressure of 0.04 MPa And developed with a shower to obtain a black pattern. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues. Further, post-exposure was performed at an exposure dose of 2, OOOmjZcm ² in the atmosphere. In this way, a dark color separation wall having an optical density of 3.9 was formed to produce a substrate with a dark color separation wall.

[Example 18]

A color filter was prepared in the same manner as in Example 1 except that the formulation of the dark color composition used for forming the dark color separation wall in Example 1 was changed from the dark color composition K1 to the dark color composition K2. A substrate was fabricated and a liquid crystal display device was fabricated.

[0210] (Comparative Examples 1-2)

A color filter substrate was prepared in the same manner as in Example 1 except that ink No. 1 was replaced with ink No. 100 or No. 101 shown in Table 2 in Example 1 and a liquid crystal substrate was prepared. A display device was produced.

[0211] (Evaluation)

Each of the color filter substrate and the liquid crystal display device obtained in the examples and comparative examples was evaluated by the following method. The evaluation results are shown in Table 4 below.

[0212] 1. Flatness

For each color filter substrate, the variation width of the thickness (thickness in the substrate normal direction) of the R pixel, G pixel, and B pixel within 10 m in the direction parallel to the substrate surface from the edge of the dark color separation wall, Measured with a stylus type film thickness meter (P10, manufactured by KLA-Tencor Co., Ltd.) Evaluation was performed according to the evaluation criteria.

[Evaluation criteria]

Α: Less than 0.5 πι

Β: Less than 0.5 μmJ¾_hO.

C: 0.55 / zm or more

[0213] -2. Display unevenness

Each liquid crystal display device is energized to display R, G, B monochromatic images, gray test signals are input, display irregularities when the images are displayed are observed with a loupe, and the following evaluation criteria are used. And evaluated.

[Evaluation criteria]

A: The power was completely uneven (very good!).

B: Slight unevenness was observed on the display, but it was within a practically acceptable range (normal). C: The display area was uneven (bad! /).

[0214] [Table 4]

Ink flatness [μ τη]

Bulkhead Display unevenness No.

R G Β evaluation

Example 1 No. 1 Transfer 0.32 0.35 0.34 AA Example 2 No. 2 Transfer 0.43 0.42 0.44 AA Example 3 No. 3 Transfer 0.35 0.37 0.36 AA Example 4 No. 4 o Transfer 0.46 0.48 0.44 AA Example 5 No. 5 Transfer 0.42 0.45 0.41 AA Example 6 No. 6 Transfer 0.46 0.42 0.47 AA Example 7 No. 7 Transfer 0.38 0.39 0.41 AA Example 8 No. 8 Transfer 0.44 0.43 0.45 AA Example 9 No. 9 Transfer 0.41 0.44 0.42 AA Example 1 0 No. 10 Transfer 0.40 0.41 0.42 AA Example 1 1 No. 1 1 Transfer 0.44 0.43 0.45 AA Example 1 2 No. 12 Transfer 0.47 0.46 0.44 AA Example 1 3 No. 13 Transfer 0.42 0.45 0.43 AA Example 1 4 No. 14 transfer 0.43 0.44 0.45 AA Example 1 5 No. 15 transfer 0.41 0.45 0.44 AA Example 1 6 No. 16 transfer 0.39 0.41 0.41 AA Example 1 7 No. 1 cloth 0.37 0.39 0.41 AA Example 1 8 No. 1 Transfer 0.32 0.35 0.34 AA Comparative Example 1 Copy 0.71 0.72 0.75 CC Comparative Example 2 No. 101 Transfer 0.57 0.61 0.58 CC

As shown in Table 4, in the examples, the colored pixel portions of the R, G, and B colors formed by ejecting ink between the dark color separation walls were excellent in flatness. Further, in the example, the occurrence of display unevenness of the display image was not recognized, and an image display with high display quality could be performed. On the other hand, in the comparative example, the flatness of the colored pixel portion was inferior, and display unevenness occurred in the display image. The disclosure of Japanese application 2005—380199 is hereby incorporated by reference in its entirety.

All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

An ink composition for an inkjet color filter used for forming a colored region formed by applying droplets by an ink jet method, comprising a colorant and a fluorosurfactant, wherein the fluorosurfactant Having at least one of structural units a derived from the monomer represented by the following general formula (a) and at least one of structural units b derived from the monomer represented by the following general formula (b), An ink composition for an ink jet power filter, which is a copolymer having a mass ratio (aZb) of the unit a to the structural unit b of 20Z80 to 60Z40.

[Chemical 1]

[Where,

R ² and R ³ each independently represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer of 2 to 14, and n represents an integer of 1 to 18. p and q each independently represent an integer of 0 to 18, and p and q do not represent 0 at the same time. ]

[2] The ink composition for an inkjet color filter according to [1], wherein the content of the fluorosurfactant is 0.01 to 0.2% by mass of the total mass of the ink composition. .

[3] At least one of the structural units a is a unit derived from a monomer in which R ¹ is a hydrogen atom, —CF is —CF m 2m + l 6 13, and n is 2. The ink composition for an inkjet color filter according to claim 1.

[4] At least one of the structural units b is such that R ² is a hydrogen atom and is an R ³ cate group. ^{4. The} ink composition for an inkjet color filter according to claim 1, wherein R ⁴ is a hydrogen atom, p is 7, and q is a unit derived from a monomer of 0. object.

[5] At least one of the structural units b is as follows: R ² is a hydrogen atom, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, p is 0, and q is 7 The ink composition for an inkjet color filter according to claim 1, wherein the ink composition is a unit derived from a monomer.

[6] The fluorinated surfactant is a binary or ternary copolymer containing 20 to 60% by mass of the structural unit a and 80 to 40% by mass of the structural unit b. The ink composition for an inkjet color filter according to claim 1.

7. The ink composition for an inkjet color filter according to claim 6, wherein the proportion of the structural unit a is 25 to 60% by mass and the proportion of the structural unit b is 60 to 40% by mass. .

[8] The ink set for an inkjet color filter according to [2], wherein the content of the fluorosurfactant is 0.05 to 0.15% by mass of the total mass of the ink composition. Adult.

[9] The ink composition for an ink jet color filter according to [1], further comprising a polymerizable compound and a polymerization initiator.

[10] A method for producing a color filter, comprising: a pixel group of two or more colors having different hues on a substrate; and a light-shielding dark color separation wall that separates the pixels constituting the pixel group from each other. A method for producing a color filter, comprising: forming a colored region by applying the ink composition for an ink-jet color filter according to claim 1 to the recesses separated by a color separation wall by an ink-jet method.

11. The method for producing a color filter according to claim 10, wherein the height of the dark color separation wall in the normal direction of the substrate is 1.0 to 6.Ο / ζ m.

[12] The colored region within the parallel to the substrate surface from the edge of the dark color separation wall

11. The method for producing a power color filter according to claim 10, wherein the fluctuation range of the thickness in the substrate normal direction is 0.5 m or less.

13. The color filter according to claim 10, further comprising a first curing step of irradiating at least one colored region formed in the step of forming the colored region with an actinic ray to cure. Manufacturing method.

[14] After the first curing step, the method further includes a second curing step of curing all the colored regions having a desired hue including red (R), green (G), and blue (B) by heat. The method for producing a color filter according to claim 13.

15. A color filter produced by the method for producing a color filter according to claim 10.

16. A liquid crystal display device comprising the color filter according to claim 15.