KR101985564B1 - Colored photosensitive composition, black photo spacer, and color filter - Google Patents

Abstract

1. A colored photosensitive composition comprising a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the pigment contains the pigment shown in (A) and the pigment shown in (B).
(A) one selected from the group consisting of CI Pigment Orange 43, CI Pigment Orange 64 and CI Pigment Orange 72
(B) CI Pigment Blue 60

Description

COLORED PHOTOSENSITIVE COMPOSITION, BLACK PHOTO SPACER, AND COLOR FILTER,

The present invention relates to a colored photosensitive composition and the like. Specifically, for example, a colored photosensitive composition preferably used for forming a black photo spacer or the like in a color filter such as a liquid crystal display, and a black photo spacer formed by using the colored photosensitive composition and a color including the black photo spacer Filter.

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

However, in the LCD using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electric characteristics of the photosensitive composition itself and the influence of the impurities contained in the photosensitive composition, thereby causing problems such as display unevenness on the display. Particularly, in a color liquid crystal display device, a member closer to the liquid crystal layer, for example, a liquid crystal panel, which is used for maintaining a constant gap between two substrates, a so-called columnar spacer, a photo spacer, Is large.

Conventionally, when a spacer having no light shielding property is used for a TFT-type LCD, a TFT serving as a switching element may malfunction due to light transmitted through a spacer. In order to prevent this, for example, Patent Document 1 discloses that the spacer is made light-shielding.

However, in order to make the spacer light-shielding, it is conceivable to add a coloring agent or the like usually containing a pigment to the photosensitive composition. However, the addition of the coloring agent reduces the curing property of the spacer layer due to the decrease of the clear component, There is a fear that characteristics may be deteriorated due to influence of impurities and the like.

In order to control the voltage holding ratio, a method of improving the curability and a method of controlling the curable resin, the dispersing agent, etc. of the photosensitive composition have been proposed.

On the other hand, recently, a method of collectively forming spacers having different heights in accordance with the change of the panel structure when manufacturing spacers by photolithography has been proposed. Patent Document 2 discloses that the shapes and steps of spacers having different desired heights can be realized by controlling the exposure amount and the residual film ratio.

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

Patent Document 2, however, relates to a spacer to which a pigment is not added. When the pigment is applied to a batch formation of a coloring spacer to which a pigment is added, since the pigment absorbs light in the ultraviolet region contributing to photopolymerization, the light transmittance It has been found that it is difficult to attain characteristics such as the shape of the desired spacer having different heights, the control of the step difference, the adhesion with the substrate, etc.

The present invention has been made in view of such circumstances. That is, a main object of the present invention is to provide a method for collectively forming black photo spacers having different heights by photolithography, which is capable of securing the light shielding ability and the voltage holding ratio of the liquid crystal, Which is capable of forming a black photo-spacer excellent in adhesion of the black photo-sensitive composition.

Another object of the present invention is to provide a black photo-spacer formed by such a colored photosensitive composition.

Another object of the present invention is to provide a color filter having such a black photo spacer.

As a result of intensive studies on the above problems, the present inventors have found out that the above problems can be solved by using a specific pigment as a colorant, and have accomplished the present invention. That is, the gist of the present invention is as follows.

[1] A colored photosensitive composition comprising a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the pigment contains the pigment shown in the following (A) and the pigment shown in (B).

(A) C.I. Pigment Orange 43, C.I. Pigment Orange 64 and C.I. Pigment Orange 72 < / RTI >

(B) C.I. Pigment Blue 60

[2] The pigment according to the above [1], wherein the pigment is C.I. Pigment Orange 64 and C.I. The colored photosensitive composition according to the above [1], which contains Pigment Blue 60.

[3] The process according to [1], wherein the pigment is a CI pigment. Pigment Red 254, C.I. Pigment Violet 23 and C.I. Pigment Violet 29. The colored photosensitive composition according to the above [1] or [2], further comprising one selected from the group consisting of Pigment Violet 29,

[4] The colored photosensitive composition according to [1], wherein the pigment contains the pigment shown in the following (1) or the pigment shown in (2).

(1) C.I. Pigment Orange 64, C.I. Pigment Blue 60 and C.I. Pigment Red 254

(2) C.I. Pigment Orange 64, C.I. Pigment Blue 60 and C.I. Pigment Violet 29

[5] A black photo-spacer formed by using the colored photosensitive composition according to any one of [1] to [4].

[6] A color filter comprising the black photo-spacer according to [5].

According to the present invention, in a method of collectively forming black photo spacers having different heights by photolithography, by appropriately combining pigment species having different light absorption characteristics and securing a balance of light absorption between the ultraviolet region and the visible region, It is possible to control the shape and the step difference while maintaining the light shielding ability and the voltage holding ratio of the liquid crystal, and realize high adhesion with the substrate.

Hereinafter, the embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. Unless the subject matter of the present invention is exceeded, It is not.

In the present invention, "(meth) acryl" and the like mean "at least one of acrylic and methacrylic", and "(meth) acrylate" and the like mean "at least one of acrylate and methacrylate Quot ;, and " (meth) acrylic acid " means " at least one of acrylic acid and methacrylic acid ". The "(meth) acryloyl" is also the same. In addition, "(an) anhydride", "(anhydrous) ..." Acid " means to include both an acid and an anhydride thereof.

The term " total solid content " means all components other than the solvent components to be contained in the colored photosensitive composition or the pigment dispersion.

In the present invention, unless otherwise stated, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of standard polystyrene as measured by GPC (Gel Permeation Chromatography). "C.I." means a color index (cI).

In the present invention, " amine value " means the amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH in terms of the amount of the basic group per 1 g of the solid content of the dispersant. The measuring method will be described later. On the other hand, "acid value" means the acid value in terms of effective solid content unless otherwise stated, and is calculated by neutralization titration.

In the present invention, the term " monomer " is meant to correspond to a so-called high molecular substance and includes not only a monomer (monomer) in a narrow sense, but also a dimer, a trimer and an oligomer.

The colored photosensitive composition of the present invention is characterized by containing a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, and containing the following (A) and (B) as a pigment, Is preferably used as a colored photosensitive composition for collectively forming black photo spacers having different heights.

(A) C.I. Pigment Orange 43, C.I. Pigment Orange 64 and C.I. Pigment Orange 72 < / RTI >

(B) C.I. Pigment Blue 60

[Batch formation method of black photo spacers having different heights]

First, a method of collectively forming black photo spacers having different heights by a photolithography method in which the colored photosensitive composition of the present invention is preferably used will be described. This method is mainly characterized by an exposure mask in an exposure process.

As the exposure mask, there is known a method of using an exposure mask having a light-shielding layer for shielding transmission of light and a plurality of apertures for transmitting light, wherein the average light transmittance of some apertures is smaller than the average light transmittance of the other apertures. (Average transmittance of 0%) and a plurality of openings, and has an average light transmittance smaller than that of the openings having the highest average light transmittance (usually 100% light transmittance, hereinafter referred to as " A light transmittance of more than 0% but less than 100%, preferably more than 5% and less than 50%. Hereinafter, this is referred to as an " intermediate transmission opening "). With this method, for example, in the case of a negative type colored photosensitive composition, a difference in the average light transmittance of the intermediate transmission opening portion and the full transmission opening portion, that is, a difference in the degree of curing of the pattern formed by the difference in exposure amount, Developing and thermal curing processes, black photo spacers having different heights can be formed.

[Colored photosensitive composition]

The constituent materials of the colored photosensitive composition of the present invention will be described below.

[1] pigments

The pigment refers to coloring the colored photosensitive composition of the present invention.

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. Examples of the structure include organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazine pigments, indanthrene pigments, and perylene pigments, and various inorganic pigments.

In the colored photosensitive composition of the present invention, the following components (A) and (B) are contained as essential components.

(A) C.I. Pigment Orange 43, C.I. Pigment Orange 64 and C.I. Pigment Orange 72 < / RTI >

(B) C.I. Pigment Blue 60

In the colored photosensitive composition of the present invention, the pigment to be used is not particularly limited except that the pigment (A) and the pigment (B) are contained as essential components, Color materials can be used. Further, it can be appropriately selected and used in combination with a black pigment, other inorganic or organic pigments, and a dye.

Specific examples of usable pigments are shown below by pigment numbers.

As the red pigment, C.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 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 48: 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 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. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red 177, 179, 209, 224, and 254. Among them, C.I. Pigment Red 254 (R254).

As the blue pigment, C.I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, , 35, 36, 56, 56: 1, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6.

As the green pigment, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, Of these, C.I. Pigment Green 7, 36 can be mentioned.

As the yellow pigment, C.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, 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: , 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 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, and 208, respectively. Of these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment Yellow 83, 138, 139, 150, and 180, respectively.

As the orange pigment, C.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. Pigment Orange 38, 43, 64, 71, 72. More preferably, C.I. Pigment Orange 43, 64, 72. More preferably, C.I. Pigment Orange 64 (Or64).

As the violet pigment, C.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. Pigment Violet 19, 23, 29, more preferably C.I. Pigment Violet 23, 29, and even more preferably C.I. Pigment Violet 29 (V29).

Examples of the black pigment include perylene black (K0084, K0086 manufactured by BASF), cyanine black, first black HB (CI 26150), Irgaphor Black S 0100 CF (manufactured by BASF), carbon black and titanium black.

Examples of commercially available products of carbon black include the following items.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400 # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31

Printex3, Printex3, Printex30, Printex30, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex, Printex L, Printex G, Printex P, Printex 1, Printex V, Printex G, Color Black FW1, Color Black FW2, Color Black FW1, Color Black FW1, Color Black FW1, Color Black S160, Color Black S170, Special Black150, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4,

Monarch120, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

Not a car Headquarters Manufacturing kolreombi: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN760, RAVEN780RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1060U, RAVEN1080U, RAVEN1100URAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1590, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Examples of commercially available products of titanium black include the following items.

Manufactured by Mitsubishi Materials Corporation: 10S, 12S, 13R, 13M, 13M-C, 14M, 15M, L-15M etc.

UV-6, F, S, C, X, etc., manufactured by Ako Chemical Co., Ltd .: Tilack DM, M-50, M-50A, M-AM,

The colored photosensitive composition of the present invention is preferably used as a pigment in terms of the light shielding ability, the voltage holding ratio of the liquid crystal, the control of the shape and the level difference, and the adhesion with the substrate. Pigment Orange 64 and C.I. Pigment Blue 60 is preferably contained.

The colored photosensitive composition of the present invention may contain, in addition to the above components (A) and (B) as pigments, C.I. Pigment Red 254, C.I. Pigment Violet 23 and C.I. Pigment Violet 29. It is preferable that the pigment contains one selected from the group consisting of < RTI ID = 0.0 >

The colored photosensitive composition of the present invention is preferably used as a pigment in order to control the light shielding property, the voltage holding ratio of the liquid crystal, the shape and the level difference, and the adhesion to the substrate, (1) or (2), from the viewpoint of the voltage holding ratio of the liquid crystal.

(1) C.I. Pigment Orange 64, C.I. Pigment Blue 60, C.I. Pigment Red 254

(2) C.I. Pigment Orange 64, C.I. Pigment Blue 60, C.I. Pigment Violet 29

(3) C.I. Pigment Orange 64, C.I. Pigment Blue 60, C.I. Pigment Violet 23

The proportion of the pigment in the colored photosensitive composition of the present invention is generally 5 to 50% by weight, preferably 10 to 45% by weight, and more preferably 20 to 42% by weight based on the total solid content. If the amount of the pigment is larger than this range, the shape of the spacer, the level difference, the adhesion with the substrate may deteriorate, the curing component may be reduced, and the pigment or the like may be eluted into the liquid crystal layer. On the other hand, if it is less than this range, sufficient light shielding property as a black photo spacer can not be ensured.

The ratio of (A) to (B) in the pigment is preferably such that the ratio of (A) to (B) in the pigment is too high or too low, (A) in an amount of 25 to 70% by weight, particularly 30 to 60% by weight, especially 35 to 60% by weight, based on 100% by weight of the total of the components (A) and (B) Is preferably used.

That is, (A) absorbs light having a wavelength in the vicinity of 330 nm to 380 nm is comparatively small, and absorption of light in the vicinity of a wavelength of 400 nm to 550 nm is large. On the other hand, (B) similarly absorbs light having a wavelength in the vicinity of 330 nm to 380 nm and absorbs light having a wavelength in the vicinity of 550 nm to 700 nm. Therefore, by using these two kinds of pigments in a well-balanced combination, it is possible to make the balance of light absorption between the ultraviolet region and the visible region to be good, to control the light shielding ability, the voltage retention rate of the liquid crystal, have.

The pigments used in the present invention may contain various pigments other than (A) and (B), but in order to sufficiently obtain the above-mentioned effect by the combined use of (A) and (B) (A) and (B) in the total of 100% by weight of the pigment contained in the colored photosensitive composition of the present invention is preferably 50% by weight or more, particularly preferably 60 to 95% by weight, particularly preferably 70 to 90% by weight .

Further, in the combination of pigments used in the present invention, (A) and (B) and further C.I. By using Pigment Red 254 (R254), it is possible to increase the absorption of the visible region while suppressing light absorption in the ultraviolet region, and to improve the light shielding ability, the voltage retention rate of the liquid crystal, Effect is exerted. In this case, 20 to 40% by weight of (A), 45 to 65% by weight of (B) and 5 to 25% by weight of R254 are contained in the total of 100% by weight of (A) and (B) It is preferable to use 25 to 35% by weight of (A), 50 to 60% by weight of (B), and 10 to 20% by weight of R254. The total amount of (A), (B) and R254 in the total pigment in the colored photosensitive composition is preferably 70% by weight or more, particularly 90% by weight or more, By weight to 100% by weight.

Further, in the combination of pigments used in the present invention, (A) and (B) and further C.I. By using Pigment Violet 23 (V23), it is possible to increase the absorption of the visible region while suppressing the absorption of light in the ultraviolet region, to further improve the light shielding ability, the voltage retention rate of the liquid crystal, . In this case, 30 to 50% by weight of (A), 30 to 50% by weight of (B) and 10 to 30% by weight of V23 are contained in the total of 100% by weight of (A), (B) It is preferable to use 35 to 45 wt% of (A), 35 to 45 wt% of (B), and 15 to 25 wt% of V23. The total amount of (A), (B) and (V) in the total pigment in the colored photosensitive composition is 70% by weight or more, particularly 90 to 90% by weight, By weight to 100% by weight.

Further, in the combination of pigments used in the present invention, (A) and (B) and further C.I. By using Pigment Violet 29 (V29), it is possible to increase the absorption of the visible region while suppressing the absorption of light in the ultraviolet region, and to further improve the light shielding ability, the voltage retention rate of the liquid crystal, . In this case, 30 to 50% by weight of (A), 30 to 50% by weight of (B) and 10 to 30% by weight of V29 are contained in a total of 100% by weight of (A), (B) It is preferable to use 35 to 45 wt% of (A), 35 to 45 wt% of (B), and 15 to 25 wt% of V29. The total amount of (A), (B) and (V29) in the total coloring photosensitive composition may be 70% by weight or more, By weight to 100% by weight.

In addition, the pigment used in the present invention is a pigment obtained by mixing (A) and (B) with C.I. It is preferable to contain Pigment Red 272 (R272). R272 is advantageous for high OD because of absorption of visible region.

[2] Binder resin

The binder resin used in the colored photosensitive composition of the present invention may be any resin as long as it is a resin of a member used in a color filter. Examples of the binder resin include an epoxy acrylate resin, a novolac resin, a polyvinyl phenol resin, , A carboxyl group-containing epoxy resin, and a carboxyl group-containing urethane resin. From the viewpoints of control of shape, level difference, and adhesion with a substrate, it is preferable to use an epoxy acrylate resin or an acrylic resin having a carboxyl group. It is more preferable to use an epoxy acrylate resin.

The epoxy acrylate resin is a resin obtained by adding an alpha, beta -unsaturated monocarboxylic acid or an alpha, beta -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety to an epoxy resin (or an epoxy compound) ≪ / RTI > Such a reaction product is not limited to "acrylate" in chemical structure and substantially does not have an epoxy group, but epoxy resin (or epoxy compound) is a raw material and "acrylate" is a representative example. It is named after him.

Examples of the epoxy resin to be used as the starting material include (o, m, p-) cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, (Or an epoxy compound) represented by the general formulas (1-a) to (1-a '' ') described above.

Particularly preferable as the binder resin in the present invention is described below.

<Alkali-soluble resin (A '') and alkali-soluble resin (A1 '')

As a particularly preferable binder resin in the present invention, a reaction product of an epoxy compound (a ") represented by the following general formula (1-a") and an unsaturated group-containing carboxylic acid (b " And an alkali-soluble resin (A '') obtained by reacting the alkali-soluble resin with at least one of the anhydrides (c '').

[Chemical Formula 1]

[In the above general formula (1-a "), X represents a linking group represented by the following general formula (2a), (2b) or (3). However, it includes at least one adamantane structure in the molecular structure. and l represents an integer of 2 or 3.

(2)

(In formulas (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group, a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, An alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent.

In the general formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. Y represents a divalent linking group containing an adamantane structure, which may have a substituent.

In the general formulas (2a), (2b) and (3), * represents a bonding site with a glycidyloxy group in the general formula (1-a "

(1) The epoxy compound (a ") represented by the general formula (1-a"

First, the group X in the epoxy compound (a ") represented by the above general formula (1-a") (hereinafter also referred to as "component (a") ") will be described.

When the group X is a structure represented by the general formula (2a) or (2b), it is preferable that each of the general formulas (2a) and (2b) has 2 to 4 adamantane structures. When the adamantane structure is 1, there is a tendency that the resolution of the developing solution is lowered and the resolving power is inferior.

When the group X is a structure represented by the general formula (3), Y in the general formula (3) may be a divalent linking group containing an adamantyl structure, which may have a substituent, But is preferably, for example, a linking group represented by the following general formula (4) or (5).

(3)

[The above general formulas (4) and (5) may have a substituent. * Represents a bonding site with the benzene ring in the general formula (3).

Especially, the epoxy compound (a '') represented by the general formula (1-a ") is preferably represented by the following general formula (6) or (7).

[Chemical Formula 4]

[The adamantane ring represented by the general formula (6) and the adamantyl group represented by the general formula (7) may have a substituent.

In the general formula (6), R ¹⁶ to R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.

In the general formula (7), R ²⁴ and R ²⁵ each independently represent an adamantyl group, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent .]

The alkyl group having 1 to 12 carbon atoms represented by R ¹ to R ²⁵ in the general formulas (2a), (2b), (3), (6) and (7) is preferably an alkyl group having 1 to 10 carbon atoms .

Examples of the substituent which these alkyl groups may have include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, .

Examples of the substituent which the phenyl group of R ¹ to R ^{25 in} the above general formulas (2a), (2b), (3), (6) and (7) may have include a halogen atom, a hydroxyl group, An alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group and a nitro group.

The adamantyl group of R ¹ to R ⁴ and R ¹³ to R ¹⁵ in the general formulas (2a) and (2b), the adamantane ring contained in Y of the general formula (3), the adamantane ring represented by the general formula (6 (7), adamantyl groups of R ²⁴ and R ^{25 in} the general formula (7), and adamantyl groups in the general formulas (4) and (5) Examples of the substituent which the adamantane ring may have include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, .

In the general formula (6), R ¹⁶ to R ²³ are preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group or a phenyl group.

In the general formula (7), R ²⁴ and R ²⁵ are preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group or a phenyl group.

 The molecular weight of X represented by the general formula (1-a ") is preferably 200 or more and 1000 or less. When the molecular weight of X is 200 or more, sufficient chemical resistance can be ensured. When the molecular weight of X is 1000 or less, good sensitivity can be ensured.

The epoxy equivalent of the epoxy compound (a ") represented by the general formula (1-a") is preferably 210 or more, more preferably 230 or more. The epoxy equivalent is preferably 450 or less, and more preferably 400 or less. When the epoxy equivalent of the epoxy compound (a '') is 210 or more, sufficient alkali resistance can be secured. When the epoxy equivalent is 450 or less, good sensitivity of the organic binder produced can be secured.

The epoxy compound (a '') may be used singly or in combination of two or more.

The epoxy compound (a '') may be a commercially available phenol compound, or may be synthesized by a known method from phenolic compounds as described below.

[Chemical Formula 5]

[R ¹ to R ¹⁵ in the general formulas (9a), (9b) and (10) have the same definitions as in general formulas (2a), (2b) and (3)

For example, an alkali metal salt such as sodium hydroxide, potassium hydroxide or the like is added to a molten mixture of a compound represented by the general formula (9a) or (9b) and an excess of epichlorohydrin or epihalohydrin, (1-a ") is reacted at a temperature of from 20 to 120 ° C for 1 to 10 hours while the hydroxide is added in advance or added thereto to obtain a compound represented by the general formula (2a) or (2b) To give the resulting epoxy compound (a '').

Alternatively, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance to the dissolution mixture of the compound represented by the general formula (10) and the epihalohydrin such as epichlorohydrin or epibromohydrin, or (A ") in which X in the general formula (1-a") is a connecting group represented by the general formula (3) can be obtained by reacting the epoxy compound (a ") at a temperature of 20 to 120 ° C. for 1 to 10 hours have.

In the reaction for obtaining the epoxy compound (a ''), an aqueous solution thereof may be used as the alkali metal hydroxide. In that case, an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or atmospheric pressure, and the liquid is separated, The halohydrin may be returned to the reaction system continuously.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added to a solution mixture of the compound represented by the general formula (9a), (9b) or (10) and epihalohydrin (9a), (9b) or (10), which is obtained by reacting the alkali metal hydroxide with a halohydrin ether compound at 50 to 150 ° C for 1 to 5 hours, (A ") represented by the general formula (1-a") can also be produced by a method in which the reaction is carried out again at a temperature of 20 to 120 ° C. for 1 to 10 hours to effect dehydrohalogenation (ring closing).

The amount of the epihalohydrin to be used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, per mol of the hydroxyl group of the compound represented by the general formula (9a), (9b) or (10) to be. The amount of the alkali metal hydroxide to be used is usually 0.8 to 15 mol, preferably 0.9 to 11 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (9a), (9b) or (10).

In the above-described reaction, an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide may be added in addition to alcohols such as methanol and ethanol in order to proceed the reaction further smoothly. When alcohols are used, the amount thereof is 2 to 20% by weight, preferably 4 to 15% by weight based on the amount of epihalohydrin. When an aprotic polar solvent is used, its amount is 5 to 100% by weight, preferably 10 to 90% by weight based on the amount of epihalohydrin.

Examples of the unsaturated carboxylic acid (b ") (hereinafter also referred to as" component (b ")") include unsaturated carboxylic acids having an ethylenic unsaturated group, (Meth) acrylic acid or the like substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group at the? -Position, or the like), acrylic acid, crotonic acid, o-vinylbenzoic acid, m- Of a monocarboxylic acid; (Meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (Meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (Meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (Meth) acryloyloxyalkyl esters; Monomers in which lactones such as? -Caprolactone,? -Propiolactone,? -Butyrolactone, and? -Valerolactone are added to (meth) acrylic acid; (Meth) acrylic acid dimer and the like.

Further, it is also possible to use methacrylic acid esters of pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, acrylic acid adduct of glycidyl methacrylate, Compounds obtained by adding an acid anhydride such as maleic anhydride, maleic anhydride, anhydrous tetrahydrophthalic acid or phthalic anhydride to an unsaturated compound containing a hydroxyl group such as an acid addition product.

Particularly preferred is (meth) acrylic acid.

These may be used singly or in combination of two or more kinds.

As a method of reacting the epoxy group in the component (a ") with the component (b"), known methods may be used. For example, the components (a ") and (b") may be reacted with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyl A carboxylic acid can be added to an epoxy compound by reacting with a quaternary ammonium salt such as triethylammonium chloride, pyridine, triphenylphosphine or the like as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several hours.

The amount of the catalyst to be used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight based on the total amount of the reaction raw material mixture (the sum of the components (a ") and (b")). In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol or phenothiazine) , And the amount thereof is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction mixture.

The ratio of adding the component (b ") to the epoxy group of the component (a") is usually from 90 to 100 mol%. Since the residual epoxy group tends to adversely affect the storage stability, the component (b ") is reacted at a ratio of usually 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, based on 1 equivalent of the epoxy group of the component (a") .

(3) a polybasic acid and its anhydride (c ")

At least one of a dibasic acid and an anhydride thereof (hereinafter, also referred to as "component (c") "or" polybasic acid (anhydride) ") (Hereinafter referred to as &quot; tribasic acid (anhydride) &quot;), at least one of a tribasic acid (anhydride), at least one of a tribasic acid and an anhydride Quot; basic acid (anhydride) &quot;).

As the tetrabasic acid (anhydride) (at least one of tetracarboxylic acid and its dianhydride), known ones can be used, and examples thereof include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl And tetracarboxylic acids such as tetracarboxylic acid, tetracarboxylic acid, and tetracarboxylic acid, and dianhydrides thereof. These may be used alone or in combination of two or more.

As the tetrabasic acid (anhydride), biphenyltetracarboxylic acid or an anhydride thereof is particularly preferable among the above exemplified compounds.

the molecular weight is increased by a cross-linking reaction by reacting a reaction product of the component (a ") and the component (b") with a quaternary acid (anhydride) as the component (c "). Therefore, it is preferable to improve the adhesion to the substrate, control the solubility, and improve the sensitivity and alkali resistance.

Examples of dibasic acid (anhydride) (at least one of dicarboxylic acid and anhydride thereof) include, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Lauric acid, methyl tetrahydrophthalic acid, and anhydrides thereof. Of these, tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These may be used alone or in combination of two or more.

(d ") as a component (c") to the reaction product of the component (a ") and the component (b") is easy to control the solubility and improves the adhesion to the substrate Do.

Examples of the tribasic acid (anhydride) (at least one of tricarboxylic acid and anhydride thereof) include trimellitic acid, hexahydrotrimellitic acid, and anhydrides thereof. Particularly preferred is trimellitic anhydride and hexahydrotrimellitic anhydride. These may be used alone or in combination of two or more.

(a ") as a component (c"), it is possible to introduce a branch into the molecule by increasing the molecular weight of the alkali-soluble resin (A ") and balance a molecular weight and viscosity. In addition, the introduction amount of the acid group into the molecule can be increased, and a resin having a balance of sensitivity, adhesion and the like can be obtained.

As the component (c "), it is particularly preferable to use a tetrabasic acid (anhydride). In this case, the addition ratio of the tetrabasic acid (anhydride) is usually 10 to 100 mol%, preferably 20 to 100 mol%, based on the hydroxyl group generated when the component (b ") is added to the component (a" , And more preferably 30 to 100 mol%. When the addition ratio of the tetrabasic acid (anhydride) as the component (c '') is set to the lower limit value or more, sufficient solubility of the alkali-soluble resin (A '') and good adhesion to the substrate can be secured.

From the viewpoint of controlling the viscosity or controlling the solubility of the colored photosensitive composition, it is preferable to replace a part of the above-described tetrabasic acid (anhydride) with a dibasic acid (anhydride).

(anhydride): 4 base acid (anhydride) = 99: 1 to 20: 80 in the case where a tetrabasic acid (anhydride) and a dibasic acid (anhydride) , More preferably from 80:20 to 30:70. By increasing the proportion of the tetrabasic acid (anhydride) to not less than the lower limit value described above, it is possible to obtain a high film property of the obtained coating film, and the dibasic acid (anhydride) The handling property can be improved.

In addition to the effects of improving the adhesion to the substrate, easily controlling the solubility, and improving the sensitivity and alkali resistance, in order to balance various factors such as molecular weight, viscosity, sensitivity, and adhesion, It is preferable to use at least one of an acid (anhydride) and a tribasic acid (anhydride) in combination.

(anhydrous) is used in combination with at least one of a tetrabasic acid (anhydride) and a dibasic acid (anhydride) as a component (c "), the use of an excess amount of a tribasic acid (anhydride) The amount of the tribasic acid (anhydride) to be used is usually 5 to 70 mol%, preferably 5 to 70 mol%, relative to the hydroxyl group generated when the component (b ") is added to the component (a" Is about 10 to 40 mol%.

is generally from 10 to 100 mol%, preferably from 20 to 100 mol%, more preferably from 20 to 100 mol%, based on the hydroxyl group generated when the component (b ") is added to the component (a" And more preferably 30 to 100 mol%. By setting the addition ratio of the component (c '') above the lower limit value or more, the solubility of the alkali-soluble resin (A '') and the adhesion to the substrate become better.

The component (b '') is added to the component (a '') in addition to the reaction of the component (c '') with respect to the hydroxyl group generated when the component (b '') (D &quot;) to be described later may be reacted with any of the hydroxyl groups present in the mixture.

As a method for adding the component (b ") to the component (a") or adding the component (c ") after mixing the polyhydric alcohol (d" Method can be used.

The reaction temperature is usually 80 to 130 占 폚, preferably 90 to 125 占 폚. If the reaction temperature exceeds 130 ° C, there is a possibility that a part of the unsaturated groups in the component (b ") is polymerized, leading to a sharp increase in molecular weight. If the reaction temperature is lower than 80 ° C, the reaction does not proceed smoothly, and the component (c ") may remain.

(4) Polyhydric alcohol (d ")

The binder resin used in the present invention is obtained by further adding a polyhydric alcohol (d ") (hereinafter referred to as" (d ") component (b") to the reaction product obtained by adding the component (A1 '') obtained by mixing the components (c '') and (c '') with respect to any of the hydroxyl groups present in the mixture.

Examples of the component (d ") include at least one member selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, It is preferable that the polyhydric alcohol is a polyhydric alcohol or higher.

By using the component (d "), the molecular weight of the alkali-soluble resin (A1 '') can be increased, branching can be introduced into the molecule, and balance of molecular weight and viscosity can be obtained. In addition, the introduction rate of an acid group into a molecule can be increased, and an organic binder having a balance of sensitivity and adhesion can be obtained.

The amount of the component (d ") used is usually from 0.01 to 0.5 wt% based on the reaction product of the component (a") and the component (b "), Fold, preferably 0.02 to 0.2 times by weight.

(5) Acid value and molecular weight of alkali-soluble resins (A ") and (A1")

The acid value of the alkali-soluble resins (A '') and (A1 '') thus obtained is generally 10 mg-KOH / g or more, preferably 50 mg-KOH / g or more. In order to achieve good developability, it is preferable that the acid value is not less than the lower limit value described above, and that sufficient alkali resistance of the colored photosensitive composition is ensured (i.e., the surface of the pattern is not roughened by the alkaline developer, , The acid value is preferably 200 mg-KOH / g or less, and more preferably 150 mg-KOH / g or less.

The weight average molecular weight (Mw) of the alkali-soluble resins (A ") and (A1") in terms of standard polystyrene as determined by gel permeation chromatography (GPC) is preferably 1,500 or more, more preferably 2,000 or more. Further, it is preferably 20,000 or less, more preferably 10,000 or less. By setting the weight average molecular weight to the lower limit value or more, the sensitivity, the coating film strength, the alkali resistance and the like are better. In addition, by setting it to the upper limit value or less, good developability and re-solubility can be obtained.

&Lt; Alkali-soluble resin (A) >

The alkali-soluble resin (A) is obtained by reacting a reaction product of a specific epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) with at least one of a polybasic acid and its anhydride (c).

(1) Epoxy resin (a)

The epoxy resin (a) is represented by the following general formula (1-a).

[Chemical Formula 6]

[In the general formula (1-a), n represents an average value and represents a number of 0 to 10. R ⁴¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. The plurality of R &lt; ⁴¹ &gt; s present in one molecule may be the same or different. G represents a glycidyl group]

R ⁴¹ in the general formula (1-a) represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group, And from the viewpoint of solubility, R &lt; ⁴¹ &gt; is particularly preferably a hydrogen atom or a methyl group. The plurality of R &lt; ⁴¹ &gt; s present in one molecule may be the same or different.

The epoxy resin (a) represented by the general formula (1-a) can be obtained, for example, by reacting a compound represented by the following general formula (1-a-1) with epihalohydrin in the presence of an alkali metal hydroxide have.

(7)

(Wherein n and R ⁴¹ have the same meanings as in the general formula (1-a)

The compound represented by the above general formula (1-a-1) can be obtained, for example, by condensation reaction of a compound represented by the following general formula (1-a-2) with phenols in the presence of an acid catalyst.

[Chemical Formula 8]

(Wherein Z represents a halogen atom, a hydroxyl group or a lower alkoxy group, and R ⁴¹ represents the same meaning as in the above-mentioned general formula (1-a)

Examples of the halogen atom in Z of the above general formula (1-a-2) include a chlorine atom and a bromine atom, and as the lower alkoxy group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group, .

On the other hand, phenols are aromatic compounds having one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, M, and p-isomers of alkylphenols typified by methylene chloride, methylene chloride, methyl ethyl ketone, methyl ethyl ketone, cyclohexyl methyl ketone, , And substituted phenols substituted with groups listed as R ⁴¹ in the general formula (1-a), such as phenylphenol. These phenols may be used singly or in combination of two or more.

When the condensation reaction is carried out, the amount of the phenols to be used is preferably 0.5 to 20 mol, and particularly preferably 2 to 15 mol, per mol of the compound represented by the general formula (1-a-2).

In the condensation reaction, it is preferable to use an acid catalyst. Various acid catalysts can be used, and examples thereof include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, And p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable. The amount of the acid catalyst to be used is not particularly limited, but it is preferably 0.1 to 30% by weight based on the compound represented by the general formula (1-a-2).

The condensation reaction can be carried out under a solventless condition or in the presence of an organic solvent. Specific examples of the organic solvent include toluene, xylene, methyl isobutyl ketone, and the like. The amount of the organic solvent to be used is preferably 50 to 300% by weight, more preferably 100 to 250% by weight based on the total weight of the injected raw materials. The reaction temperature is preferably in the range of 40 to 180 DEG C, and the reaction time is preferably 1 to 8 hours.

After completion of the reaction, neutralization or washing treatment is carried out to adjust the pH value of the product to 3 to 7, preferably 5 to 7. In the case of washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogenphosphate, diethylenetriamine, triethylenetetramine, And various basic substances such as organic amines such as diamines may be used as a neutralizing agent. The washing treatment may be carried out according to a conventional method. For example, a method in which water in which the neutralizing agent has been dissolved is added to the reaction mixture, and the liquid extraction operation is repeated.

After the neutralization treatment or the water washing treatment, unreacted dihydroxybenzenes and a solvent are distilled off under reduced pressure and the product is concentrated to obtain a compound represented by the above general formula (1-a-1) .

As a method for obtaining the epoxy resin (a) related to the present invention represented by the above general formula (1-a) from the compound represented by the above general formula (1-a-1), a known method can be adopted. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolution mixture of a compound represented by the general formula (1-a-1) and an epihalohydrin such as excess epichlorohydrin or epibromohydrin The epoxy resin (a) represented by the general formula (1-a) can be obtained by previously carrying out the reaction at a temperature of 20 to 120 ° C for 1 to 10 hours while being added or added.

In the reaction for obtaining the epoxy resin (a), an aqueous solution of the alkali metal hydroxide may be used. In this case, an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the reaction is carried out under reduced pressure or continuously under normal pressure The epihalohydrin may be continuously returned to the reaction system by draining water and epihalohydrin, and separating and removing water.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolution mixture of the compound represented by the above general formula (1-a-1) and epihalohydrin, A solid or an aqueous solution of an alkali metal hydroxide is added to the halohydrin ether compound of the compound represented by the general formula (1-a-1), which is obtained by reacting at 50 to 150 ° C for 1 to 5 hours, Followed by reaction at a temperature of 1 to 10 hours to effect dehydrohalogenation (ring closure).

The amount of the epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1). The amount of the alkali metal hydroxide to be used is generally 0.8 to 15 mol, preferably 0.9 to 11 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1).

In addition, alcohols such as methanol and ethanol and an aprotic polar solvent such as dimethylsulfone and dimethylsulfoxide may be added in order to proceed the reaction smoothly. When alcohols are used, the amount thereof is 2 to 20% by weight, preferably 4 to 15% by weight based on the amount of epihalohydrin. When an aprotic polar solvent is used, its amount is 5 to 100% by weight, preferably 10 to 90% by weight based on the amount of epihalohydrin.

The reaction product of the epoxidation reaction is washed with water or without heating, under reduced pressure, for example, under conditions of 110 to 250 DEG C and a pressure of not more than 1.3 mmHg (10 mmHg) And the desired epoxy resin (a) is obtained.

Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added and the reaction is carried out So that the closure can be made definite. In this case, the amount of the alkali metal hydroxide to be used is preferably 0.01 to 0.3 mol, particularly preferably 0.05 to 0.2 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1) used for the epoxidation. The reaction temperature is 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the resulting salt is removed by filtration, washing with water, and then a solvent such as toluene or methyl isobutyl ketone is distilled off under reduced pressure and heat to obtain an epoxy resin (a) represented by the above general formula (1-a) Can be obtained.

(2) unsaturated group-containing carboxylic acid (b)

Examples of the unsaturated carboxylic acid (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include (meth) acrylic acid, crotonic acid, o-, m-, Benzoic acid, monocarboxylic acids such as haloalkyl, alkoxyl, halogen, nitro and cyano substituents at the α-position of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (Meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acrylic acid (Meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid with? -Caprolactone,? -Propiolactone,? -Butyrolactone (Anhydrous) phthalic acid, (anhydride) phthalic acid, (methacrylic acid), and (meth) acrylic acid, which are obtained by adding lactones such as lactone and δ- valerolactone, Maleic anhydride), (meth) acrylic acid dimer, and the like.

Of these, (meth) acrylic acid is particularly preferable in terms of sensitivity. These may be used alone, or two or more of them may be used in combination.

(3) Reaction between an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b)

As a method for reacting the epoxy group in the epoxy resin (a) with the unsaturated carboxylic acid (b), a known technique may be used. For example, the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) are reacted with a tertiary amine such as triethylamine, benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, A carboxylic acid can be added to the epoxy resin by reacting with a quaternary ammonium salt such as benzyltriethylammonium chloride, pyridine, triphenylphosphine or the like as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several tens of hours .

The amount of the catalyst to be used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight based on the total amount of the reaction raw material mixture (the sum of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b)).

In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.) And the amount thereof to be used is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the reaction mixture.

The ratio of adding the unsaturated carboxylic acid (b) to the epoxy group of the epoxy resin (a) is usually 90 to 100 mol%. The unsaturated group-containing carboxylic acid (b) is usually reacted at a ratio of 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, per equivalent of epoxy group of the epoxy resin (a), since the residual epoxy group adversely affects the storage stability .

(4) polybasic acid and its anhydride (c)

As the polybasic acid and its anhydride (c) which are added to the hydroxyl group of the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), known ones can be used, and maleic acid, succinic acid, itaconic acid, phthalic acid, , Hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicar A dibasic carboxylic acid such as a carboxylic acid or its anhydride; Polybasic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and biphenyltetracarboxylic acid, and anhydrides thereof. Among them, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone, or two or more of them may be used in combination.

The addition ratio of at least one of the polybasic acid and the anhydride (c) is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 10 to 100 mol%, of the hydroxyl groups generated when the unsaturated carboxylic acid (b) is added to the epoxy resin (a) 100 mol%, and more preferably 30 to 100 mol%. If the addition ratio is too large, the residual film ratio at the time of development may be lowered, and if it is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient. When a polybasic acid and its anhydride are used in combination, the addition rate represents the addition rate of the polybasic acid and the anhydride thereof in total.

As a method of adding at least one of the polybasic acid and its anhydride (c) after adding the unsaturated group-containing carboxylic acid (b) to the epoxy resin (a), a known method may be used.

In the present invention, the epoxy group-containing compound (d) may be added to a part of the resulting carboxyl groups after addition of at least one of the polybasic acid and the anhydride (c). In this case, as the epoxy group-containing compound (d), glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group Of a glycidyl ether compound having no polymerizable unsaturated group may be added in order to add an epoxy group-containing unsaturated compound or to improve developability, or both of them may be used in combination. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (trade name: Denacol EX-111, Denacol EX-121, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192).

The alkali-soluble resin (A) related to the present invention is a resin obtained by reacting a reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) with at least one of a polybasic acid and its anhydride (c) , Or a resin obtained by adding such an epoxy group-containing compound (d) to a part of the carboxyl group.

(5) Property of the alkali-soluble resin (A)

The weight average molecular weight (Mw) of the alkali-soluble resin (A) used in the present invention in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1500 or more, preferably 2000 or more, Is not more than 30000, more preferably not more than 10000. When the weight average molecular weight of the alkali-soluble resin (A) is too small, the sensitivity is inferior. When the weight average molecular weight is too large, the solubility in a developer is insufficient.

The acid value (mgKOH / g) of the alkali-soluble resin (A) used in the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. If the acid value of the alkali-soluble resin (A) is too low, sufficient solubility may not be obtained. If the acid value is too high, the curability tends to be insufficient and the surface property of the coating film tends to deteriorate.

Further, the condensation reaction of the compound represented by the above general formula (1-a-2) with the phenolic compound and the reaction of the compound represented by the above general formula (1-a-1) obtained by the condensation reaction with the epihalohydrin , The addition reaction of the unsaturated group-containing carboxylic acid (b) and at least one of the polybasic acid and the anhydride thereof (c) can be carried out by a known method. For example, It can be carried out by the method described in JP-A-2005-55814.

<Alkali-soluble resin (A ')>

As another example of the binder resin particularly preferred in the present invention, a reaction product of an epoxy compound (a ') represented by the following general formula (1-a') and an unsaturated group-containing carboxylic acid (b ' And an alkali-soluble resin (A ') obtained by reacting with at least one of the anhydrides (c').

[Chemical Formula 9]

[In the general formula (1-a '), p and q each independently represent an integer of 0 to 4, and R ³¹ and R ³² each independently represent an alkyl group or a halogen atom. R ³³ and R ³⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more;

(1) The epoxy compound (a ') represented by the general formula (1-a')

First, the epoxy compound (a ') represented by the general formula (1-a') (hereinafter sometimes referred to as "component (a ')") will be described.

In the general formula (1-a '), the alkyl group of R ³¹ and R ³² is preferably an alkyl group having 1 to 10 carbon atoms, and examples of the halogen atom include Cl, Br and F. R ³¹ and R ³² each independently represent an alkyl group having 1 to 5 carbon atoms.

Although the details of the mechanism of the action of the alkyl group and the halogen atom of R ³¹ and R ³² are not clear, it is presumed that they affect the three-dimensional structure of the molecule and control the solubility in the developer.

Therefore, from the above viewpoint, p and q in the general formula (1-a ') each independently represent an integer of 0 to 4, preferably 1 or 2.

The bonding position of R ³¹ and R ^{32 to} the benzene ring is not particularly limited,

[Chemical formula 10]

or

(11)

The o-position is preferred.

R ³¹ and R ³² may be the same group or different groups, but it is preferable that they are the same groups in terms of production cost.

The alkylene groups represented by R ³³ and R ³⁴ include alkylene groups having 1 to 10 carbon atoms, and particularly preferably each independently is an ethylene group or a propylene group.

x and y each independently represent an integer of 0 or more, usually 0 to 6, preferably 0 to 3; In general, the larger x and y are, the higher the solubility is, but when the x and y are too large, the sensitivity may be lowered.

R ³³ and R ³⁴ may be the same group or different groups, but it is preferable that they are the same groups in terms of production cost.

The molecular weight of the component (a ') is a weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC), usually in the range of 200 to 200,000, preferably 300 to 100,000. When the molecular weight is at least the lower limit value, the film-forming property is improved. When the molecular weight is not more than the upper limit value, gelation during addition reaction such as unsaturated group-containing carboxylic acid (b ') described later is suppressed.

(2) The unsaturated group-containing carboxylic acid (b ')

(A '') and &lt; alkali-soluble resin (A1 ') &gt; as the unsaturated group-containing carboxylic acid (b' , The same compounds as those listed above as the unsaturated group-containing carboxylic acid (b '') can be used. Of these, (meth) acrylic acid is preferable among the?,? - unsaturated carboxylic acids, and acrylic acid is particularly preferred because of its high reactivity. Among the?,? - unsaturated carboxylic acid esters having a carboxyl group in the ester moiety, 2- (meth) acryloyloxyethyl phthalic acid and 2- (meth) acryloyloxyethyl maleic acid are preferred.

The amount of the component (b ') used is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group in the component (a'), more preferably in the range of 0.7 to 1.1 equivalents.

By setting the amount of the component (b ') to be at least the lower limit value, a sufficient amount of the unsaturated group can be introduced, and the reaction with at least one of the subsequent polybasic acid and its anhydride (c') is also sufficient. It is also preferable that a large amount of epoxy groups do not remain. (b ') is set to be not more than the upper limit value, the component (b') does not remain as unreacted components. By satisfying the above range, high light curing properties can be obtained.

(3) a polybasic acid and its anhydride (c ')

Examples of the polybasic acid and its anhydride (c ') include the same compounds as listed as the polybasic acid and its anhydride (c' ') in the alkali-soluble resin (A' ') and the alkali-soluble resin (A1' ') , Among which tetrahydrophthalic acid, biphenyltetracarboxylic acid and anhydrides thereof are preferable.

The addition ratio of at least one of the polybasic acid and the anhydride (c ') is preferably such that the acid value of the finally obtained alkali-soluble resin (A') is 10 to 150 mg-KOH / g, more preferably 20 to 140 mg-KOH / g Is more preferable. When the acid value is set to the lower limit value or more, alkali developability is improved, and when the acid value is not more than the upper limit value, sufficient light curability is obtained.

It is also possible to add multifunctional alcohols (d ') such as trimethylolpropane, pentaerythritol and dipentaerythritol at the time of the addition reaction of the component (c'). Examples of the polyhydric alcohol (d ') include the same compounds as those described above as the polyhydric alcohol (d ") in the <alkali-soluble resin (A") and alkali-soluble resin (A1 " , Preferred compounds and preferred amounts are also the same.

The synthesis reaction of the alkali-soluble resin (A ') such as the addition reaction of at least one of the unsaturated group-containing carboxylic acid (b') and the polybasic acid and the anhydride (c ') to the epoxy compound (a' And can be carried out by referring to, for example, the methods described in JP-A-2005-126685, JP-A-2005-325331 and JP-A-2006-241224.

The weight average molecular weight (Mw) of the alkali-soluble resin (A ') measured by gel permeation chromatography (GPC) in terms of standard polystyrene is usually 1,000 or more, preferably 1,500 or more and usually 30,000 or less, Or less, more preferably 10,000 or less, and particularly preferably 8,000 or less. When the weight average molecular weight is less than the above upper limit value, the developability is improved. When the weight average molecular weight is not lower than the lower limit value, the alkali resistance is improved.

&Lt; Alkali-soluble resin (A &quot; ') >

As another example of a particularly preferable binder resin in the present invention, a reaction product of an epoxy resin (a '' ') and an unsaturated group-containing carboxylic acid (b' '') represented by the following general formula (1-a ' Soluble resin (A '' ') obtained by reacting an alkali-soluble resin (A' '') with at least one of a polybasic acid and its anhydride (c '' ').

[Chemical Formula 12]

Wherein R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵² represents a divalent polyhydric hydrocarbon group having 5 to 16 carbon atoms, R ⁵³ and R (in the general formula (1-a ' ⁵⁴ each independently represent a hydrogen atom or a glycidyl group. s represents 1 or 2; t and z represent the ratio of each repeating unit, and t? z? 0.5t.]

In the general formula (1-a '''), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group from the viewpoint of photo-curability. S represents 1 or 2, but is preferably 1.

R ⁵² represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms. Such a group can be obtained by using an unsaturated polycyclic hydrocarbon ring compound having at least two carbon-carbon double bonds in the same skeleton (hereinafter sometimes simply referred to as &quot; unsaturated polycyclic hydrocarbon compound &quot; .

Examples of the unsaturated polycyclic hydrocarbon ring compound as a raw material include, but are not limited to, the following compounds.

[Chemical Formula 13]

Among them, a crosslinked carbon ring is more preferable, and dicyclopentadiene is particularly preferable.

The epoxy resin (a '' ') represented by the general formula (1-a' '') is obtained by glycidylating the hydroxyl groups of the reaction product of the unsaturated polycyclic hydrocarbon compound described above and the phenol compound represented by the following general formula .

[Chemical Formula 14]

[ ^Wherein R ⁵¹ and s have the same meanings as defined in the general formula (1-a ''').]

As the epoxy resin (a '' '), a compound represented by the following general formula (1-a' '' - 1) wherein glycidylation of a dicyclopentadiene and a mid part reactant of the phenolic compound is particularly preferable .

[Chemical Formula 15]

^Wherein R ⁵³ , R ⁵⁴ , t and z have the same meanings as defined in the general formula (1-a ''') in the general formula (1-a'

The introduction ratio of the glycidyl group in the general formula (1-a '' ') and the general formula (1-a' '' - 1) is preferably 50 to 100 in the phenolic hydroxyl group in the phenol resin before glycidylation T and z in the formula (1-a '' ') and the formula (1-a' '' - 1) need to have a relationship of t? Z? 0.5t, It is preferable that 70 to 100 mol% is substituted with a glycidyl group.

The alkali-soluble resin (A '' ') is obtained by reacting a reaction product of an epoxy resin (a' '') represented by the general formula (1-a '' ') and an unsaturated group- And the anhydride (c '' ').

Examples of the unsaturated group-containing carboxylic acid (b '' ') include the unsaturated group-containing carboxylic acid (b' ') in the alkali-soluble resin (A' ') and the alkali- The same compounds as those described above can be used, and preferable compounds and the reasons thereof are the same as above.

The ratio of adding the unsaturated group-containing carboxylic acid (b '' ') to the epoxy group of the epoxy resin (a' '') is usually 90 to 100 mol%. The unsaturated group-containing carboxylic acid (b '' ') is usually used in an amount of 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin (a' '') since the epoxy group adversely affects storage stability. The reaction is carried out at a ratio of &lt; RTI ID = 0.0 &gt;

As the polybasic acid and its anhydride (c '' '), the same compounds as listed as the polybasic acid and its anhydride (c' ') in the <alkali-soluble resin (A' ') and alkali- And preferable compounds and their reasons are the same as above.

The addition ratio of at least one of the polybasic acid and the anhydride (c '' ') is usually in the range of from 15 to 80 mol% of the hydroxyl group generated when the unsaturated group-containing carboxylic acid (b' '') is added to the epoxy resin (a ' And the acid value of the finally obtained alkali-soluble resin (A '' ') is preferably 45 to 160 mg-KOH / g. By reducing the addition ratio to the upper limit value or less, it is possible to prevent the reduction of the residual film ratio at the time of development. By setting the addition ratio to the lower limit value or more, good solubility and adhesiveness to the substrate can be obtained. When the polybasic acid and its anhydride are used in combination, the addition rate represents the addition rate of the polybasic acid and the anhydride thereof in total.

(B '' ') and a polybasic acid and an anhydride thereof (c' ''), a reaction between an unsaturated polycyclic hydrocarbon compound and a phenolic compound, a glycidylation reaction of a hydroxyl group in the phenolic resin obtained by the reaction, ) Can be carried out by a known method. For example, with reference to the method described in JP-A-5-214048, the reaction of synthesizing an alkali-soluble resin (A ' .

The weight average molecular weight of the alkali-soluble resin (A '' ') is usually 1,500 to 4,000, preferably 2,000 to 3,500, and more preferably 2,500 to 3,000. If the weight average molecular weight is too small, there is a possibility that the development solubility is too high. If the weight average molecular weight is too large, there is a possibility that the development solubility is too low.

In the present invention, these binder resins may be used alone, or two or more of them may be used in combination.

As the binder resin in the colored photosensitive composition of the present invention, it is preferable that among the alkali-soluble resins (A), (A '), (A' '), (A' '' The alkali-soluble resins (A) and (A '' ') are preferable from the viewpoint of the balance of the adhesion with the control and the substrate.

The content of the binder resin is generally 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, based on the total solid content of the colored photosensitive composition of the present invention. By controlling the content of the binder resin to the above-mentioned lower limit value or more, it becomes possible to control the shape and level difference, and the solubility of the unexposed portion in the developer can be secured. In addition, by setting it to be not more than the upper limit value, it is possible to suppress occurrence of wrinkles due to excessive shrinkage upon thermal curing.

[3] Photopolymerizable monomer

In the present invention, the photopolymerization initiator is used together with a photopolymerizable monomer such as an ethylenically unsaturated compound.

The ethylenically unsaturated compound used herein means a compound having at least one ethylenic unsaturated bond in the molecule, but is preferably a compound having at least one ethylenic unsaturated bond in the molecule, which is excellent in polymerizability and crosslinkability, and in which the difference in solubility between the exposed portion and the non- (Meth) acryloyloxy group is preferable, and the ethylenically unsaturated bond is more preferably a (meth) acrylate compound derived from a (meth) acryloyloxy group .

The use of a compound having three or more ethylenic unsaturated bonds in the molecule is preferable from the viewpoint of the voltage holding ratio.

Examples of the compound having at least one ethylenic unsaturated bond in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid and citraconic acid, , (Meth) acrylonitrile, (meth) acrylamide, and styrene.

Representative examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of an unsaturated carboxylic acid and a polyhydroxy compound, phosphates containing a (meth) acryloyloxy group, hydroxy (meth) acrylate compounds and Urethane (meth) acrylates of a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound.

Specific examples of the esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.

Specific examples of the sugar alcohol include ethylene glycol, polyethylene glycol (adduct 2 to 14), propylene glycol, polypropylene glycol (adduct 2 to 14), trimethylene glycol, tetramethylene glycol , Hexamethylene glycol, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol and the like.

The reaction product of the unsaturated carboxylic acid and the alkylene oxide adduct of the sugar alcohol; the sugar alcohol is the same as described above. Specific examples of the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts.

Reaction products of unsaturated carboxylic acid and alcohol amine: Specific examples of the alcohol amines include diethanolamine, triethanolamine and the like.

Specific examples of esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide adduct tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and the same crotonate, isocroton Nate, maleate, itaconate, citraconate, etc.

Examples of other esters of an unsaturated carboxylic acid and a polyhydroxy compound include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, and bisphenol A, and ethylene oxide adducts thereof And the like. Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] The reaction product of the same unsaturated carboxylic acid with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, a reaction product of tris (2-hydroxyethyl) isocyanurate with di (Meth) acrylate, tri (meth) acrylate and the like, reaction products of an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyhydroxy compound, such as a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensation products of (meth) acrylic acid, adipic acid, butanediol and glycerin .

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

[Chemical Formula 16]

(In the formulas (6), (7) and (8), R ^A represents a hydrogen atom or a methyl group, e and g are integers of 1 to 25, and f is 1, 2 or 3.)

Here, e and g are preferably from 1 to 10, especially from 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate , (Meth) acryloyloxyethylene glycol phosphate, and the like, each of which may be used alone or as a mixture.

Examples of the urethane (meth) acrylates of the hydroxy (meth) acrylate compound and the polyisocyanate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethane tri (Meth) acrylate, and alicyclic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, Alicyclic polyisocyanates such as 4,4-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate; aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanate phenyl) thiophosphate; Isocyanate, isocyanurate, etc. And a reaction product with a polyisocyanate compound such as cyclic polyisocyanate.

Examples of such resins include UA-306A, UA-MC340H, UA-MC340H, U6LPA, and the like, which are available from Shin Nakamura Chemical Co.,

Among them, a compound having at least four urethane bonds [-NH-CO-O-] and at least four (meth) acryloyloxy groups in one molecule is preferable, and the compound is, for example, pentaerythritol, A compound obtained by reacting a compound having four or more hydroxyl groups in a molecule such as polyglycerin with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, or the like, or a compound obtained by reacting ethylene glycol Durenate 22A-75PX ", durenate 21S-75E", durenate 18H-75E "manufactured by Asahi Chemical Industry Co., Ltd., 70B ", and other duct types such as" DURANATE P-301-75E ", DURANATE E-402-90T and DURANATE E-405-80T. Preferably at least 6 isocyanate groups in a molecule such as a compound obtained by reacting a compound having 3 or more isocyanate groups in a molecule with a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Acrylate and dipentaerythritol penta (meth) acrylate, which have at least one hydroxyl group and at least two, preferably at least three (meth) acryloyloxy groups per molecule have.

Examples of the epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds include (meth) acrylic acid, or hydroxy (meth) (Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (Poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, (O-, m-, p-) cresol novolac polyepoxy compounds, bisphenol novolac polyepoxy compounds, brominated phenol novolak polyepoxy compounds, Aromatic polyepoxy compounds such as A polyepoxy compounds and bisphenol F polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate. And a reaction product with a polyepoxy compound such as a heterocyclic polyepoxy compound.

As other ethylenically unsaturated compounds, for example, allyl esters such as (meth) acrylamides such as ethylenebis (meth) acrylamide and diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate , Thioether bond-containing compounds in which the ether bond of an ether bond-containing ethylenically unsaturated compound is sulphated by sulfur pentasulfide or the like to change to a thioether bond, thereby improving the crosslinking speed, and Japanese Patent Publication No. 3164407 and Japanese Patent Laid- (Meth) acrylate compound and a silica sol 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 organosilica sol ("MEK-ST" manufactured by Nissan Chemical Industries, Ltd.), methyl isobutyl ketone-dispersed organosilica sol Produced by Mitsubishi Chemical Corporation, manufactured by Mitsubishi Chemical Corporation, etc.) with an isocyanate group or a mercapto group-containing silane coupling agent to react and bond the ethylenically unsaturated compound with a silica sol via a silane coupling agent, And a compound having improved strength and heat resistance.

In the present invention, the ethylenically unsaturated compound is preferably an ester (meth) acrylate or a urethane (meth) acrylate, and among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate, and the like are particularly preferable.

These ethylenically unsaturated compounds may be used alone or in combination of two or more.

The proportion of the photopolymerizable monomer in the colored photosensitive composition of the present invention is usually 1 to 60% by weight, preferably 5 to 40% by weight, and particularly preferably 12 to 30% by weight based on the total solid content. If the proportion of the photopolymerizable monomer is larger than this range, the curing degree is lowered as the proportion of the other components decreases, and the voltage holding ratio tends to deteriorate. On the other hand, if the amount is too small, the amount of the alkali resin is increased and thus the developability tends to decrease.

[4] Photopolymerization initiator

The photopolymerization initiator is usually used as a mixture with the accelerator (photopolymerization initiator system), and a sensitizing dye or the like to be added as needed is used in combination.

The photopolymerization initiator system is a component having a function of absorbing light directly or increasing or decreasing the light to generate a decomposition reaction or a hydrogen withdrawing reaction to generate polymerization activity radicals.

As the photopolymerization initiator constituting the photopolymerization initiator-based component, for example, various compounds described in International Publication No. 2008/153000 and the like can be used.

As the photopolymerization initiator used in the colored photosensitive composition of the present invention, an oxime ester-based compound is particularly preferable in view of the good efficiency of generating a polymerizable radical. Among them, the compounds exemplified below can be preferably used .

[Chemical Formula 17]

[Chemical Formula 18]

Examples of accelerators and sensitizing dyes constituting the photopolymerization initiator component include various compounds described in, for example, International Publication No. 2008/153000, and preferred compounds are the same as those described in International Publication No. 2008/153000 Do.

The content of the photopolymerization initiator system component (mixture of photopolymerization initiator and accelerator) is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the total solid content in the colored photosensitive composition of the present invention. If the content is too low, the sensitivity to the exposure light may be lowered. On the other hand, if the content is too high, the solubility of the unexposed portion in the developer may be lowered, resulting in poor development.

The proportion of the sensitizing dye contained in the colored photosensitive composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, based on all solids in the colored photosensitive composition.

[5] Dispersing agent / dispersing aid

It is preferable that the colored photosensitive composition of the present invention is used in combination with at least one of a pigment dispersing agent and a dispersion auxiliary agent for improving the dispersibility of the pigment and improving the dispersion stability. Among them, the use of a polymer dispersant as a pigment dispersant is particularly preferable because of excellent dispersion stability over time. Here, the polymer dispersant is a polymer which is completely different in structure from the pigment in order to secure the dispersion stability of the pigment, and the dispersion auxiliary agent refers to a pigment derivative or the like for enhancing the dispersibility of the pigment.

Examples of the polymeric dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester- have. Specific examples of these dispersants include, but are not limited to, EFKA (manufactured by BASF), DisperBYK (manufactured by Bigkemis), Diparron (manufactured by Kusumoto Chemical Co.), SOLSPERSE (manufactured by Zeneca), KP (Manufactured by Kyowa Chemical Industry Co., Ltd.).

These polymer dispersants may be used singly or as a mixture of two or more.

Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, And derivatives thereof such as thiophenol, thiophene, thiophene, thiophene, thiophene, thiophene, thiophene, thiophene and thiophene. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. directly to the pigment skeleton or through an alkyl group, an aryl group, And preferably a sulfonic acid group. These substituents may be substituted by plural substituents on one pigment skeleton.

Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfonic acid derivative .

These pigment derivatives may be used singly or in combination of two or more kinds.

In the colored photosensitive composition of the present invention, the content of at least one of the dispersing agent and the dispersion auxiliary agent is usually 5% by weight or more and 120% by weight or less, preferably 5% by weight or more and 90% by weight or less, 5 wt% or more and 60 wt% or less, particularly preferably 5 wt% or more and 40 wt% or less. If the content of the dispersing agent and the dispersing aid is too small, sufficient dispersibility may not be obtained. When the content is too large, the proportion of the other components may be decreased and the voltage holding ratio may be lowered. When the dispersing agent and the dispersion auxiliary agent are used in combination, the content represents the total content of the dispersant and the dispersion auxiliary agent.

When a pigment derivative is used, the amount of the pigment derivative to be used is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.1 to 5% by weight based on the pigment in the colored photosensitive composition Weight%.

[6] Solvent

The colored photosensitive composition of the present invention is generally prepared by dissolving or dispersing the solid components of the above-mentioned pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, dispersant, dispersion auxiliary, and other components described below in a solvent.

The solvent has a function of controlling viscosity by dissolving or dispersing a pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and the like in the colored photosensitive composition of the present invention.

As the solvent, it is preferable to select one having a boiling point in the range of 100 to 300 占 폚. And more preferably a solvent having a boiling point of 120 to 280 ° C.

Such a solvent includes, for example, various solvents described in International Publication No. 2008/153000 and the like.

These solvents may be used alone, or two or more solvents may be used in combination.

Particularly, when a black photo spacer is formed by a photolithography method, it is preferable to select a solvent that has a boiling point in the range of 100 to 200 ° C (under the condition of a pressure of 1013.25 [hPa], the same applies to all boiling points) desirable. And particularly preferably a boiling point of 120 to 170 ° C.

Glycol alkyl ether acetates are preferred from the viewpoints of a good balance of coatability, surface tension and the like among the solvents described in International Publication No. 2008/153000 and the like, and relatively high solubility of the components in the composition.

The glycol alkyl ether acetates may be used alone or in combination with other solvents. Especially preferred as the solvent to be used are glycol monoalkyl ethers. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of the constituent components in the composition. Further, since the glycol monoalkyl ether has a high polarity, if the addition amount is excessively large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored photosensitive composition tends to increase with time, and therefore the glycol monoalkyl The ratio of ethers is preferably 5% by weight to 30% by weight, more preferably 5% by weight to 20% by weight.

It is also preferable to use an organic solvent having a boiling point of 150 ° C or higher (hereinafter sometimes referred to as a "high boiling point solvent") in combination. When such a high boiling point solvent is used in combination, the colored photosensitive composition is not dried well, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being broken by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among the various solvents described in the aforementioned International Publication No. 2008/153000, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate and diethylene glycol mono Ethyl ether acetate is preferred.

The content of the high boiling point solvent in the solvent is preferably 3 wt% to 50 wt%, more preferably 5 wt% to 40 wt%, and particularly preferably 5 wt% to 30 wt%. By setting the amount of the high boiling point solvent to the lower limit value or more, it is possible to prevent the occurrence of foreign matter defects due to precipitation and solidification of pigments or the like at the tip of the slit nozzle. By setting the amount to be the upper limit value or less, The drying speed of the composition can be appropriately maintained so as not to cause problems such as tack in the reduced pressure drying process and pin marks on the prebake in the process.

The high boiling point solvent having a boiling point of 150 캜 or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a high boiling point solvent having a boiling point of 150 캜 or more may not be separately contained.

As preferred high boiling point solvents, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate , 1,6-hexanoldiacetate, triacetin, and the like.

The content of the solvent in the entire colored photosensitive composition of the present invention is not particularly limited, but is usually 99% by weight or less, usually 50% by weight or more, preferably 55% by weight or more, and more preferably 60% by weight or more. By setting the ratio of the solvent to the upper limit value or less, it is possible to contain a sufficient amount of solids such as pigment, binder resin, photopolymerizable monomer and the like in the colored photosensitive composition. Further, by setting the content at or above the lower limit value, the thickening can be suppressed, and good coating properties and film thickness uniformity of the coating film can be obtained.

In view of the above circumstances, the colored photosensitive composition of the present invention is prepared by using a solvent so that the solid concentration thereof is usually 5 to 50% by weight, preferably 10 to 30% by weight.

[7] Other components

The colored photosensitive resin composition of the present invention may contain, in addition to the above components, a polymerization accelerator, a sensitizer, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, a plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, Acid anhydrides, development improvers, thermal polymerization inhibitors, and the like.

[7-1] Photo acid generator

The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and by the action of an acid generated upon exposure, a crosslinking agent such as a melamine compound is present, thereby causing the crosslinking reaction to proceed. Among these photoacid generators, those having a high solubility in a solvent, particularly, a solvent used in a colored photosensitive composition are preferred, and examples thereof include diphenyl iodonium, ditolyl iodonium, phenyl (p-anisyl) iodine Iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl ( diaryl iodonium such as p-tolyl) iodonium and p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium such as triphenylsulfonium chloride, bromide, or boronate, hexafluoro (Pentafluorophenyl) borate salts and the like, sulfonium organic boron complexes such as diphenylphenazylsulfonium (n-butyl) triphenylborate, and the like, Or 2-methyl-4,6-bistricloromethyltriazine, 2 - (4-methoxyphenyl) -4,6-bistricloromethyltriazine, and the like, but the present invention is not limited thereto.

These photoacid generators may be used singly or in combination of two or more.

When a photoacid generator is used, its content is preferably 0 to 20% by weight, particularly preferably 2 to 15% by weight based on the total solid content of the colored photosensitive composition.

[7-2] Crosslinking agent

In the colored photosensitive composition of the present invention, a crosslinking agent may be further added, and for example, a melamine or guanamine-based compound may be used. Examples of the crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (XI).

[Chemical Formula 19]

When 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 If R ⁶¹ is an aryl group, the remainder of R ^62, R ^63, R ⁶⁴ and one R ⁶⁵ represents a group _{^{-CH 2 OR 68, R 62,}} R 63, R 64, R 65, R 66 and R ⁶⁷ are each Independently represents a hydrogen atom or a -CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or an alkyl group.

Here, the aryl group is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and the phenyl group or the naphthyl group may have a substituent such as an alkyl group, an alkoxy group or a halogen atom. The alkyl group and the alkoxy group may each have 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is generally a methyl group or an ethyl group, particularly a methyl group.

Examples of the melamine compound corresponding to the formula (XI), that is, the compound represented by the formula (XI-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethyl Melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, and the like.

[Chemical Formula 20]

^Wherein one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a -CH ₂ OR ⁶⁸ group when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or an alkyl group.

Also, examples of the guanamine compound corresponding to the formula (XI), that is, the compound wherein R ⁶¹ in the formula (XI) is an aryl group include tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo Guanamine, tetraethoxymethylbenzoguanamine, and the like.

A crosslinking agent having a methylol group or a methylol alkyl ether group may also be used. Examples thereof are listed below.

(Hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl- -1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis (hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (also known as dimethyloluron) or a dimethyl ether thereof, tetramethylolglyoxaldiurene or tetramethyl ether thereof.

These crosslinking agents may be used alone or in combination of two or more.

When the crosslinking agent is used, the amount is preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content of the colored photosensitive composition.

[7-3] Adhesion improving agent

The colored photosensitive composition of the present invention may contain an adhesion improver to sufficiently adhere fine lines or dots.

As the adhesion improver, a compound containing a nitrogen atom, a compound containing a phosphoric acid group, a silane coupling agent and the like are preferable, and as a compound containing a nitrogen atom, for example, diamines (JP-A 11-184080 Adhesiveness enhancer, etc.) or azoles are preferable. Among them, azoles are preferable, and imidazoles (adhesion improvers described in Japanese Patent Application Laid-Open No. 9-236923, etc.), benzoimidazoles, benzotriazoles (in Japanese Unexamined Patent Application Publication No. 2000-171968 Enhancers, etc.) are preferable, and imidazoles and benzimidazoles are most preferable. Among these, from the viewpoint that blackening hardly occurs and adhesion can be greatly improved, it is preferable to use 2-hydroxybenzoimidazole, 2-hydroxyethylbenzoimidazole, benzoimidazole, 2-hydroxyimidazole, imidazole, 2 -Mercaptoimidazole and 2-aminoimidazole are preferable, and 2-hydroxybenzoimidazole, benzimidazole, 2-hydroxyimidazole and imidazole are particularly preferable. As the silane coupling agent, various epoxy compounds, methacrylic compounds, amino compounds and the like can be used, and particularly, epoxy compounds and isocyanate-based silane coupling agents are preferred.

These may be used singly or in combination of two or more.

When these adhesion improvers are compounded, the compounding ratio thereof is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the total solid content of the colored photosensitive composition, although it varies depending on the kind of the adhesion- . If the amount is less than this range, sufficient adhesion improving effect may not be obtained, and if it is excessively large, the developing property may be lowered.

[7-4] Increasing dye

As the sensitizing dye, for example, Japanese Patent Application Laid-Open Nos. 4-221958 and 4-219756, Japanese Laid-Open Patent Application No. 3-239703, Japanese Laid-Open Patent Application No. 5-289335 , 3-ketocumarin compounds described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, pyromethene compounds described in Japanese Patent Application Laid-Open No. 6-19240 Pigments, and in addition, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A- -112681, 58-15503, 60-88005, 59-56403, 59-26, 57, 57-56403, JP-A- -168088, JP-A-5-107761, JP-A-5-210240, Japan And a dye having a dialkylaminobenzene skeleton described in JP-A-4-288818.

These may be used singly or in combination of two or more.

When the sensitizing dye is compounded, the content of the sensitizing dye in the total solid content in the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If the amount is less than the above range, the effect of increasing or decreasing may not be exhibited, and if it is excessively large, the developability may be lowered.

[7-5] Surfactant

As the surfactant, one or more of various kinds such as anionic, cationic, nonionic, amphoteric surfactants and the like can be used. In view of low possibility of adversely affecting all properties, a nonionic surfactant is used . In addition, fluorine-based or silicone-based ones are effective in terms of application.

When a surfactant is used, the blending ratio thereof is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, most preferably 0.01 to 5% by weight based on the total solid content in the colored photosensitive composition Is in the range of 0.03 to 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 exhibited. In some cases, smoothness and uniformity of the coating film may not be exhibited, have.

[7-6] Organic carboxylic acid, organic carboxylic acid anhydride

The colored photosensitive composition of the present invention may contain at least one of an organic carboxylic acid and an organic carboxylic acid anhydride for the purpose of improving developability and improving contamination of the substrate.

Examples of the organic carboxylic acid include an aliphatic carboxylic acid and an aromatic carboxylic acid.

Specific examples of the aliphatic carboxylic acid include monoalcohols such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, But are not limited to, carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, , Dicarboxylic acids such as tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, tricarbalic acid, aconitic acid and camphoronic acid And tricarboxylic acid.

Specific examples of the aromatic carboxylic acid include aromatic carboxylic acids such as benzoic acid, toluic acid, cumic acid, hemellitic acid, mesitylene acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melomatic acid, pyromellitic acid , Carboxy-bonded carboxy groups such as phenylacetic acid, hydroacetic acid, hydro atropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropathic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, A carboxylic acid in which a carboxyl group is bonded through a carbon bond from a phenyl group, and the like.

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, usually 50 or more. If the molecular weight of the organic carboxylic acid is excessively large, the effect of improving the contamination of the substrate may be insufficient. If the molecular weight is too small, there is a possibility that the amount of the organic carboxylic acid to be added is decreased and the process contamination is caused by sublimation or volatilization.

Examples of the organic carboxylic anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples of the aliphatic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, anhydrous tetrahydro Phthalic acid, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, anhydroglutaric acid, 1,2-cyclohexene dicarboxylic acid anhydride, n-octadecylsuccinic acid anhydride, anhydrous 5-norbornene- , 3-dicarboxylic acid, and other aliphatic carboxylic acid anhydrides. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous naphthalic acid.

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 excessively large, the effect of improving the contamination of the substrate may be insufficient. If the molecular weight is too small, there is a possibility that the amount of the organic carboxylic acid anhydride is decreased or the process contamination is caused by sublimation or volatilization.

These organic carboxylic acids and organic carboxylic anhydrides may be used singly or in combination of two or more kinds.

When these organic carboxylic acids and organic carboxylic anhydrides are used, the addition amount thereof is usually 0.01% by weight to 5% by weight, preferably 0.03% by weight to 3% by weight, based on the total solid content of the colored photosensitive composition of the present invention % to be. If the addition amount is too small, a sufficient addition effect may not be obtained. On the other hand, if the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and an undissolved peeling strip may be generated.

[7-7] Thermal polymerization inhibitor

As the thermal polymerization inhibitor, for example, at least one of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, .

The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight based on the total solid content in the colored photosensitive composition, and if it is more than that, the sensitivity of the colored photosensitive composition may deteriorate in some cases.

[7-8] Plasticizers

Examples of the plasticizer include one or more selected from the group consisting of dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, Two or more species are used.

The blending ratio of these plasticizers is preferably in the range of 0 to 5% by weight based on the total solid content in the colored photosensitive composition, and if it is more than this, the curing point of the black photo-spacers is lowered.

[Method of preparing colored photosensitive composition]

The colored photosensitive composition of the present invention is prepared according to a conventional method. The method for preparing the colored photosensitive composition in the present invention is not limited to the method described below.

From the viewpoint of ensuring the dispersion stability of the pigment, the colored photosensitive composition of the present invention is preferably a preparation method of preparing a pigment dispersion in advance and mixing other components with the pigment dispersion as described below.

[1] Manufacturing method of pigment dispersion

A pigment, a solvent and a dispersant, and, if necessary, a dispersion aid are weighed in a predetermined amount, and the pigment is dispersed in the dispersion treatment step to obtain a liquid pigment dispersion. In this dispersion processing step, a paint conditioner (paint shaker), a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used. Since the pigment is converted into fine particles by carrying out the dispersion treatment, the colored photosensitive composition using the pigment dispersion thus prepared is improved in patterning characteristics such as coating properties, shape and linearity.

When dispersing is carried out using a sand grinder or a paint shaker, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to 8 mm. The temperature at the time of 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 dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition (pigment, solvent, dispersant, etc.) of the pigment dispersion and the size of the apparatus.

In this case, it is the standard of dispersion that the gloss of the pigment dispersion is controlled so that the 20-degree specular gloss in JIS Z8741 (1997) is in the range of 100 to 200. When the gloss of the pigment dispersion is low, the dispersion treatment is not sufficient and rough pigment particles often remain, which may be insufficient in terms of developability, adhesion, resolution and the like. In addition, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, and dispersion stability tends to be rather deteriorated.

When the pigment is subjected to the dispersion treatment, the above-mentioned binder resin or dispersion aid may be appropriately used in combination. By containing the binder resin, the dispersion stability at the time of producing the pigment dispersion can be improved.

In this case, the amount of the binder resin added is preferably 5 to 100% by weight, and more preferably 10 to 60% by weight based on the pigment in the pigment dispersion. By setting the addition amount of the binder resin to the above-mentioned lower limit value or more, it is possible to have higher dispersion stability and patterning characteristics, and by setting it below the upper limit value, a high pigment concentration can be ensured and a higher light shielding property can be obtained.

The solid content concentration of the pigment dispersion is usually 10 to 40% by weight.

Here, &quot; total solid content &quot; refers to the total components of the pigment dispersion other than the solvent.

[2] Method for producing colored photosensitive composition

The colored photosensitive composition of the present invention is prepared by adding other components contained in the colored photosensitive composition to the pigment dispersion obtained by the above process and mixing them to obtain a homogeneous solution. Further, in a dispersion treatment in a liquid in which all the components to be blended as a colored photosensitive composition are simultaneously mixed, highly reactive components may be denatured due to heat generated during dispersion. Further, in the production process, since fine dust is often mixed in the liquid, the resulting colored photosensitive composition solution is preferably subjected to filtration treatment with a filter or the like.

[Black Photo Spacer]

Although the colored photosensitive composition of the present invention is used for the same purpose as the known colored photosensitive composition for a color filter, a specific example of a method of forming a black photo spacer using the colored photosensitive composition of the present invention .

Usually, the colored photosensitive composition solution is supplied on a substrate on which a black photo spacer is to be formed, in a film or pattern form by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as photolithography in which exposure-development is performed. Thereafter, a black photo spacer is formed on the substrate by performing additional exposure or thermal curing if necessary.

[1] Method of supplying to substrate

The colored photosensitive composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. The supplying method can be carried out by a conventionally known method, for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, a spray coat method and the like. It may also be supplied in the form of a pattern by an injection method, a printing method or the like. Among them, the die coating method is preferable from the viewpoint of comprehensive view that the amount of the coating liquid to be used is greatly reduced, there is no influence of mist or the like adhering to the spin coating method, and the generation of foreign matter is suppressed.

The coating amount varies depending on the application. For example, in the case of a black photo spacer, the dry film thickness is usually in the range of 0.5 탆 to 10 탆, preferably 1 탆 to 9 탆, particularly preferably 1 탆 to 7 탆 to be. It is also important that the dry film thickness or the height of the finally formed spacer is uniform over the entire substrate. When the deviation is large, uneven defects are caused in the liquid crystal panel.

However, when the black photosensitive spacers having different heights are collectively formed by the photolithography method of the colored photosensitive composition of the present invention, the height of the finally formed black photo spacers is different.

As the substrate, a known substrate such as a glass substrate can be used. The substrate surface is preferably flat.

[2] Drying method

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. It is also possible to combine the vacuum drying method in which the drying is performed in the decompression chamber without raising the temperature.

The drying conditions can be appropriately selected depending on the kind of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 40 to 130 占 폚 for 15 seconds to 5 minutes, preferably 50 to 110 占 폚, depending on the kind of the solvent component, the performance of the dryer to be used, 30 seconds to 3 minutes.

[3] Exposure method

Exposure is performed by overlapping a negative mask pattern on a coating film of the colored photosensitive composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In the case of performing exposure using an exposure mask, there are a method of bringing the exposure mask close to the coating film of the colored photosensitive composition, a method of disposing the exposure mask at a position away from the coating film of the colored photosensitive composition, Or by a method of projecting light. Alternatively, a scanning exposure method using a laser beam not using a mask pattern may be used. At this time, in order to prevent deterioration of the sensitivity of the photopolymerizable layer due to oxygen, if necessary, it may be carried out in a deoxygenated atmosphere, or an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer, .

In a preferred embodiment of the present invention, when the black photo spacers having different heights are simultaneously formed by photolithography, for example, as described above, the light shielding portion (light transmittance: 0%) and the average light transmittance An exposure mask having an opening portion (intermediate transmission opening portion) having a small average light transmittance with respect to the highest opening portion (full permeation opening portion) is used. This method causes a difference in the residual film ratio depending on the difference in the average light transmittance (generally, 5% to 40%) of the intermediate transmission opening portion and the full transmission opening portion, that is, the difference in exposure amount.

It is known that the intermediate transmission opening is manufactured by, for example, a matrix-type shielding pattern having a light-shielding unit with a small polygon. Also known is a method of manufacturing an absorber by controlling the light transmittance by a film of a material such as chromium, molybdenum, tungsten, or silicon.

The light source used for the above exposure is not particularly limited. Examples of the light source include a lamp light source such as 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 laser light source such as an excimer laser, a nitrogen laser, a helium cardium laser, a blue violet semiconductor laser, and a near infrared semiconductor laser. An optical filter may be used when irradiating light of a specific wavelength.

The optical filter may be, for example, a thin film and a type capable of controlling the light transmittance at an exposure wavelength. In this case, for example, a Cr compound (oxide, nitride, oxynitride, MoSi, Si, W, and Al.

The exposure dose is usually 1 mJ / cm2 or more, preferably 5 mJ / cm2 or more, more preferably 10 mJ / cm2 or more, usually 300 mJ / cm2 or less, preferably 200 mJ / Lt; 2 &gt; / cm &lt; 2 &gt;

In the proximity exposure method, the distance between the object to be exposed and the mask pattern is usually 10 占 퐉 or more, preferably 50 占 퐉 or more, more preferably 75 占 퐉 or more, usually 500 占 퐉 or less, preferably 400 占 퐉 or less , More preferably not more than 300 mu m.

[4] Development method

After the above-described 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 buffer, a complexing agent, a dye or a pigment.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, Mono-di- or triethanolamine, mono- or di- or trimethylamine, mono- or di- or triethylamine, mono- or di- or tri-alkylamine, or an inorganic or organic compound such as sodium dihydrogenphosphate, potassium dihydrogenphosphate or ammonium hydroxide, And organic alkaline compounds such as diisopropylamine, n-butylamine, mono- di- or triisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline and the like. 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 and monoglyceride alkyl esters; Anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid salts, alkylsulfonic acid salts and sulfosuccinic acid ester salts; and amphoteric surfactants such as alkyl betaines 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 may be used alone or in combination with an aqueous solution.

The method of development processing is not particularly limited, but is usually carried out at a developing temperature of 10 to 50 캜, preferably 15 to 45 캜, by a method such as immersion, spraying, brushing, or ultrasonic development .

[5] Additional exposure and heat curing treatment

The substrate after development may be subjected to additional exposure by the same method as the above-described exposure method, if necessary, or may be subjected to heat curing treatment. The heat curing treatment condition at this time is selected in the range of 100 占 폚 to 280 占 폚, preferably 150 占 폚 to 250 占 폚, and the time is selected in the range of 5 minutes to 60 minutes.

The size, shape and the like of the black photo spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which the black photo spacer is applied. However, the colored photosensitive composition of the present invention is particularly suitable for use in a black photopattern having a height of a spacer and a sub- In this case, the height of the spacers is usually 2 to 7 占 퐉, and the sub-spacers have a height which is usually lower than the spacers by 0.2 to 1.5 占 퐉.

[Color Filter]

The color filter of the present invention comprises the above-described black photo spacer of the present invention. For example, a black matrix and red, green and blue pixel coloring layers and an overcoat layer are formed on a glass substrate as a transparent substrate A black photo-spacer is formed, and then an alignment film is formed.

The liquid crystal display device can be manufactured by forming a liquid crystal cell by bonding the color filter of the present invention having the black photo spacer of the present invention and the liquid crystal driving side substrate and injecting liquid crystal into the formed liquid crystal cell.

Example

Next, the present embodiment will be described in more detail with reference to Examples and Comparative Examples, but the present embodiment is not limited to the following Examples unless it exceeds the gist of the present invention. In the following, &quot; part &quot; represents &quot; part by weight &quot;.

The components of the colored photosensitive composition used in the following Examples and Comparative Examples are as follows.

&Lt; Binder Resin-1 &

ZCR-1569H "(MW = 3000-4000, acid value = about 100 mg-KOH / g) manufactured by Nippon Kayaku Co.,

This binder resin-1 corresponds to &quot; alkali-soluble resin (A) &quot; in the present invention.

&Lt; Binder Resin-2 &

"ZCR-1642H" (MW = 5000 to 6500, acid value = about 100 mg-KOH / g) manufactured by Nippon Kayaku Co.,

This binder resin-2 corresponds to &quot; alkali-soluble resin (A) &quot; in the present invention.

&Lt; Binder Resin-3 &

A resin (MW = 3500 to 4500, acid value = about 110 mg-1) obtained by reacting a reaction product of an epoxy compound and acrylic acid of the following structure (11) with trimethylolpropane (TMP) and biphenyltetracarboxylic acid dianhydride KOH / g)

[Chemical Formula 21]

The binder resin-3 can be synthesized according to the following method.

&Lt; Synthesis Example 1: Synthesis of Binder Resin-3 &

50 g of the epoxy compound (epoxy equivalent 264) of the above structure (11), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine and 0.032 g of paramethoxyphenol were charged into a flask equipped with a thermometer, And the mixture is reacted at 90 캜 with stirring until the acid value becomes 5 mgKOH / g or less. The reaction requires 12 hours and an epoxy acrylate solution is obtained.

25 parts by weight of the above epoxy acrylate solution, 0.74 part by weight of trimethylol propane (TMP), 3.95 parts by weight of biphenyltetracarboxylic acid dianhydride (BPDA) and 2.7 parts by weight of tetrahydrophthalic anhydride (THPA) And the mixture was slowly heated to 105 DEG C while stirring to react.

When the resin solution became transparent, it was diluted with methoxybutyl acetate and adjusted to have a solid content of 50% by weight to obtain a binder resin-3.

This binder resin-3 corresponds to &quot; alkali-soluble resin (A1 &quot;) &quot; in the present invention.

<Dispersant>

&Quot; DisperBYK-2000 &quot;

<Dispersion aid>

&Quot; S12000 &quot;

<Surfactant>

Megapox F-475 &quot; manufactured by Dainippon Ink and Chemicals, Inc.

<Solvent-1>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-2>

MB: 3-methoxybutanol

&Lt; Photopolymerization initiator &gt;

The following compounds.

[Chemical Formula 22]

&Lt; Photopolymerizable monomer >

DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

<Pigment dispersion - Preparation of 1 to 10>

The pigments, dispersants, dispersion aids, binder resins and solvents described in Table 1 were mixed at the weight ratios shown in Table 1. Then, zirconia beads (average particle size: 0.3 mm) of 80% of the volume of the dispersion vessel were mixed, filled in a picomill dispersion vessel and dispersed at the required retention time (RT) shown in Table 1, Lt; / RTI &gt;

[Examples 1 to 5, Comparative Examples 1 to 6]

The thus prepared pigment dispersion and other components shown in Table 2 were compounded in the ratios shown in Table 2 and stirred to prepare a colored photosensitive composition.

Using this colored photosensitive composition, each evaluation was carried out as follows, and the results are shown in Table 2.

[Evaluation of step (? H), adhesion, optical density (OD)] [

&Lt; Method for collectively forming cured products having different heights >

Each colored photosensitive composition was applied on a glass substrate ("AN100" manufactured by AGC Corporation) using a spinner. Subsequently, the coating film was formed by heating and drying at 110 DEG C for 70 seconds on a hot plate.

The obtained coating film was subjected to exposure treatment using an exposure mask having a semi-permeable opening portion of a circular pattern of various diameters of 5 to 50 mu m in diameter and an intermediate transmission opening portion of a circular pattern of various diameters of 5 to 50 mu m in diameter, Respectively. The intermediate transmission opening is a thin film of Cr oxide and has a light transmittance of 10 2% at a wavelength of 365 nm. The exposure gap (distance between the mask and the coated surface) was 250 占 퐉. Ultraviolet rays having a wavelength of 365 nm at a wavelength of 32 mW / cm 2 were used as the light irradiation path, and the exposure amount was set at 6 levels of 40 to 90 mJ / cm 2. The ultraviolet irradiation was performed under air.

Subsequently, a developer comprising an aqueous solution containing 0.05% by weight of potassium hydroxide and 0.08% by weight of a nonionic surfactant (&quot; A-60 &quot;, produced by Kao Corporation) was used and a shower phenomenon at a water pressure of 0.15 MPa , Development was stopped with pure water, and the resultant was washed with a water spray. The shower developing time was adjusted within a range of 10 to 120 seconds, and was set to 1.5 times the time during which the uncoated coating film was dissolved and removed.

By these operations, a pattern in which unnecessary portions were removed was obtained. The substrate on which the pattern was formed was heated in an oven at 230 DEG C for 20 minutes to cure the pattern to obtain a roughly cylindrical spacer pattern.

&Lt; Evaluation of step difference &

(Step difference DELTA H) between the completely transparent openings of the circular pattern having a diameter of 15 mu m and the height of the intermediate transmission openings of the circular pattern having a diameter of 35 mu m were calculated and the maximum value at an exposure amount of 40 to 90 mJ / Together, the value of? H was evaluated based on the following criteria.

(Evaluation Criteria of Step Difference? H)

0.5 μm or more: ○

0.3 占 퐉 or more and less than 0.5 占 퐉:?

Less than 0.3 탆: x

&Lt; Evaluation of substrate adhesion &

The minimum aperture diameter (占 퐉) in which the pattern is well-resolved in the full-penetration opening portion of the circular pattern of 5 to 50 占 퐉 and the intermediate transmission opening portion of 5 to 50 占 퐉 in the exposure amount at which the height difference? ) Are shown in Table 2 as minimum adhesion. The smaller this value is, the better the substrate adhesion is. In addition, good resolution remained means that 24 patterns of the same size are formed and all the patterns are formed normally.

&Lt; Evaluation of optical density (OD) >

The optical density (OD) of the printed portion was measured with a transmission densitometer ("D200-II" manufactured by GretagMarkbeth). The film thickness of the measurement point was also measured, and the optical density per unit film thickness (unit OD) was calculated and evaluated according to the following criteria. Also, the OD value is a numerical value indicating the light shielding ability, and the larger the numerical value is, the higher the light intensity is.

(Evaluation standard of unit OD)

0.8 or higher: Yes

Less than 0.8: x

[Evaluation of voltage holding ratio (VHR)] [

&Lt; Production of liquid crystal cell &

An electrode substrate A (glass ITO beta for evaluation and manufacture of EHC) on which an ITO film was formed on the whole surface of 5 cm in width and 5 cm and a central portion of one side of a copper glass substrate of 2.5 cm in length and 2.5 cm in width, And an electrode substrate B (glass SZ-B111MIN (B) for evaluation and manufacture of EHC) on which an ITO film of 1 cm in length and length connected thereto was formed.

Each colored photosensitive composition was coated on the electrode substrate A, vacuum-dried for 1 minute, and then prebaked on a hot plate at 90 DEG C for 1.5 minutes to obtain a coated film having a dried film thickness of 2.0 mu m. Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed under an exposure condition of 50 mJ / cm 2 using a 3 kW high-pressure mercury lamp, respectively. Subsequently, using a developer comprising an aqueous solution containing about 0.06% by weight of potassium hydroxide and about 0.14% by weight of a nonionic surfactant ("A-60" manufactured by Kao Corporation) After performing the shower phenomenon, development was stopped with pure water and rinsed with a water spray. The shower developing time was adjusted to be about 10 to 120 seconds, and was set to about 1.5 times of the time (break time) during which the non-photosensitive layer was dissolved and removed.

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

On the other hand, a polyimide solution was coated on the electrode substrate B, pre-baked on a hot plate at 70 占 폚 for 2 minutes, and post-baked at 220 占 폚 for 24 minutes to complete an electrode substrate for evaluation B.

Thereafter, an epoxy resin sealant containing silica beads having a diameter of 5 占 퐉 was applied to the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A was placed on the surface (sealing side) of the electrode substrate B, The applied surface was squeezed, and the empty cell was completed. And heated at 180 캜 for 2 hours in a hot air circulation furnace.

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

&Lt; Evaluation of voltage holding ratio (VHR) >

The liquid crystal cell was subjected to annealing (heating at 105 DEG C for 2.5 hours in a hot air circulation furnace) and then applied to the evaluation electrode substrates A and B under the conditions of a voltage of 5 V, 0.6 Hz and a frame time of 1667 msec. (Model VHR-6254, manufactured by Toyo Technica Co., Ltd.).

The results of Table 2 show that the colored photosensitive composition of the present invention containing Or64 and B60 as essential components as pigments and the colored photosensitive composition of the present invention containing Or72 and B60 as essential components are excellent in light blocking property, And the cured products having different heights are formed at the same time using the same material.

While the invention has been described in detail and with reference to specific embodiments thereof, it is evident 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 Japanese patent application (patent application No. 2012-018337) filed on January 31, 2012, the content of which is incorporated herein by reference.

Claims (8)

1. A colored photosensitive composition comprising a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the pigment contains the pigment shown in (A) and the pigment shown in (B).
(A) one selected from the group consisting of CI Pigment Orange 43, CI Pigment Orange 64 and CI Pigment Orange 72
(B) CI Pigment Blue 60 The method according to claim 1,
Wherein the pigment contains CI Pigment Orange 64 and CI Pigment Blue 60. The method according to claim 1,
Wherein the pigment further contains one selected from the group consisting of CI Pigment Red 254, CI Pigment Violet 23 and CI Pigment Violet 29. The method according to claim 1,
Wherein the pigment contains the pigment shown in the following (1) or the pigment shown in (2).
(1) CI Pigment Orange 64, CI Pigment Blue 60 and CI Pigment Red 254
(2) CI Pigment Orange 64, CI Pigment Blue 60 and CI Pigment Violet 29 The colored photosensitive composition according to any one of claims 1 to 4, which is used for forming a black photo spacer. A black photo-spacer formed by using the colored photosensitive composition according to any one of claims 1 to 4. A color filter comprising the black photo spacer according to claim 6. A liquid crystal display device having the black photo spacer according to claim 6.