JP6143298B2 - Colored photosensitive composition, colored spacer, color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a colored photosensitive composition and the like. More specifically, the present invention relates to a colored photosensitive composition that is preferably used as a colored spacer in a color filter such as a liquid crystal display, and a colored spacer, a color filter, and a liquid crystal display device formed thereby.

  A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage to the liquid crystal. On the other hand, each member forming an LCD cell is often formed using a photosensitive composition typified by photolithography. The range of application of the photosensitive composition tends to further expand in the future because it is easy to form a fine structure and it is easy to process a substrate for a large screen.

  However, in an LCD using a photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electrical characteristics of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, thereby causing display display. Problems such as unevenness occur. Particularly, a member closer to the liquid crystal layer in a color liquid crystal display device, for example, a so-called columnar spacer, photospacer, or the like used to keep the distance between two substrates constant in a liquid crystal panel has a great influence.

  Conventionally, when a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT. In order to prevent this, for example, Patent Document 1 describes that a spacer is made light-shielding.

  In recent years, when manufacturing spacers by photolithography, a method has been proposed in which spacers having different heights are collectively formed as the structure of the panel changes. Patent Document 2 discloses that the spacer shape and level difference having different desired heights can be realized by controlling the exposure amount and the remaining film ratio.

Japanese Unexamined Patent Publication No. 8-234212 Japanese Unexamined Patent Publication No. 2009-31778

  However, as described in Patent Document 1, in order to make the spacer light-shielding, it is conceivable to add a colorant or the like including a pigment to the photosensitive composition, but it is clear as the colorant is added. There is a possibility that the electrical properties may be impaired due to the decrease in the curability of the spacer layer due to the decrease in the components and the influence of impurities derived from the pigment.

  Further, Patent Document 2 relates to a spacer to which no pigment is added, and when applied to the batch formation of colored spacers to which a pigment is added, the pigment absorbs light in the ultraviolet region contributing to photopolymerization, and thus the light transmittance of the opening. It has been found that a pattern having a small number has poor curability, and it is difficult to achieve characteristics such as spacer shapes having different heights, step control, and adhesion to a substrate.

The present invention has been made in view of such circumstances. That is, the main problem of the present invention is that, in the method for forming colored spacers having different heights by photolithography, the liquid crystal voltage holding ratio is ensured, formation of a desired shape, step control, An object of the present invention is to provide a colored photosensitive composition having excellent adhesion.
Another object of the present invention is to provide a colored spacer formed from such a colored photosensitive composition.

Still another object of the present invention is to provide a color filter having such a colored spacer.
Still another object of the present invention is to provide a liquid crystal display device having such a color filter.
Still another object of the present invention is to provide a method for collectively forming colored spacers having different heights using such a colored photosensitive composition by a photolithography method.

As a result of intensive studies on the above problems, the present inventors use a specific alkali-soluble resin and a dispersant, and specify the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound and the content ratio of the specific alkali-soluble resin. By setting it as the range of this, it discovered that the said subject could be solved and came to complete this invention. That is, the gist of the present invention is as follows.
[1] Photolithography containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. A colored photosensitive composition used to collectively form colored spacers having different heights by a method,
(B) As an alkali-soluble resin, including at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2),
(F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included,
(D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7,
The coloring photosensitive composition whose total ratio of alkali-soluble resin (A-1) and alkali-soluble resin (A-2) with respect to the total solid in a coloring photosensitive composition is 12 weight% or more.
<Alkali-soluble resin (A-1)>
Resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting with a polybasic acid anhydride <Alkali-soluble resin (A-2)>
Adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting a polyhydric alcohol and a polybasic acid anhydride. The resin [2] obtained by the above [1], wherein the total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20% by weight or more. The colored photosensitive composition described in 1.
[3] The colored photosensitive composition according to the above [1] or [2], wherein the content ratio of (a) the colorant is less than 30% by weight with respect to the total solid content in the colored photosensitive composition.
[4] The colored photosensitivity according to any one of [1] to [3], wherein (a) the content ratio of the colorant is 25% by weight or more based on the total solid content in the colored photosensitive composition. Composition.
[ 5 ] (f) AB block comprising, as a dispersant, an A block having at least one of a quaternary ammonium base and an amino group in a side chain, and a B block having no quaternary ammonium base and an amino group The colored photosensitive composition according to any one of the above [1] to [ 4 ], comprising at least one of a copolymer and a B-A-B block copolymer.
[ 6 ] (f) As a dispersant, an AB block copolymer comprising an A block having a quaternary ammonium base and an amino group in a side chain, and a B block having no quaternary ammonium base and an amino group, and The colored photosensitive composition according to any one of [1] to [ 4 ], including at least one of B-A-B block copolymers.
[ 7 ] (f) As a dispersant, an AB block comprising an A block having an amino group without a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base and an amino group. The colored photosensitive composition according to any one of [1] to [ 4 ], including at least one of a polymer and a B-A-B block copolymer.
[ 8 ] (c) The colored photosensitive composition according to any one of [1] to [ 7 ] above, which contains an oxime ester compound as a photopolymerization initiator.
[ 9 ] Colored spacers having different heights that are collectively formed from the colored photosensitive composition according to any one of [1] to [ 8 ].
[ 10 ] A color filter including the colored spacer according to [ 9 ].
[ 11 ] A liquid crystal display device comprising the color filter according to [ 10 ] above.
[ 12 ] A method for collectively forming colored spacers having different heights by photolithography using the colored photosensitive composition according to any one of [1] to [ 8 ].

According to the present invention, in a method for collectively forming colored spacers having different heights by photolithography, it is possible to secure a voltage holding ratio of liquid crystal, to form a desired shape, to control a step, and to adhere to a substrate. Can be realized.

1A and 1B are diagrams for explaining the shape of the substantially cylindrical spacer pattern of the embodiment, and FIG. 1A is a plan view of the spacer pattern, and FIG. ) Is a cross-sectional view of a spacer pattern.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. , Not specified in these contents.
In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and (meth) acrylic, (meth) acrylate, (meth) acryloyl groups, and the like have the same meaning. And “(co) polymer” means to include both a single polymer (homopolymer) and a copolymer (copolymer), and “(acid) anhydride”, “(anhydrous) ... acid”. "Is meant to include both acids and anhydrides.
In the present invention, the term “monomer” has a meaning corresponding to a so-called polymer substance, and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense. Here, the “total solid content” indicates the total of all components other than the solvent contained in the colored photosensitive composition of the present invention.

[1] Batch forming method of colored spacers having different heights A method for forming colored spacers having different heights by photolithography is mainly characterized by an exposure mask in an exposure process.
As an exposure mask, the exposure mask has a light shielding layer that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings. A method of using is known. This has a light-shielding layer (light transmittance 0%) and a plurality of openings, and averages over the opening having the highest average light transmittance (usually light transmittance 100%, hereinafter referred to as a perfect transmission opening). This is a method using an exposure mask having an opening having a small light transmittance (average light transmittance is more than 0% and less than 100%, preferably more than 5% and less than 50%, hereinafter referred to as an intermediate transmission opening). With this method, for example, in the case of a negative type colored photosensitive composition, the degree of cure of the formed pattern depends on the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. Differences can be made and then colored spacers of different heights can be formed through development and thermosetting processes.

[2] Colored photosensitive composition The colored photosensitive composition according to the present invention comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, ( e) a colored photosensitive composition used for collectively forming colored spacers having different heights by a photolithography method, comprising a solvent, and (f) a dispersant,
(B) As an alkali-soluble resin, including at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2),
(F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included,
(D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7,
The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by weight or more.
<Alkali-soluble resin (A-1)>
Resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting with a polybasic acid anhydride .
<Alkali-soluble resin (A-2)>
Adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting a polyhydric alcohol and a polybasic acid anhydride. Resin obtained by

[2-1] (a) Colorant A pigment is usually used as the colorant. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

Examples of black pigments include perylene black (BASF K0084, K0086), cyanine black, and first black HB (C.I. 26150).
In the colored photosensitive composition of the present invention, a single black color material or a black color material obtained by mixing red, green, blue and the like can be used. These black color materials can be appropriately selected from inorganic or organic pigments and dyes such as carbon black and titanium black, and can be used alone or in combination.

Examples of commercially available carbon black include the following brands.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.
Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Sck, 350, S350, 250, 350

  Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACKPEARLS 480, PEARL.

Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.
Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.
The colored photosensitive composition of the present invention comprises (a) the following red pigment as (1) as a colorant, and at least one of the following (2) blue pigment and the following (3) purple pigment: It is preferable from the viewpoint of light shielding properties.

(1) C.I. I. Red pigment selected from pig instrument red 177,254 (2) C. I. Pig instrument Blue 15: 6 blue pigment (3) C. I. Violet pigment among them is a pig instrument Violet 23, (1) and may include (2), ensuring the voltage holding ratio of the liquid crystal, the control of the step, from the viewpoint of adhesion to the substrate. In addition, C.I. I. Pig instrument Red 254 and C. I. It is preferable from the viewpoint of improving the light-shielding property in the visible light region including the 6: pig instrument Blue 15.

  In the colored photosensitive composition of the present invention, the content ratio of (a) the colorant is preferably 35% by weight or less, and less than 30% by weight based on the total solid content in the colored photosensitive composition. Is more preferable. If it is 35% by weight or less, the difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is preferably increased. If it is less than 30% by weight, the difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening exceeds 0.35 μm. The preferred range is 5% to 28% by weight, more preferably 10% to 25% by weight. (A) When the content ratio of the colorant is too large, the sensitivity of the colored photosensitive composition is lowered, and there may be a case where spacers having different heights and steps cannot be formed. On the other hand, when the content ratio of the colorant is too small, there may be a case where sufficient light shielding properties as the colored spacer cannot be ensured.

[2-2] (b) Alkali-soluble resin The alkali-soluble resin (A-1) used in the present invention is an α, β-unsaturated monocarboxylic acid or ester moiety having a carboxyl group in an epoxy resin. It can be obtained by adding an unsaturated monocarboxylic acid ester and further reacting with a polybasic acid anhydride to impart alkali solubility. Such a reaction product has substantially no epoxy group due to its chemical structure.

  As the raw material epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolak type epoxy resin, An epoxy resin, an adamantyl group-containing epoxy resin, a fluorene type epoxy resin, or the like that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin can be suitably used.

  The molecular weight of the epoxy resin is measured by gel permeation chromatography (GPC), and as a weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”), Mw is usually in the range of 200 to 200,000, preferably 300 to 100,000. It is. When the molecular weight is less than the above range, it may be difficult to obtain a preferable Mw alkali-soluble resin (A-1). Conversely, when the molecular weight exceeds the above range, α, β-unsaturated monocarboxylic acid Gelation is likely to occur during the addition reaction, and production may be difficult.

  Examples of the α, β-unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is rich in reactivity. preferable. In addition, α, β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-maleinoyloxyethyl, and acrylic acid-2-phthaloyloxy. Ethyl, acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexa And hydrophthaloyloxyethyl and crotonic acid-2-succinoyloxyethyl.

  The addition reaction between the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester portion and the epoxy resin can be carried out using a known method. The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is 0.5 to 1.2 relative to 1 equivalent of the epoxy group of the raw material epoxy resin. The range of equivalent is preferable, More preferably, it is the range of 0.7-1.1 equivalent. When the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid anhydride The reaction may be insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof may remain as an unreacted product. In either case, the curing characteristics of the coating film may be deteriorated.

In the present invention, even if it does not go through an epoxy resin as a manufacturing process, if the final resin structure is the same, in the present application, it is also within the category of the alkali-soluble resin (A-1). Define. Examples thereof include a method of reacting, for example, a novolac resin and an unsaturated group-containing epoxy compound.
As a polybasic acid anhydride to be further added to a product obtained by adding an α, β-unsaturated monocarboxylic acid to an epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety, an anhydrous maleic anhydride is used. Acid, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, end methylenetetrahydro anhydride Examples include phthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, preferably maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Pyromellitic anhydride, trimellitic anhydride Biphenyl tetracarboxylic dianhydride, particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic acid dianhydride.

  A known method can also be used for addition reaction of polybasic acid anhydride. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 mgKOH / g to 150 mgKOH / g, more preferably in the range of 20 mgKOH / g to 140 mgKOH / g. preferable. When the acid value is below the above range, the alkali developability is poor, and when it exceeds the above range, a tendency to be inferior in curing performance is recognized.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A-1) used in the present invention is usually 1500 or more, preferably 2000 or more, and usually 50000 or less. Preferably it is 30000 or less, More preferably, it is 10,000 or less. If the weight average molecular weight of the alkali-soluble resin (A-1) is too small, the sensitivity tends to decrease, and if it is too large, the solubility in the developer may be insufficient.

The alkali-soluble resin (A-2) used in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester portion to an epoxy resin, and It is obtained by reacting a polyhydric alcohol and a polybasic acid anhydride.
All components other than the synthesis method and polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-1) can be used for the synthesis of the alkali-soluble resin (A-2). The alkali-soluble resin (A-2) is usually a reaction formed by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin. The product is obtained by mixing a polyhydric alcohol and a polybasic acid anhydride and heating. In this case, there is no restriction | limiting in particular in the mixing order of a polyhydric alcohol and a polybasic acid anhydride.

Examples of the polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-2) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that it is 1 type, or 2 or more types of polyhydric alcohol chosen.
By using a polyhydric alcohol, it is possible to increase the molecular weight of the alkali-soluble resin (A-2), introduce branching into the molecule, and balance the molecular weight and viscosity. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.

If the amount of polyhydric alcohol is too small, the effect is thin, and if it is too large, there is a possibility of thickening or gelation. It is about 0.01 to 0.5 weight times normally with respect to the reaction material with the (alpha), (beta)-unsaturated monocarboxylic acid ester component which has, Preferably it is about 0.02 to 0.2 weight times.
The acid value of the alkali-soluble resin (A-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more. If the acid value is less than 10 mgKOH / g, developability may be insufficient. If the acid value is excessively high, there is a problem with the alkali resistance of the colored photosensitive composition (that is, the alkaline developer may cause roughening of the pattern surface or film loss). It is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

  The weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A-2) is preferably 1,500 or more, and more preferably 2,000 or more. . Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less. If the weight average molecular weight is too small, there may be a problem in sensitivity, coating strength, and alkali resistance, and if it is too large, a problem may occur in developability and re-solubility.

The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition of the present invention is 12% by weight or more, preferably 20% by weight or more. More preferably, it is 30% by weight or more, usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. If the proportion of the alkali-soluble resin is too large than this range, the developability is lowered, and at the same time, the proportion of the pigment is too small, so that the necessary light-shielding properties tend not to be ensured. May not be possible.
As alkali-soluble resin, you may use together alkali-soluble resin other than alkali-soluble resin (A-1) and alkali-soluble resin (A-2).

[2-3] (c) Photopolymerization initiator
The photopolymerization initiator according to the present invention is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat.
Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
Halomethylated oxadiazole derivatives;

2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. An imidazole derivative of
Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzanthrone derivatives;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- Acetophenone derivatives such as (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;

Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluoro Feni-1-i , Di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

As photopolymerization initiators, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity, and are disadvantageous in terms of sensitivity when using an alkali-soluble resin containing a phenolic hydroxyl group. Therefore, oxime derivatives (oxime and ketoxime compounds) excellent in such sensitivity are particularly useful.
Examples of the oxime compound include a compound containing a structural moiety represented by the following general formula (2), and preferably include an oxime ester compound represented by the following general formula (3).

(In the formula (2), R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. 3 to 8 cycloalkanoyl group, 3 to 20 alkoxycarbonylalkanoyl group, 8 to 20 phenoxycarbonylalkanoyl group, 3 to 20 heteroaryloxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.)

(In Formula (3), R ^1a is hydrogen or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms. , C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, C1-C20 aminoalkyl Group, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroarylloyl group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 2 to 10 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.
R ^1b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^1a may form a ring together with R ^1b , and the linking group thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) _r. -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3).
R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms. , An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, and a carbon number carbon An aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown. )

R ² in the general formula (2) and R ^2a in the general formula (3) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Of the cycloalkanoyl group.

R ^1a in the general formula (3) is preferably an unsubstituted methyl group, ethyl group, propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.
In addition, R ^1b in the general formula (3) is preferably a carbazoyl group which may be substituted, a thioxanthonyl group which may be substituted, or a phenyl sulfide group which may be substituted.

  Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.

  Examples of the ketoxime compound include a compound containing a structural moiety represented by the following general formula (4), and preferably an oxime ester compound represented by the following general formula (5).

(In the general formula (4), R ⁴ has the same meaning as R ² in the general formula (2).)

(In the above general formula (5), R ^3a is a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroaryl having 1 to 20 carbon atoms, each of which may be substituted. An alkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or heteroary Ruthioalkyl group, C1-C20 aminoalkyl group, C2-C12 alkanoyl group, C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 aryloyl group , A C1-C20 heteroaryloyl group, a C2-C10 alkoxycarbonyl group, or a C7 To 20 aryloxycarbonyl groups.

R ^3b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^3a may form a ring together with R ^3b , and the linking group thereof may have a substituent, an alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) _r -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3).

R ^4a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, carbon Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group. )

R ⁴ in the general formula (4) and R ^4a in the general formula (5) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. And a cycloalkanoyl group and an aryloyl group having 7 to 20 carbon atoms.

R ^3a in the general formula (5) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.
Moreover, as R ^<3b> in the said General formula (5), Preferably the carbazoyl group which may be substituted and the phenyl sulfide group which may be substituted are mentioned.

  Specific examples of the ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but the ketoxime ester-based compound is not limited to these compounds.

These oxime and ketoxime ester compounds are known compounds per se, and for example, a series of compounds described in Japanese Unexamined Patent Publication No. 2000-80068 and Japanese Unexamined Patent Publication No. 2006-36750. It is a kind.
The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
The ratio of the photopolymerization initiator in the light-shielding photosensitive resin composition of the present invention is usually 0.4 to 15% by weight, preferably 0.5 to 10% by weight, based on the total solid content. If the ratio of the photopolymerization initiator is too much within this range, the developability tends to be lowered, while if it is too small, the preferred voltage holding ratio, the shape of the colored spacer, and the formation of a step may not be formed.

  The colored photosensitive composition according to the present invention is characterized in that the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is less than 7. The alkali-soluble resin in this case means the total of all alkali-soluble resins including at least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). The weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is usually 1 or more, preferably 1.5 or more, more preferably 2 or more, preferably 6 or less, and more preferably 5 or less. If it is 7 or more, the required step may not be formed, and if it is too small, the developability may be deteriorated. When a large amount of alkali-soluble resin having a long dissolution time with respect to the developer is used, the developability may be lowered even if it is 7 or more.

[2-4] (d) Ethylenically unsaturated compound
Said photoinitiator is used with an ethylenically unsaturated compound.
As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith. From the viewpoint that the difference in solubility can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.

Furthermore, it is preferable for the voltage holding ratio to use a compound having three or more ethylenically unsaturated bonds in the molecule.
Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

  The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

Specific examples of esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.

Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.
Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.

  Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

  Other esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts. And the reaction product. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.

  As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formulas (6), (7) and (8) are preferable.

(In formulas (6), (7) and (8), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.)
Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (Meth) acryloyloxyethylene glycol phosphate and the like may be mentioned, and these may be used alone or as a mixture.

  Examples of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate. ) Acrylate compound, aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tris Aromatic polyisocyanates such as isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like.

Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.
Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, etc. manufactured by Asahi Kasei Corporation Biuret type, same A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. The compound obtained, or a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as Asahi Kasei Kogyo “Duranate ME20-100”, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. 1 or more hydroxyl groups and 2 in one molecule Above, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.

  Examples of epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, etc. Aromatic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, heterocyclic polyepoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanurate, and reactants with polyepoxy compounds such as .

  Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds in which the ether bond of the ethylenically unsaturated compound is sulfurized with phosphorus pentasulfide or the like to change to a thioether bond to improve the crosslinking rate, and for example, Japanese Patent No. 3164407 and Japan Polyfunctional (meth) acrylate compounds described in JP-A-9-100111 and silica sols having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd.), methyl ethyl ketone-dispersed organo Silica sol (manufactured by Nissan Chemical Co., Ltd.) MEK-ST "), methyl isobutyl ketone-dispersed organosilica sol (" MIBK-ST "manufactured by Nissan Chemical Co., Ltd.)] and the like] using an isocyanate group or a mercapto group-containing silane coupling agent. Examples thereof include compounds that have improved the strength and heat resistance as a cured product by reacting and bonding an unsaturated compound with a silica sol via a silane coupling agent.

In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Those having 5 or more functional groups are particularly preferred.
The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

The ratio of the ethylenically unsaturated compound in the light-shielding photosensitive resin composition of the present invention is usually 1 to 60% by weight, preferably 5 to 40% by weight, particularly preferably 12 to 30% by weight, based on the total solid content. It is. If the ratio of the ethylenically unsaturated compound is too much within this range, the developability tends to be lowered. On the other hand, if the amount is too small, it tends to be difficult to ensure the voltage holding ratio and to form the colored spacer and the step.
In the present invention, the above-mentioned alkali-soluble resin is not included in the ethylenically unsaturated compound.

[2-5] (e) Solvent
Each component contained in the colored photosensitive composition of the present invention described above is usually dissolved or dispersed in a solvent and used as a colored photosensitive composition solution.
Examples of the solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Luketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropion Acid, 3-e Methyl xylpropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, Examples include butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.

  In the colored photosensitive composition of the present invention, the content of the solvent is not particularly limited, but is usually 90% by weight or less and usually 60% by weight from the viewpoint of ease of application during film formation and film thickness control. In particular, the content is preferably 70% by weight or more. That is, the colored photosensitive composition of the present invention is preferably prepared so that the total solid content concentration is usually 10% by weight or more, usually 40% by weight or less, particularly 30% by weight or less.

[2-6] (f) Dispersant In the photosensitive resin composition of the present invention, a dispersant is used for improving the dispersibility of the colorant and improving the dispersion stability.
In the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant. The acrylic block copolymer containing such nitrogen atoms has a nitrogen atom contained therein having an affinity for the colorant surface, and a portion other than the nitrogen atom increases the affinity for the medium, It is estimated that it contributes to the improvement of dispersion stability.

The performance of a dispersant is its adsorption behavior on the solid surface. The reason why the block copolymer is excellent in the adsorption behavior is unknown in detail, but the following is presumed.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically at the time of copolymerization. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may be an obstacle when adsorbing to the colorant. On the other hand, in a resin whose molecular arrangement is controlled, such as a block copolymer, a portion that prevents adsorption of the dispersant can be disposed at a position away from the adsorption portion of the pigment and the dispersant. That is, an optimum portion for adsorption can be arranged in the adsorbing portion between the colorant and the dispersing agent, and a portion suitable for it can be arranged in a portion requiring solvent affinity. In particular, the dispersion of a coloring material containing a colorant having a small crystallite size is presumed that this molecular arrangement affects the good dispersibility.

  An acrylic block copolymer containing a nitrogen atom is preferable in that the colorant used in the present invention can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed to the colorant. As an acrylic block copolymer, an AB block copolymer comprising an A block having at least one of a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group. At least one of a polymer and a B-A-B block copolymer is preferable.

When the A block has a quaternary ammonium base, the quaternary ammonium base is preferably —N ⁺ R ²¹ R ²² R ²³ · M ⁻ (wherein R ²¹ , R ²² and R ²³ are each independently hydrogen Represents an optionally substituted cyclic or chain hydrocarbon group, or two or more of R ²¹ , R ²² and R ²³ may be bonded to each other to form a cyclic structure; M ⁻ represents a counter anion. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ²¹ R ²² R ²³ , as a cyclic structure formed by combining two or more of R ²¹ , R ²² and R ²³ with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following. These cyclic structures may further have a substituent.

(In the above formula, R represents any group of R ^{21 to} R ^23. )
As ^R 21 ^{to R 23} in ^{-N + R 21 R 22 R 23} , more preferred are optionally substituted alkyl group having 1 to 3 carbon atoms, which may have a substituent phenyl Or a benzyl group which may have a substituent.
In addition, the A block having a quaternary ammonium base is particularly preferably one containing a partial structure represented by the following general formula (VI).

(In the above formula (VI), R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ²¹ , R ²² and Two or more of R ²³ may be bonded to each other to form a cyclic structure, R ²⁴ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and M ⁻ represents Represents a counter anion.)
In the general formula (VI), the hydrocarbon groups of R ²¹ , R ²² , and R ²³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (VI), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ²⁵ —, —COO—R ²⁶ — (provided that R ²⁵ and R ²⁶ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ²⁷ —O—R ²⁸ —: R ²⁷ and R ²⁸ are each independently an alkylene group). And the like, and preferably —COO—R ²⁶ —.
Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

  Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done.

The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, it is not included in the A block.
In addition, the A block of the acrylic block copolymer described above may have an unreacted tertiary amino group that is not quaternized.

When the A block has an amino group, the amino group may be any of primary to tertiary. The content ratio of the monomer having the primary to tertiary amino group is preferably 20 mol% or more, more preferably 50 mol in the monomer composition constituting the acrylic block copolymer. % Or more.
This amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

The primary to tertiary amino group is preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable. As a partial structure including this (repeating unit), preferred examples include the following: A structure represented by the general formula can be given.

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.

(In the above general formula, R ⁴⁴ has the same meaning as described above.)
Furthermore, the partial structure containing the said amino group may be contained 2 or more types in one A block. In that case, two or more types of amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. A partial structure not containing an amino group may be partially contained in the A block, and examples of such a partial structure include a partial structure derived from a (meth) acrylic acid ester monomer. . The content of such a partial structure not containing an amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, but such an amino group-free partial structure is contained in the A block. Most preferably it is not included.

The A block may have either one of a quaternary ammonium base or an amino group, or may have both. The solubility of a quaternary ammonium base is low and the solubility of an amino group is high in a solvent with low polarity. Therefore, when many solvents with low polarity are used in the resist, from the viewpoint of improving the solubility of the dispersant in the resist solvent, the A block has a quaternary ammonium base and an amino group or quaternary ammonium. It preferably has an amino group without a group, and more preferably has an amino group without a quaternary ammonium group.
On the other hand, the B block constituting the acrylic block copolymer has no quaternary ammonium base and amino group as described above, and is composed of a monomer that can be copolymerized with the monomer constituting the A block as described above. There is no particular limitation. The B block is a solvophilic site that does not have a nitrogen atom-containing functional group serving as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .

  Examples of the B block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. Acid butyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (Meth) acrylate monomers such as (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N , N-di Vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylamide monomers such as chill aminoethyl acrylamide N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such.

  As the B block, one containing a partial structure derived from a (meth) acrylic acid ester monomer represented by the following formula (VIII) is particularly preferable.

(In the above formula (VIII), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.)
Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.

When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99% by weight, more preferably 0 to 85% by weight.
The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by a living polymerization method.

The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. For example, the method described in Japanese Patent Application Laid-Open No. 2007-270147 can be mentioned.
The amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the A block has a quaternary ammonium base and when it does not. It is different. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of acid necessary for neutralizing the amino group in 1 g of the copolymer.

That is, in the AB block copolymer and the B-A-B block copolymer according to the present invention, when the A block has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is Usually, it is preferably 0.1 to 10 mmol, and outside this range, it may not be possible to combine good heat resistance and dispersibility.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 80 mgKOH / g. . More preferably, it is 1-50 mgKOH / g.

When the quaternary ammonium base is not included in the A block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH / g. Hereinafter, it is more preferably 90 to 150 mgKOH / g.
The acid value of such an acrylic block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g. g or less, more preferably 40 mgKOH / g or less.

The molecular weight of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-reduced weight average molecular weight (Mw) measured by GPC. When the molecular weight of the acrylic block copolymer is too small, the dispersion stability decreases, and when it is too large, the developability and resolution tend to decrease.
In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

  In the present invention, the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by weight or more and 90% by weight or less, preferably 5% by weight or more and 60% by weight or less based on the pigment. Or 5 to 40% by weight. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained. If it is too much, the proportion of other components will decrease and the voltage holding ratio will decrease. On the other hand, the shape of the colored spacer and the formation of the step may not be possible.

In the present invention, a dispersant other than an acrylic block copolymer containing a nitrogen atom may be used in combination. The dispersant used in combination is preferably a polymer dispersant, and is preferably a polymer having a completely different structure from the colorant.
Examples of the dispersant used in combination include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene diester-based dispersant, Examples thereof include polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

In the colored photosensitive composition of the present invention, it is preferable to use a dispersion aid together in order to improve the dispersion stability of the colorant. Here, the dispersion aid means a pigment derivative or the like for improving the dispersibility of the colorant.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.
These pigment derivatives can be used alone or in combination of two or more.
When a pigment derivative is used, the amount used is usually from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight, more preferably from 0.1 to 10% by weight, still more preferably from 0.1 to 30% by weight based on the pigment. 1 to 5% by weight.

[2-7] Other ingredients
In addition to the above components, the light-shielding photosensitive resin composition of the present invention further includes a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, a plasticizer, and a storage. A stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic acid anhydride, a development improver, a thermal polymerization inhibitor and the like may be contained.

[2-7-1] Photoacid generator The photoacid generator is a compound capable of generating an acid by ultraviolet rays. For example, a crosslinking agent such as a melamine compound is generated by the action of the acid generated upon exposure. If there is, it will advance a crosslinking reaction. Among such photoacid generators, those having a high solubility in a solvent, particularly in a solvent used in a colored photosensitive composition, are preferable, for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl). Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p -Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Triazine compounds such as bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4,6-bistrichloromethyltriazine can be exemplified, but not limited thereto.

[2-7-2] Crosslinking agent
A cross-linking agent can be further added to the colored photosensitive composition of the present invention, and for example, a melamine or guanamine compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XI).

(In the formula, R ⁶¹ represents —NR ⁶⁶ R ⁶⁷ group or aryl, and when R ⁶¹ is —NR ⁶⁶ R ⁶⁷ group, one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ ) And when R ⁶¹ is aryl, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, and R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ The rest, independently of one another, represent hydrogen or a —CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents hydrogen or alkyl.)

Here, the aryl is typically phenyl, 1-naphthyl or 2-naphthyl, and a substituent such as alkyl, alkoxy or halogen may be bonded to the phenyl or naphthyl. Alkyl and alkoxy can each have about 1 to 6 carbon atoms. Among the above, alkyl represented by R ⁶⁸ is generally methyl or ethyl, especially methyl.

  Melamine compounds corresponding to the general formula (XI), that is, compounds of the following general formula (XI-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.

(In the formula, when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is aryl, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group. , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and the remainder of R ⁶⁷ independently of one another represent hydrogen or a —CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents hydrogen or alkyl.)

Further, guanamine compounds corresponding to the general formula (XI), that is, compounds in which R ⁶¹ in the general formula (XI) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.
In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the crosslinking agent used is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, based on the total solid content of the light-shielding photosensitive resin composition.

[2-7-3] Adhesion improver The light-shielding photosensitive resin composition of the present invention may contain an adhesion improver in order to sufficiently adhere fine lines and dots.
As the adhesion improver, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent, or the like is preferable. Examples of the compound containing a nitrogen atom include diamines (described in JP-A-11-184080). And other azoles are preferred. Among them, azoles are preferable, and in particular, imidazoles (adhesion improvers described in JP-A-9-236923, etc.), benzimidazoles, benzotriazoles (adhesion improvement described in JP-A-2000-171968). Agents, etc.) are preferred, and imidazoles and benzimidazoles are most preferred. Among these, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve adhesion. -Aminoimidazole is preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferable. Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.

These can be used alone or in combination of two or more.
When blending these adhesion improvers, the blending ratio varies depending on the type of adhesion improver used, but is 0.01 to 5% by weight, particularly 0.05, based on the total solid content of the colored photosensitive composition. It is preferable to set it to -3 weight%. If it is less than this, sufficient adhesion improving effect may not be obtained, and if it is too much, developability may be lowered.

[2-7-4] Sensitizing dye
Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335. JP-A-3-239703, JP-A-5-289335, a 3-ketocoumarin compound described in JP-A-6-19240, and JP-A-6-19240. Pyrromethene dyes, etc., Japanese Patent Application Publication No. 47-2528, Japanese Patent Application Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Application Publication No. 48-84183, Japan JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56 No. 03, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088, Japanese Unexamined Patent Publication No. 5-107761, Japanese Unexamined Patent Publication No. 5-210240, Japanese Unexamined Patent Publication No. 4-4 Examples thereof include a dye having a dialkylaminobenzene skeleton described in JP-A-288818.

These can be used alone or in combination of two or more.
When mix | blending a sensitizing dye, the content rate of the sensitizing dye in the total solid in a colored photosensitive composition is 0.01 to 5 weight% normally, Preferably it is 0.05 to 3 weight%. If it is less than this, the sensitization effect may not be obtained, and if it is too much, developability may be lowered.

[2-7-5] Surfactant
As the surfactant, one or more of various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. It is preferable to use an ionic surfactant. In addition, fluorine-based and silicon-based materials are effective in terms of coating properties.
The blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0. 0% by weight with respect to the total solid content in the colored photosensitive composition. It is in the range of 5% by weight, most preferably 0.03-0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the addition amount is large, the smoothness and uniformity of the coating film may not be expressed, and other characteristics may be exhibited. It may get worse.

[2-7-6] Organic Carboxylic Acid, Organic Carboxylic Anhydride The colored photosensitive composition of the present invention is at least one of an organic carboxylic acid and an organic carboxylic anhydride for the purpose of improving developability and improving background stains. May be included.
Examples of the organic carboxylic acid include at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid.

  Specific examples of the aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid, aconitic acid and camphoric acid. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include a carboxylic acid in which a carboxyl group is directly bonded to a group, and a carboxylic acid in which a carboxyl group is bonded from a phenyl group through a carbon bond.

Among the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.
The molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving background stains may be insufficient. If the molecular weight is too small, the addition amount may decrease or process contamination may occur due to sublimation or volatilization.

  Examples of the organic carboxylic acid anhydride include at least one of an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples of the aliphatic carboxylic acid anhydride include acetic anhydride, trichloroacetic anhydride, and anhydrous Trifluoroacetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene anhydride Examples include aliphatic carboxylic acid anhydrides such as 2,3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving scumming may be insufficient. If the molecular weight is too small, the amount added may be reduced or process contamination may occur due to sublimation or volatilization.

One of these organic carboxylic acids and organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.
The amount of these organic carboxylic acid and organic carboxylic acid anhydride added is usually 0.01% by weight to 5% by weight, preferably 0.03% in the total solid content of the light-shielding photosensitive resin composition of the present invention. % By weight to 3% by weight. If the addition amount is too small, a sufficient addition effect may not be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and undissolved peeling pieces may be generated.

[2-7-7] Thermal polymerization inhibitor
As the thermal polymerization inhibitor, for example, one or more of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used.
The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the light-shielding photosensitive resin composition. Sensitivity may be reduced.

[2-7-8] Plasticizer
As the plasticizer, for example, one or more of dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like are used. It is done.
The blending ratio of these plasticizers is preferably in the range of 5% by weight or less with respect to the total solid content in the light-shielding photosensitive resin composition, and if it is more than this, the curing point of the resin black matrix is lowered.

[3] Method for producing colored photosensitive composition
Next, the manufacturing method of the coloring photosensitive composition of this invention is demonstrated.
Hereinafter, a colored photosensitive composition using a pigment as a colorant will be described.
First, a pigment dispersion is produced using (a) a pigment, (f) a dispersant and necessary components. Next, the pigment dispersion obtained above, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent are mixed to give a colored photosensitive composition. Manufacturing. If necessary, the other components described above may be mixed.

[3-1] (a) Method for producing pigment dispersion
Various methods can be adopted as a method for producing the pigment dispersion according to the present invention. An example is shown below.
First, a predetermined amount of each of the pigment, the solvent, and the dispersant / dispersion aid is weighed, and in the dispersion treatment step, the pigment is dispersed to obtain a liquid pigment dispersion. As the pigment, the solvent, and the dispersant / dispersion aid, those described as the constituent components of the above-mentioned colored photosensitive composition can be used.

In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads.
Since the pigment is formed into fine particles by this dispersion treatment, the colored photosensitive composition using the pigment dispersion is improved in plate making performance such as coating characteristics and linearity.

When dispersing the pigment, the above alkali-soluble resin or the like may be appropriately used in combination.
The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The appropriate dispersion time depends on the composition of the pigment dispersion (pigment, solvent, dispersant / dispersion aid, etc.), the size of the sand grinder apparatus, and the like.

The content of the pigment (a) in the pigment dispersion is usually 5% by weight or more and 50% by weight or less, and preferably 10% by weight or more and 40% by weight or less.
The content of the dispersant (f) in the pigment dispersion is usually 5% by weight to 90% by weight, preferably 5% by weight to 60% by weight, more preferably 5% by weight, based on the pigment. It is 40 weight or less.

The content of the dispersion aid in the pigment dispersion is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and still more preferably based on the pigment. Is 0.1 to 5% by weight.
The content of the alkali-soluble resin (b) in the pigment dispersion is usually 0 to 100% by weight, preferably 5 to 80% by weight, more preferably 5% by weight based on the pigment. % To 60% by weight.

[3-2] Method for producing colored photosensitive composition
Next, the pigment dispersion (ink) obtained by the above dispersion treatment and the above-mentioned other components necessary as a colored photosensitive composition component are added and mixed with stirring to obtain a uniform colored photosensitive composition solution. In this manufacturing process, fine dust is often mixed in the liquid. Therefore, it is desirable to filter the obtained colored photosensitive composition solution with a filter or the like.
In addition, the coloring photosensitive composition using other than a pigment (for example, dye) as a coloring agent can be manufactured by a well-known method.

[4] Method for forming colored spacer The colored photosensitive composition of the present embodiment is used in the same manner as a known colored photosensitive composition for a color filter. explain.
Usually, a colored photosensitive composition solution is supplied into a film or pattern by a method such as coating on a substrate on which a colored spacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a photolithography method in which exposure and development are performed. Then, if necessary, a colored spacer is formed on the substrate by performing additional exposure or thermosetting treatment.

[4-1] Supplying method to substrate
The colored photosensitive composition of the present embodiment is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.

The coating amount varies depending on the application. For example, in the case of a colored spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. Further, it is important that the dry film thickness or the height of the finally formed colored spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.
A known substrate such as a glass substrate can be used as the substrate. The substrate surface is preferably a flat surface.

[4-2] Drying method
The drying after supplying the colored photosensitive composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a decompression chamber, without raising temperature.
Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used. The temperature is selected in the range of 30 seconds to 3 minutes.

[4-3] Exposure method
The exposure is performed by overlaying a negative mask pattern on the coating film of the colored photosensitive composition and irradiating an ultraviolet or visible light source through this mask pattern. When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the colored photosensitive composition, or the exposure mask is placed at a position away from the coating film of the colored photosensitive composition, and the exposure is performed. A method of projecting exposure light through a mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.

  The light source used for said exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

The optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
Further, in the method for forming colored spacers having different heights by photolithography, the exposure mask includes a light shielding layer that blocks light transmission and an opening portion that transmits light, and a part of the opening portions. Using an exposure mask whose average light transmittance is smaller than the average light transmittance of other openings, that is, an opening having a light shielding layer (light transmittance 0%) and a plurality of openings, and having the highest average light transmittance A method using an exposure mask having an opening (intermediate transmission opening) having a small average light transmittance relative to a portion (usually light transmittance of 100%, hereinafter referred to as a complete transmission opening) can be used.

  As a method for forming the intermediate transmission opening, the above optical filter is arbitrarily arranged in the opening (translucent part) of the mask pattern, that is, the opening provided with the optical filter (intermediate transmission opening) and the opening not provided. A method using a mask in which portions (completely transmissive openings) are appropriately arranged can be employed. This makes it possible to form patterns with different photopolymerization rates in accordance with the light transmittance of the openings by a single exposure process, for example, simultaneously forming patterns having different heights in a single exposure process. Is possible.

As another method for forming the intermediate transmission opening, as described in Japanese Patent Application Laid-Open No. 2003-344860, the light-shielding portion and the complete transmission portion are formed into a fine matrix pattern or a fine slit pattern. The exposure mask having an intermediate transmission opening whose average light transmittance is adjusted (the light transmission is smaller than that of the complete transmission opening) can be formed.
The exposure amount in the present embodiment, usually, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200 mJ / cm ² Hereinafter, it is more preferably 150 mJ / cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[4-4] Development method
After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
Although there is no restriction | limiting in particular about the method of image development processing, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development, at the image development temperature of 10 to 50 degreeC, Preferably it is 15 to 45 degreeC. .

[4-5] Additional exposure and thermosetting treatment
If necessary, the substrate after development may be subjected to additional exposure by a method similar to the above exposure method, or may be subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature ranges from 100 ° C. to 280 ° C., preferably from 150 ° C. to 250 ° C., and the time ranges from 5 minutes to 60 minutes.

  The colored photosensitive composition of the present embodiment is a colored photosensitive composition that is suitably used when forming a black matrix, an overcoat, a rib, a colored spacer, and the like in a color filter such as a liquid crystal display. In particular, a colored photosensitive composition suitable for a method for simultaneously forming colored spacers having different heights by a photolithography method can be provided. In addition, according to this embodiment, a high-quality color filter, a liquid crystal display device, and the like can be provided.

[5] Colored spacer
The colored spacer formed from the colored photosensitive composition of the present invention preferably has a substantially cylindrical spacer pattern.
The lower cross-sectional diameter of the colored spacer pattern of the complete transmission opening is usually more than 15 μm and less than 45 μm, preferably more than 18 μm and less than 40 μm. If it is lower than this range, the compression characteristics tend to be poor. If it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.

The lower cross-sectional diameter of the colored spacer pattern of the intermediate transmission opening is usually more than 20 μm and less than 50 μm, preferably more than 30 μm and less than 40 μm. If it is lower than this range, the compression characteristics tend to be poor. If it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.
The difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is that the height of the colored spacer pattern in the completely transmissive opening exceeds 2.8 μm and less than 3.2 μm. In this case, it is usually 0.25 μm or more and 1.0 μm or less, preferably 0.35 μm or more and 0.80 μm or less, more preferably 0.4 μm or more and 0.6 μm or less. When it is lower than this range, the load resistance tends to deteriorate, and when it is higher than this range, the compression limit tends to be exceeded.

[6] Color filter The color filter of the present invention comprises the colored spacer of the present invention as described above. For example, a black matrix and red, green, and blue pixel colored layers on a glass substrate as a transparent substrate. And an overcoat layer are laminated to form a colored spacer, and then an alignment film is formed. As the alignment film, a resin film such as polyimide is suitable.

[7] Liquid crystal display device The liquid crystal display device of the present invention is provided with the color filter having the colored spacer of the present invention as described above. For example, the above-described color filter and a liquid crystal driving side substrate are bonded together to form a liquid crystal cell. Form. Manufactured by injecting liquid crystal into the formed liquid crystal cell.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.
The components of the colored photosensitive composition used in the following examples and comparative examples are as follows.
In the following, “part” represents “part by weight”.

<Alkali-soluble resin-1>
“ADEP02” manufactured by Shin-Nakamura Chemical Co., Ltd. ((MW = 3500-4500, acid value = about 110 mg-KOH / g, corresponding to alkali-soluble resin (A-2))
<Alkali-soluble resin-2>
“ZCR-1664H” manufactured by Nippon Kayaku Co., Ltd. (MW = 5000 to 6000, acid value = about 60 mg-KOH / g, corresponding to alkali-soluble resin (A-1))
<Alkali-soluble resin-3>
“SPCM-82” (Showa Polymer Co., Ltd.) (MW = about 10,000, acid value = about 24 mg-KOH / g, acrylate-based alkali-soluble resin)

<Alkali-soluble resin-4>
In a 500 mL four-necked flask, 61.2 g of styrene / acrylic acid resin, Jonkrill 680 (BASF Japan Ltd.) was uniformly dissolved in 138.6 g of propylene glycol monomethyl ether acetate at 80 ° C. To this, 0.24 g of tetraammonium chloride and 0.09 g of p-methoxyphenol were added and dissolved, 71.4 g of propylene glycol monomethyl ether acetate and 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A400 Daicel Chemical Co., Ltd.) 19 .9 g of the mixed solution was dropped over 40 minutes. The reaction solution was stirred for 32 hours while maintaining at 80 ° C. to obtain a resin having a weight average molecular weight of 6700 and an acid value of 106 mgKOH / g.

<Alkali-soluble resin-5>
“SPCM-121B” manufactured by Showa Polymer Co., Ltd. (MW = about 8300, acid value = about 80 mg-KOH / g, acrylate-based alkali-soluble resin)

<Dispersant-1>
“DisperBYK-2000” (acrylic AB block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block not having a quaternary ammonium base)
<Dispersant-2>
“DisperBYK-LPN21116” (acrylic AB block copolymer consisting of an A block having a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group in the side chain. )
<Dispersant-3>
“DisperBYK-167” manufactured by Big Chemie (urethane-based dispersant)
<Dispersing aid>
“S12000” manufactured by Loop Resor

<Surfactant>
Mega Japan F-475 manufactured by Dainippon Ink & Chemicals, Inc.
<Solvent-1>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-2>
MB: 3-methoxybutanol <Solvent-3>
MBA: 3-methoxybutyl acetate <Solvent-4>
CHN: cyclohexanone <photopolymerization initiator>
A compound represented by the following formula.

<Ethylenically unsaturated compound>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate
<Preparation of pigment dispersions-1 to 4>
The pigment, dispersant, dispersion aid, alkali-soluble resin, and propylene glycol monomethyl ether acetate (PGMEA) and methoxybutyl acetate (MBA) as a solvent described in Table 1 were mixed at a weight ratio described in Table 1. Here, 80% of the volume of the dispersion container was mixed with zirconia beads, filled in a picomill dispersion container, and dispersed for a required retention time to prepare each pigment dispersion.

[Examples 1 to 3, Comparative Examples 1 to 4]
The pigment dispersion prepared above and the components shown in Table 2 were blended in the proportions shown in Table 2 and stirred to prepare colored photosensitive composition coating solutions. Using the obtained colored photosensitive composition solution by the method described below, to form a substantially cylindrical spacer pattern was evaluated shape, stepped, adhesiveness and voltage holding ratio between the substrate (VHR). The results are shown in Table 2.

[Method of forming colored spacers with different heights at once]
The said photosensitive composition was apply | coated using the spinner on this ITO film | membrane of the glass substrate which formed the ITO film | membrane on the surface. Subsequently, the coating film was formed by heating and drying on a hot plate at 110 ° C. for 70 s. The dry film thickness was 3.5 μm.
The obtained coating film was subjected to exposure treatment using an exposure mask having a circular transmission pattern having a circular pattern with a diameter of 15 μm and an intermediate transmission opening having a circular pattern with a diameter of 35 μm. The intermediate transmission opening is a thin film of Cr oxide having a light transmittance of 12.1% at a wavelength of 365 nm, a light transmittance of 405 nm at 16.5%, and a light transmittance at 436 nm of 19.6%. . The light transmittance before and after the three points is continuous, and there is no inflection point. The exposure gap (distance between the mask and the coated surface) was 250 μm.
Further, ultraviolet rays having an intensity at 365 nm of 32 mW / cm ² were used. The exposure amount was 50 mJ / cm ² . Moreover, ultraviolet irradiation was performed under air. Next, spray development was performed for 1.6 times the minimum development time using a 0.1% potassium hydroxide aqueous solution at 25 ° C., and further rinsed with pure water. Those that did not melt even after 120 seconds could not be developed.
By these operations, a pattern from which unnecessary portions were removed was obtained. The board | substrate with which the said pattern was formed was heated at 230 degreeC for 20 minute (s) in oven, the pattern was hardened, and the substantially cylindrical spacer pattern was obtained.

[Measurement of colored spacer pattern shape]
About the said substantially cylindrical colored spacer pattern, the longitudinal cross section which passes along the central axis of a colored spacer pattern was profiled, and the cross-sectional diameter of the height of a colored spacer pattern and an upper and lower bottom face was measured. For measurement, a three-dimensional non-contact surface shape measurement system Micromap MM3500-M100 manufactured by Ryoka System Co., Ltd. was used.

  FIG. 1A and FIG. 1B are views for explaining the shape of the substantially cylindrical spacer pattern. In FIG. 1A, the colored spacer pattern 1 is formed in a convex shape on a glass substrate 2 and has a substantially circular outline in plan view. FIG. 1B is an XX cross-sectional view passing through the central axis 3 of the colored spacer pattern 1 of FIG. In FIG. 1B, the colored spacer pattern 1 has a substantially rectangular outline. Such an outline is defined as a profile 4 of the colored spacer pattern 1, and intersections between the pattern side surface 41 of the profile 4 and the glass substrate 2 are defined as intersections A and A '. The distance from the surface of the glass substrate 2 to the highest point of the profile 4 is the pattern height H, and the distance between the intersection A and the intersection A ′ is the lower cross-sectional diameter L.

[Evaluation of steps]
The difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is more than 0.35 μm and not more than 0.8 μm. The thing was made into (triangle | delta) and less than 0.25 micrometer was set to x. The results are shown in Table 2.

[Evaluation of adhesion]
As described above, the size of the intermediate transmission opening is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35. 24 patterns of different sizes were formed using a mask provided with 24 intermediate transmission openings of 40, 45, and 50 μm. The size (diameter) of the smallest intermediate transmission aperture where no 24 patterns disappeared was measured. Those having a size of 15 μm or less were rated as “◯” and those having a size exceeding 15 μm were rated as “×”. The results are shown in Table 2.

[Evaluation of voltage holding ratio (VHR)]
The voltage holding ratio (VHR) was evaluated by the method described below, and the results are shown in Table 2.
<Production of liquid crystal cell>
An extraction substrate having a width of 2 mm was connected to the center of one side of the glass substrate of 2.5 cm square and an electrode substrate A (manufactured by ECH Co., Ltd., glass ITO solid for evaluation) having an ITO film formed on the entire surface of a 5 cm square An electrode substrate B (manufactured by ECH, evaluation glass SZ-B111MIN (B)) on which a 1 cm square ITO film was formed was prepared.

Each colored photosensitive composition solution was applied onto the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked at 110 ° C. for 70 s on a hot plate to obtain a coating film having a dry film thickness of 3.5 μm. Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed using 3 kW high-pressure mercury under exposure conditions of 50 mJ / cm ² . Next, shower development with a water pressure of 0.15 MPa was performed at 25 ° C. using an approximately 0.1 wt% potassium hydroxide aqueous solution at 25 ° C., and then development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was about 1.6 times the time (break time) during which the photosensitive layer was dissolved and removed. Those that did not melt even after 120 seconds could not be developed.

  The electrode substrate thus imaged was post-baked at 230 ° C. for 20 minutes to obtain a resist-coated electrode substrate (resist substrate). Thereafter, a polyimide solution was applied to the resist substrate, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes. The resist substrate thus obtained was cut into a 2.5 cm square substrate to complete an evaluation electrode substrate A.

On the other hand, a polyimide solution was applied also onto the electrode substrate B, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes to complete an evaluation electrode substrate B.
Thereafter, an epoxy resin sealant containing silica beads having a diameter of 5 μm is applied on the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A for evaluation is placed on the front side (the sealant side) of the electrode substrate B. The application surface was pasted and bonded to complete the empty cell. Heating was performed at 180 ° C. for 2 hours in a hot air circulating furnace.

  A liquid crystal (MLC-6608 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.

<Evaluation of voltage holding ratio (VHR)>
After the above liquid crystal cell is annealed (heated at 105 ° C. for 2.5 hours in a hot air circulating furnace), it is applied to the electrode substrates A and B for evaluation at a voltage of 5 V, 0.6 Hz, and a frame time of 1667 msec. The voltage holding ratio was measured by “VHR-6254 type” manufactured by Toyo Corporation.

  From the results of Table 2, according to the colored photosensitive composition of the present invention, the formation of the shape of the completely transmissive opening portion and the intermediate transmissive opening portion pattern, the control of the level difference, the good adhesion, and the liquid crystal voltage holding ratio are excellent. It can be seen that it is possible to obtain colored spacers, which is useful for a method of forming colored spacers having different heights at once.

  Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on October 25, 2011 (Japanese Patent Application No. 2011-233900), the contents of which are incorporated herein by reference.

  The colored photosensitive composition of the present invention is a colored photosensitive composition that is suitably used when forming a colored spacer or the like in a color filter such as a liquid crystal display, and is a colored spacer having a different height by a photolithography method in particular. In the case of forming all together, it is excellent in shape formation, level difference, adhesion, and liquid crystal electrical reliability. The present invention can provide a high-quality color filter, a liquid crystal display device, and the like.

Claims (14)

(A) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, A colored photosensitive composition used to collectively form colored spacers having different thicknesses,
(B) As an alkali-soluble resin, including at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2),
(F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included,
(D) The weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is 2 or more and less than 7,
The coloring photosensitive composition whose total ratio of alkali-soluble resin (A-1) and alkali-soluble resin (A-2) with respect to the total solid in a coloring photosensitive composition is 12 weight% or more.
<Alkali-soluble resin (A-1)>
Resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting with a polybasic acid anhydride <Alkali-soluble resin (A-2)>
Adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting a polyhydric alcohol and a polybasic acid anhydride. Resin obtained by   The colored photosensitive composition according to claim 1, wherein the total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20% by weight or more. .   The colored photosensitive composition according to claim 1 or 2, wherein the content ratio of (a) the colorant is less than 30% by weight with respect to the total solid content in the colored photosensitive composition.   The colored photosensitive composition according to any one of claims 1 to 3, wherein the content ratio of (a) the colorant is 25% by weight or more based on the total solid content in the colored photosensitive composition. (A) The coloring photosensitive composition of any one of Claims 1 thru | or 4 containing the black color material by multiple types mixing as a coloring agent. (F) AB block copolymer comprising, as a dispersant, an A block having at least one of a quaternary ammonium base and an amino group in a side chain, and a B block having no quaternary ammonium base and an amino group. And the colored photosensitive composition according to any one of claims 1 to 5 , comprising at least one of a B-A-B block copolymer. (F) AB block copolymer and B-A comprising A block having a quaternary ammonium base and amino group in the side chain, and a B block having no quaternary ammonium base and amino group as a dispersant. The colored photosensitive composition according to any one of claims 1 to 5 , comprising at least one of -B block copolymers. (F) As a dispersant, an AB block copolymer comprising an A block having no amino group in the side chain and an amino group, and a B block having no quaternary ammonium base and no amino group, and The colored photosensitive composition according to any one of claims 1 to 5 , comprising at least one of B-A-B block copolymers. (C) The colored photosensitive composition according to any one of claims 1 to 8 , comprising an oxime ester compound as a photopolymerization initiator. The colored photosensitive composition according to any one of claims 1 to 9, which is used to collectively form light-shielding spacers having different heights by a photolithography method. Colored spacers having different heights which are collectively formed by a colored photosensitive composition according to any one of claims 1 to 10. A color filter comprising the colored spacer according to claim 11 . A liquid crystal display device comprising the color filter according to claim 12 . A method for collectively forming colored spacers having different heights by photolithography using the colored photosensitive composition according to any one of claims 1 to 10 .

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