WO2013115268A1

WO2013115268A1 - Colored photosensitive composition, black photo spacer, and color filter

Info

Publication number: WO2013115268A1
Application number: PCT/JP2013/052082
Authority: WO
Inventors: 訓志岩田; 良尚沢井; 麗華裴
Original assignee: 三菱化学株式会社
Priority date: 2012-01-31
Filing date: 2013-01-30
Publication date: 2013-08-08
Also published as: KR20190058671A; CN110244513A; KR101985564B1; TW201337460A; JP6409936B2; JPWO2013115268A1; CN104081280B; JP6229210B2; JP6036708B2; KR102078989B1; CN104081280A; KR20140121824A; TWI585529B; JP2017033023A; CN110244513B; JP2018009194A

Abstract

A colored photosensitive composition containing a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, wherein the pigment contains the following: (A) one pigment selected from the group consisting of C.I. pigment orange 43, C.I. pigment orange 64, and C.I. pigment orange 72; and (B) C.I. 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 in a color filter such as a liquid crystal display, a black photo spacer formed using the colored photosensitive composition, and a color including the black photo spacer Regarding filters.

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

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

Conventionally, when a spacer that does not have a light shielding property is used in a TFT type LCD, a TFT as a switching element sometimes malfunctions due to light transmitted through the spacer. In order to prevent this, for example, Patent Document 1 describes that a spacer is made light-shielding.
However, in order to make the spacer shielding property, it is conceivable to add a coloring agent including ordinary pigment in the photosensitive composition, curable spacer layer by a decrease in the clear component as the addition of a colorant There is a risk that the properties are impaired due to the effect of impurities and impurities derived from the pigment.

In order to control the voltage holding ratio, a technique for improving curability, a technique for controlling a curable resin, a dispersant, and the like of the photosensitive composition have been proposed.

On the other hand, in recent years, when a spacer is manufactured by a photolithography method, a method has been proposed in which spacers having different heights are collectively formed as the structure of the panel changes. Patent Document 2 discloses that spacer shapes and steps having different desired heights can be realized by controlling the exposure amount and the remaining film ratio.

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

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

The present invention has been made in view of such circumstances. That is, a main object of the present invention is a method of collectively forming different black photospacer height by photolithography, after securing the light shielding property and a voltage holding ratio of the liquid crystal, can control the shape or steps, An object of the present invention is to provide a colored photosensitive composition capable of forming a black photospacer excellent in adhesion to a substrate.
Another object of the present invention is to provide a black photospacer formed from such a colored photosensitive composition.
Still 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 that the above problems can be solved by using a specific pigment as a colorant, and have completed the present invention. That is, the gist of the present invention is as follows.

[1] A colored photosensitive composition containing a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, wherein the pigment contains a pigment shown in (A) below and a pigment shown in (B) Photosensitive composition.
(A) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. One selected from the group consisting of CI Pigment Orange 72 (B) C.I. I. Pigment Blue 60
[2] The pigment is C.I. I. Pigment orange 64 and C.I. I. The colored photosensitive composition according to the above [1], comprising CI Pigment Blue 60.
[3] The pigment is C.I. I. Pigment red 254, C.I. I. Pigment violet 23, and C.I. I. The colored photosensitive composition according to the above [1] or [2], further comprising one selected from the group consisting of CI Pigment Violet 29.
[4] The colored photosensitive composition according to [1], wherein the pigment includes the pigment shown in (1) below or the pigment shown in (2).
(1) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, and C.I. I. Pigment Red 254
(2) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, and C.I. I. Pigment Violet 29
[5] A black photospacer formed 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 the method of collectively forming black photo spacers having different heights by photolithography, pigment types having different light absorption characteristics are appropriately combined to ensure a balance between light absorption in the ultraviolet region and visible region. Thus, while maintaining the light shielding property and the voltage holding ratio of the liquid crystal, it is possible to control the shape and the level difference and realize high adhesion with the substrate.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the contents of.

In the present specification, “(meth) acryl” and the like mean “at least one of acryl and methacryl”, and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. Etc., and “(meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”. The same applies to “(meth) acryloyl”. In addition, “(acid) anhydride” and “(anhydrous)... Acid” mean that both an acid and its anhydride are included.
Further, “total solid content” means all components other than the solvent components described later, which are contained in the colored photosensitive composition or the pigment dispersion.

Moreover, in this invention, unless there is particular notice, a weight average molecular weight refers to the weight average molecular weight (Mw) of standard polystyrene conversion by GPC (gel permeation chromatography). “C.I.” means a color index (c.I.).
Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

In the present invention, the term “monomer” means a so-called high-molecular substance and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense.

The colored photosensitive composition of the present invention includes a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, and includes the following (A) and (B) as the pigment: In particular, it is preferably used as a colored photosensitive composition for collectively forming black photo spacers having different heights by photolithography.
(A) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. One selected from the group consisting of CI Pigment Orange 72 (B) C.I. I. Pigment Blue 60

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

As an exposure mask, the exposure mask has a light shielding layer that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings. A method of using is known. This has a light shielding layer (light transmittance of 0%) and a plurality of openings, and has the highest average light transmittance (usually light transmittance of 100%, hereinafter referred to as “completely transmissive opening”). And using an exposure mask having an opening having a small average light transmittance (average light transmittance exceeding 0% and less than 100%, preferably exceeding 5% and less than 50%, hereinafter referred to as “intermediate transmission opening”). is there. With this method, for example, in the case of a negative type colored photosensitive composition, the degree of cure of the formed pattern depends on the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. Differences can be made, and then black photo spacers of different heights can be formed through development and thermosetting processes.

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

[1] Pigment The pigment refers to one that colors 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. As its structure, organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, perylene, and various inorganic pigments can be used. is there.

The colored photosensitive composition of the present invention contains the following (A) and (B) as essential components as pigments.
(A) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. One selected from the group consisting of CI Pigment Orange 72 (B) C.I. I. Pigment Blue 60
In the colored photosensitive composition of the present invention, the pigment to be used is not particularly limited, except that it contains the above-mentioned (A) and (B) as essential components, and it depends on the mixing of each color such as red, green, and blue. A black color material can be used. Furthermore, black pigments, other inorganic or organic pigments, and dyes can be appropriately selected and used in combination.

Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

As red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 179, 209, 224, 254. Among them, C.I. I. And CI Pigment Red 254 (R254).

As blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. And CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, and 15: 6.

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

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

】 As orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. Pigment orange 38, 43, 64, 71, 72. More preferably, C.I. I. Pigment orange 43, 64, 72. More preferably, C.I. I. CI pigment orange 64 (Or64).

As purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, 29, more preferably C.I. I. Pigment violet 23, 29, more preferably C.I. I. And CI Pigment Violet 29 (V29).

Examples of black pigments include perylene black (BA0084, K0084, K0086), cyanine black, first black HB (CI. 26150), Irgaphor Black S 0100 CF (BASF), carbon black, and titanium black. it can.

Examples of commercially available carbon black include the following brands.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 , # 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
Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Cabot Corporation: Monarch120, Monarch280, 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
Koronbiyan Carbon Co., Ltd.: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN760, RAVEN780RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1060U, RAVEN1080U, RAVEN1100URAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U , RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750 , RAVEN 7000

Examples of commercially available titanium black include the following brands.
Mitsubishi Materials Corporation: 10S, 12S, 13R, 13M, 13M-C, 14M, 15M, L-15M, etc. Akaho Kasei Co., Ltd .: TilacD M, M-50, M-50A, M-AM, V, UV-3 , UV-6, F, S, C, X, etc.

The colored photosensitive composition of the present invention includes C.I. as a pigment from the viewpoint of light shielding properties, voltage holding ratio of liquid crystal, control of shape and level difference, and adhesion to a substrate. I. Pigment orange 64 and C.I. I. Pigment Blue 60 is preferably included.
In addition to the above (A) and (B), the colored photosensitive composition of the present invention may further contain C.I. I. Pigment red 254, C.I. I. Pigment violet 23, and C.I. I. It is preferable to include one selected from the group consisting of CI Pigment Violet 29.
The colored photosensitive composition of the present invention has, as a pigment, the following (1) to (1) to the following to improve the light shielding property, the voltage holding ratio of liquid crystal, the control of shape and level difference, and the adhesion to the substrate. It is preferable to include the three types of pigments shown in any one of (3), and in particular, from the viewpoint of the voltage holding ratio of the liquid crystal, it is preferable to include the three types of pigments shown in (1) or (2).
(1) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, C.I. I. Pigment Red 254
(2) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, C.I. I. Pigment Violet 29
(3) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, C.I. I. Pigment Violet 23

The proportion of the pigment in the colored photosensitive composition of the present invention is usually 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 20 to 42% by weight, based on the total solid content. If there is more pigment than this range, the spacer shape and level difference, adhesion to the substrate may deteriorate, or the curable component may decrease and the pigment etc. may elute into the liquid crystal layer may cause a decrease in voltage holding ratio. is there. On the other hand, if it is less than this range, sufficient light shielding properties as a black photo spacer may not be ensured.

In addition, the ratio of (A) and (B) in the pigment may be either too much or too little, and the light shielding property and voltage holding ratio, shape, and level difference of the liquid crystal according to the present invention by using these in combination. Control and the effect of improving the adhesion to the substrate may not be sufficiently obtained, so that (A) is 25 to 70 wt% with respect to 100 wt% of (A) and (B) in total. %, Particularly 30 to 60% by weight, especially 35 to 60% by weight.
That is, in (A), the absorption of light in the vicinity of wavelengths from 330 nm to 380 nm is relatively small, and the absorption of light in the vicinity of wavelengths from 400 nm to 550 nm is large. On the other hand, in (B), the absorption of light in the vicinity of wavelengths from 330 nm to 380 nm is similarly small, and the absorption of light in the vicinity of wavelengths from 550 nm to 700 nm is large. Therefore, by using these two types of pigments in a well-balanced combination, the light absorption balance in the ultraviolet region and the visible region is improved, the light shielding property, the voltage holding ratio of the liquid crystal, the shape and step control, and the substrate. Adhesion can be improved.

In addition, the pigment used in the present invention may contain various pigments other than (A) and (B). However, in order to sufficiently obtain the above-described effect by the combined use of (A) and (B). The total proportion of (A) and (B) in the total 100% by weight of the pigments contained in the colored photosensitive composition of the present invention is 50% by weight or more, particularly 60 to 95% by weight, especially 70 to 90%. It is preferable that it is weight%.

Also, in the combination of pigments used in the present invention, (A) and (B) and further C.I. I. By using CI Pigment Red 254 (R254), absorption in the visible region can be increased while suppressing light absorption in the ultraviolet region, and the light shielding property, voltage holding ratio of liquid crystal, control of shape and level difference, and adhesion to the substrate The effect that the property can be enhanced is exhibited. In this case, in a total of 100% by weight of (A), (B) and R254, (A) is 20 to 40% by weight, (B) is 45 to 65% by weight, R254 is 5 to 25% by weight, In particular, it is preferable to use (A) in a proportion of 25 to 35% by weight, (B) in a proportion of 50 to 60% by weight, and R254 in a proportion of 10 to 20% by weight. Although pigments other than (A), (B) and R254 may be used, the total ratio of (A), (B) and R254 in all pigments in the colored photosensitive composition is 70% by weight or more, In particular, it is preferably used so as to be 90 to 100% by weight.

Also, in the combination of pigments used in the present invention, (A) and (B) and further C.I. I. By using Pigment Violet 23 (V23), the absorption in the visible region can be further increased while suppressing the absorption of light in the ultraviolet region, the light shielding property, the voltage holding ratio of the liquid crystal, the control of the shape and step, and the substrate The effect that the adhesiveness of can be improved is produced. In this case, in a total of 100% by weight of (A), (B) and V23, (A) is 30 to 50% by weight, (B) is 30 to 50% by weight, V23 is 10 to 30% by weight, In particular, it is preferable to use (A) in a proportion of 35 to 45% by weight, (B) in a proportion of 35 to 45% by weight, and V23 in a proportion of 15 to 25% by weight. Although pigments other than (A), (B), and V23 may be used, the total ratio of (A), (B), and V23 in all pigments in the colored photosensitive composition is 70% by weight or more. In particular, it is preferably used in an amount of 90 to 100% by weight.

Also, in the combination of pigments used in the present invention, (A) and (B) and further C.I. I. By using Pigment Violet 29 (V29), the absorption in the visible region can be further increased while suppressing the light absorption in the ultraviolet region, and the light shielding property, the voltage holding ratio of the liquid crystal, the control of the shape and level difference, and the substrate The effect that the adhesiveness of can be improved is produced. In this case, in a total of 100% by weight of (A), (B) and V29, (A) is 30 to 50% by weight, (B) is 30 to 50% by weight, V29 is 10 to 30% by weight, In particular, it is preferable to use (A) in a proportion of 35 to 45% by weight, (B) in a proportion of 35 to 45% by weight, and V29 in a proportion of 15 to 25% by weight. Although pigments other than these (A), (B), and V29 may be used, the total ratio of (A), (B), and V29 in all pigments in the colored photosensitive composition is 70% by weight or more. In particular, it is preferably used in an amount of 90 to 100% by weight.

The pigments used in the present invention are (A) and (B), and C.I. I. Pigment Red 272 (R272) is preferably included. Since R272 has a large absorption in the visible region, it is advantageous for high OD. *

[2] The binder resin used in the colored photosensitive composition of the binder resin present invention, if the resin member used for the color filter can be used without particular limitations, epoxy acrylate examples based resin, novolac resin , Polyvinyl phenol resin, acrylic resin, carboxyl group-containing epoxy resin, carboxyl group-containing urethane resin, etc., from the viewpoint of shape and step control, adhesion to the substrate, epoxy acrylate resin having a carboxyl group, It is preferable to use an acrylic resin, and it is more preferable to use an epoxy acrylate resin having a carboxyl group.

The above-mentioned epoxy acrylate resin means that an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin (or epoxy compound), and further a polybasic It is synthesized by reacting an acid or its anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin (or epoxy compound) is a raw material, and “acrylate” is representative. Since it is an example, it is named in this way according to common usage.

The raw material epoxy resin includes (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, or Examples thereof include epoxy resins (or epoxy compounds) represented by the general formulas (1-a) to (1-a ′ ″) described.

The particularly preferable binder resin in the present invention will be described below.

<Alkali-soluble resin (A ″), alkali-soluble resin (A1 ″)>
One particularly preferable binder resin in the present invention is 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 at least one of a polybasic acid and its anhydride (c ″).

[In the general formula (1-a ″), X represents a linking group represented by the following general formula (2a), (2b) or (3). However, one or more adamantane structures are included in the molecular structure. l represents an integer of 2 or 3.

(In the above general formulas (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently have an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. And an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group.
In the general formula (3), R ⁵ to R ¹² may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a substituent. Represents a phenyl group; Y represents a divalent linking group containing an adamantane structure, which may have a substituent.
In the above general formulas (2a), (2b) and (3), * represents a bonding site with the glycidyloxy group in the general formula (1-a ″). )]

(1) Epoxy compound (a ″) represented by general formula (1-a ″)
First, the group X in the epoxy compound (a ″) represented by the general formula (1-a ″) (hereinafter sometimes referred to as “component (a ″)”) will be described.

When the group X has a structure represented by the general formula (2a) or (2b), it is preferable that the general formulas (2a) and (2b) each have an adamantane structure of 2 or more and 4 or less. When the adamantane structure is 1, the developer resistance tends to decrease and the resolution tends to be inferior.

When the group X is a structure represented by the general formula (3), Y in the general formula (3) is “a divalent linking group including an adamantyl structure which may have a substituent”. If it is, there is no restriction | limiting in particular other than that, For example, it is preferable that it is a coupling group represented by the following general formula (4) or (5).

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

In particular, the epoxy compound (a ″) represented by the general formula (1-a ″) is preferably represented by the following general formula (6) or (7).

[The adamantane ring represented by the general formula (6) and the adamantyl group represented by (7) may have a substituent.
In the general formula (6), R ¹⁶ to R ²³ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. Indicates a group.
In the general formula (7), R ²⁴ and R ²⁵ are each independently an adamantyl group which may have a substituent, a hydrogen atom, or 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 formulas (2a), (2b), (3), (6) and (7), the alkyl group having 1 to 12 carbon atoms of R ¹ to R ²⁵ is preferably an alkyl group having 1 to 10 carbon atoms. Is mentioned.
Examples of the substituent that 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, an amino group, a nitro group, etc. are mentioned.

In addition, examples of the substituent that the phenyl group of R ¹ to R ^{25 in} the general formulas (2a), (2b), (3), (6), and (7) may have include a halogen atom, a hydroxyl group, Examples thereof include 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, an amino group, and a nitro group.

Further, 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 in the general formula (6), The adamantyl group in the general formula (7), the adamantyl group of R ²⁴ and R ²⁵ in the general formula (7), and the adamantane ring in the general formulas (4) and (5) may have a halogen Examples thereof include an 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, an amino group, and a nitro group.

In the general formula (6), R ¹⁶ to R ²³ are particularly 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 particularly 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 secured, and when it is 1000 or less, good sensitivity can be secured.

The epoxy equivalent of the epoxy compound (a ″) represented by the general formula (1-a ″) is preferably 210 or more, and 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, and when it is 450 or less, good sensitivity of the organic binder to be produced can be secured. .

As the epoxy compound (a ″), one type may be used alone, or two or more types may be used in combination.

As the epoxy compound (a ″), a commercially available product may be used, or it may be synthesized from a phenol compound as described below by a known method.

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

For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance to a dissolved mixture of the compound represented by the general formula (9a) or (9b) and an excess of epihalohydrin such as epichlorohydrin or epibromhydrin. By adding or reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours, X in the general formula (1-a ″) is represented by the general formula (2a) or (2b). An epoxy compound (a ″) as a group can be obtained.

In addition, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance or added to a dissolved mixture of the compound represented by the general formula (10) and an epihalohydrin such as excess epichlorohydrin or epibromohydrin. The epoxy compound (a ″) in which X in the general formula (1-a ″) is represented by the general formula (3) is obtained by reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours. Can do.

In the reaction for obtaining the epoxy compound (a ″), an aqueous solution thereof may be used as an alkali metal hydroxide. In that case, the 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 normal pressure. Epihalohydrin may be continuously returned to the reaction system.

Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is catalyzed to a dissolved mixture of the compound represented by the general formula (9a), (9b) or (10) and epihalohydrin. To the halohydrin etherified product of the compound represented by the general formula (9a), (9b), or (10) obtained by reacting at 50 to 150 ° C. for 1 to 5 hours. The epoxy compound represented by the general formula (1-a ″) can also be obtained by adding a solid or aqueous solution of the product and reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure). a ″) can be produced.

The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by formula (9a), (9b), or (10). It is. The amount of the alkali metal hydroxide used is usually 0.8 to 15 mol, preferably 0.9 to 0.1 mol per 1 equivalent of the hydroxyl group of the compound represented by the general formula (9a), (9b), or (10). 11 moles.

In the above reaction, in addition to the alcohols such as methanol and ethanol, an aprotic polar solvent such as dimethyl sulfone and dimethyl sulfoxide may be added to carry out the reaction smoothly. When alcohols are used, the amount used 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, the amount used is 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of epihalohydrin.

(2) Unsaturated group-containing carboxylic acid (b ″)
Examples of the unsaturated group-containing carboxylic acid (b ″) (hereinafter sometimes referred to as “(b ″) component”) include unsaturated carboxylic acids having an ethylenically unsaturated group. , (Meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, α-position is haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group monocarboxylic acids such as substituted (meth) acrylic acid in; 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalate 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2 (Meth) acryloyloxy propyl adipate, 2- (meth) acryloyloxy propyl tetrahydrophthalic acid, 2- (meth) acryloyloxy propyl phthalate, 2- (meth) acryloyloxy propyl maleate, 2- ( meth) acryloyloxy butyl acid, 2- (meth) acryloyloxyethyl butyl adipate, 2- (meth) acryloyloxy butyl phthalate, 2- (meth) acryloyloxy-butyl phthalate, 2- (meth ) (Meth) acryloyloxyalkyl esters of dibasic acids such as acryloyloxybutylmaleic acid; (meth) acrylic acid and lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone Monomers added with aldehydes; (meth) acrylic acid dimer, etc. The
Also, anhydrous hydroxyl-containing unsaturated compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, glycidyl methacrylate acrylic acid adduct, and glycidyl methacrylate methacrylic acid adduct. The compound which added acid anhydrides, such as succinic acid, maleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, is also mentioned.
Particularly preferred is (meth) acrylic acid.
These may be used alone or in combination of two or more.

As a method of reacting the epoxy group in the component (a ″) with the component (b ″), a known method can be used. For example, the component (a ″) and the component (b ″) are mixed with tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride and the like. Carboxylic acid can be added to the epoxy compound by reacting with a quaternary ammonium salt, pyridine, triphenylphosphine or the like 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 used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on 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, phenothiazine, etc.). The amount is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.

The ratio of adding the (b ″) component to the epoxy group of the (a ″) component is usually 90 to 100 mol%. Since the remaining epoxy group tends to adversely affect the storage stability, the component (b ″) is usually 0.8 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the component (a ″). In particular, the reaction is preferably carried out at a ratio of 0.9 to 1.1 equivalents.

(3) Polybasic acid and its anhydride (c ″)
As at least one of the polybasic acid and its anhydride (c ″) (hereinafter sometimes referred to as “component (c ″)” or “polybasic acid (anhydride)”), a dibasic acid and as at least one of the anhydride (hereinafter referred to as "tribasic acid (anhydride)") (hereinafter, referred to as "dibasic acid (anhydride)"), 3 at least one of the nucleotide acid and its anhydride, At least one of the 4-basic acid and its anhydride (hereinafter referred to as “4-basic acid (anhydride)”) or the like can be used.

As the 4-basic acid (anhydride) (at least one of tetracarboxylic acid and dianhydride thereof), known ones can be used, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid. And tetracarboxylic acids such as these, or their dianhydrides. These may be used individually by 1 type and may be used in combination of 2 or more type.
As the 4-basic acid (anhydride), among the above exemplified compounds, biphenyltetracarboxylic acid or an anhydride thereof is particularly preferable.

By reacting the reaction product of the component (a ″) and the component (b ″) with a 4-basic acid (anhydride) as the component (c ″), the molecular weight is increased by a crosslinking reaction. For this reason, there exist effects, such as an adhesive improvement to a board | substrate, adjustment of solubility, an improvement of a sensitivity or alkali tolerance, and it is preferable.

Examples of the dibasic acid (anhydride) (dicarboxylic acid and / or its anhydride) include, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid , Chlorendic acid, methyltetrahydrophthalic acid, or anhydrides thereof. Among these, tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

By reacting a reaction product of the component (a ″) and the component (b ″) with a dibasic acid (anhydride) as the component (c ″), it is possible to easily adjust the solubility and to the substrate. This is preferable because of improving the adhesion.

Examples of the tribasic acid (anhydride) (tricarboxylic acid and at least one of the anhydrides) include trimellitic acid, hexahydrotrimellitic acid, and anhydrides thereof. Particularly preferred are trimellitic anhydride and hexahydrotrimellitic anhydride. These may be used individually by 1 type and may be used in combination of 2 or more type.

By using a tribasic acid (anhydride) as the component (c ″), the molecular weight of the alkali-soluble resin (A ″) can be increased, branching can be introduced into the molecule, and the balance between molecular weight and viscosity can be improved. Can take. Moreover, the amount of acid groups introduced into the molecule can be increased, and a resin having a good balance of sensitivity, adhesion, and the like can be obtained.

As the (c ″) component, it is particularly preferable to use tetrabasic acid (anhydride). In this case, the addition rate of the 4-basic acid (anhydride) is usually 10 to 100 mol%, preferably 10 to 100 mol%, based on the hydroxyl group produced when the component (b ″) is added to the component (a ″). It is 20 to 100 mol%, more preferably 30 to 100 mol%. By setting the addition rate of the 4-basic acid (anhydride) as the component (c ″) to the above lower limit or more, sufficient solubility of the alkali-soluble resin (A ″) and good adhesion to the substrate can be obtained. Can be secured.

In addition, it is preferable to replace a part of the 4-basic acid (anhydride) described above with a dibasic acid (anhydride) from the viewpoint of adjusting the viscosity and solubility of the colored photosensitive composition.

In the case of using a 4-basic acid (anhydride) and a 2-basic acid (anhydride) in combination as the component (c ″), the molar ratio is as follows: dibasic acid (anhydride): 4-basic acid (anhydride) = 99: It is preferably 1 to 20:80, and more preferably 80:20 to 30:70. By setting the ratio of 4-basic acid (anhydride) to the above lower limit value or higher, it becomes possible to obtain high film properties of the resulting coating film, and dibasic acid (anhydride) is set to the above lower limit value or more. As a result, an increase in the viscosity of the resulting resin solution can be suppressed and the handleability can be improved.

In addition to the effects of improving adhesion to the substrate, easy adjustment of solubility, improvement of sensitivity and alkali resistance, etc., in order to achieve various balances such as molecular weight, viscosity, sensitivity, and adhesion, 4-basic acid is used. It is preferable to use at least one of (anhydride) and dibasic acid (anhydride) in combination with tribasic acid (anhydride).

(C '') When using at least one of four basic acids (anhydrides) and two basic acids (anhydrides) as a component and three basic acids (anhydrides) in combination, the amount of the three basic acids (anhydrides) used If the amount is too small, the effect is diminished and the alkali resistance may be lowered. Therefore, the amount of tribasic acid (anhydride) used is when (b '') component is added to (a '') component. The amount is usually 5 to 70 mol%, preferably 10 to 40 mol%, based on the hydroxyl group produced.

The total addition rate of the component (c ″) is usually 10 to 100 mol%, preferably 20 to 20%, based on the hydroxyl group produced when the component (b ″) is added to the component (a ″). 100 mol%, more preferably 30 to 100 mol%. By setting the addition rate of the component (c ″) to the above lower limit value or more, the solubility of the alkali-soluble resin (A ″) and the adhesion to the substrate are improved.

In addition, the component (c ″) can be added to the component (a ″) (b ′) in addition to reacting with the hydroxyl group produced when the component (b ″) is added to the component (a ″). ') When a component is added and a polyhydric alcohol (d ″) described later is mixed, it may be reacted with any hydroxyl group present in the mixture.
As a method of adding the component (c ″) after adding the component (b ″) to the component (a ″) or mixing the polyhydric alcohol (d ″) described later to this component, A known method can be used.

The reaction temperature is usually 80 to 130 ° C, preferably 90 to 125 ° C. When the reaction temperature exceeds 130 ° C., polymerization of a part of unsaturated groups in the component (b ″) occurs, which may lead to a rapid increase in molecular weight. Further, when the 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 adding a polyhydric alcohol (d ″) (hereinafter referred to as “(d ″)” to the reaction product obtained by adding the component (b ″) to the component (a ″) described above. An alkali-soluble resin (A1 ″) obtained by mixing the above component (c ″) with any hydroxyl group present in the mixture. It may be.

Examples of the component (d ″) include one or two or more kinds selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. A monohydric alcohol is preferred.

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 the molecular weight and the viscosity can be balanced. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.

If the amount of component (d ″) used is too small, the effect will be diminished, and if it is too large, there is a possibility of thickening or gelation, so the reaction product of component (a ″) and component (b ″) On the other hand, it is usually 0.01 to 0.5 times by weight, preferably 0.02 to 0.2 times by weight.

(5) Acid value and molecular weight of alkali-soluble resins (A ″) and (A1 ″) The acid values of the alkali-soluble resins (A ″) and (A1 ″) thus obtained are usually 10 mg− KOH / g or more, preferably 50 mg-KOH / g or more. In order to ensure good developability, the acid value is preferably not less than the above lower limit value, and sufficient alkali resistance of the colored photosensitive composition is ensured (that is, the rough surface of the pattern surface 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) in terms of standard polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resins (A ″) and (A1 ″) is preferably 1,500 or more, and 2,000. More preferably. Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less. By setting the weight average molecular weight to the above lower limit value or more, sensitivity, coating film strength, alkali resistance and the like are improved. Moreover, favorable developability and re-dissolution property can be obtained by setting it as the said upper limit or less.

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

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

[In the above general formula (1-a), n represents an average value and represents a number from 0 to 10. R ⁴¹ represents any one 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, and a biphenyl group. A plurality of R ⁴¹ 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. As represented, from the viewpoint of sensitivity and solubility, R ⁴¹ is particularly preferably a hydrogen atom or a methyl group. A plurality of R ⁴¹ present in one molecule may be the same or different.

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

[Wherein, n and R ⁴¹ represent the same meaning as in formula (1-a). ]

The compound represented by the general formula (1-a-1) is obtained, for example, by subjecting a compound represented by the following general formula (1-a-2) and a phenol to a condensation reaction in the presence of an acid catalyst. be able to.

[In formula, Z represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R ⁴¹ represents the same meaning as in the general formula (1-a). ]

In Z of the above general formula (1-a-2), the halogen atom is preferably a chlorine atom, a bromine atom or the like, and the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group. As a group.

On the other hand, phenols are aromatic compounds having one phenolic hydroxyl group per molecule. Specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol. Various o-, m-, and p-isomers of alkylphenols typified by xylenol, methylbutylphenol, di-t-butylphenol, etc., or cycloalkylphenols typified by cyclopentylphenol, cyclohexylphenol, cyclohexylresole, etc., or And substituted phenols substituted with the groups listed as R ⁴¹ in the general formula (1-a), such as phenylphenol. These phenols can be used individually by 1 type or in combination of 2 or more types.

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

In the above condensation reaction, an acid catalyst is preferably used, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. In particular, p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are preferable. The amount of the acid catalyst 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 above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples in the case of using an organic solvent include toluene, xylene, methyl isobutyl ketone and the like. The amount of the organic solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials. The reaction temperature is preferably in the range of 40 to 180 ° C., and the reaction time is preferably 1 to 8 hours.

After completion of the reaction, neutralization treatment or water washing treatment is performed to adjust the pH value of the product to 3-7, preferably 5-7. When performing the water washing treatment, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylenetriamine, What is necessary is just to process using various basic substances, such as organic amines, such as a triethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent. Moreover, what is necessary is just to perform a washing process according to a conventional method. For example, a method in which water in which the neutralizing agent is dissolved is added to the reaction mixture and the liquid separation extraction operation is repeated can be employed.

After the neutralization treatment or the water washing treatment, the unreacted dihydroxybenzenes and the solvent are distilled off under heating under reduced pressure to concentrate the product, which is represented by the general formula (1-a-1). Can be obtained.

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

In the reaction for obtaining the epoxy resin (a), an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the pressure is reduced. Alternatively, water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, water may be removed, and epihalohydrin may be continuously returned to the reaction system.

Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added to a dissolved mixture of the compound represented by the general formula (1-a-1) and epihalohydrin as a catalyst, To the halohydrin etherified product of the compound represented by the general formula (1-a-1) obtained by reacting at ˜150 ° C. for 1 to 5 hours, a solid or aqueous solution of an alkali metal hydroxide is added, and again 20 Alternatively, the reaction may be carried out at a temperature of ˜120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure).

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

Furthermore, in order to make the reaction proceed smoothly, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol. When alcohols are used, the amount used 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, the amount used is 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of epihalohydrin.

Epihalohydrin and other added solvents can be obtained after washing the reaction product of such an epoxidation reaction with or without washing with water under reduced pressure by heating, for example, at 110 to 250 ° C. and a pressure of 1.3 kPa (10 mmHg) or less. Are removed to obtain the desired epoxy resin (a).

In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly with respect to 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1) used for epoxidation. The amount is preferably 0.05 to 0.2 mol. 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 produced salt is removed by filtration, washing with water, and the like, and the solvent represented by the general formula (1-a) is removed by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure. Resin (a) can be obtained.

(2) Unsaturated group-containing carboxylic acid (b)
Examples of the unsaturated group-containing carboxylic acid (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p -Monocarboxylic acids such as vinyl benzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid , 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxy propyl acid 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (Meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) Acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid with ε-caprolactone, β-propiolactone, γ- Monomers to which lactones such as butyrolactone and δ-valerolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, ( Monomer) to which acid (anhydride) such as maleic acid is added, (meth) acrylic acid dye Chromatography and the like.

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

(3) Reaction of epoxy resin (a) with unsaturated group-containing carboxylic acid (b) Known method for reacting epoxy group in epoxy resin (a) with unsaturated group-containing carboxylic acid (b) Can be used. For example, an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) are converted into a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, etc. Carboxylic acid can be added to the epoxy resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using a quaternary ammonium salt, pyridine or triphenylphosphine as a catalyst.

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

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.). The amount is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the reaction raw material mixture.

The proportion of the unsaturated group-containing carboxylic acid (b) added to the epoxy group of the epoxy resin (a) is usually 90 to 100 mol%. Residual epoxy groups adversely affect storage stability. Therefore, the unsaturated group-containing carboxylic acid (b) is usually 0.8 to 1.5 equivalents, particularly 0, to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to carry out the reaction at a ratio of 9 to 1.1 equivalents.

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

The addition rate of at least one of the polybasic acid and its anhydride (c) is usually 10 to 100 of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy resin (a). The mol%, preferably 20 to 100 mol%, more preferably 30 to 100 mol%. If the addition rate is too high, the remaining film rate during development may decrease, and if it is too low, the solubility may be insufficient or the adhesion to the substrate may be insufficient. In addition, when using a polybasic acid and its anhydride together, the said addition rate represents the total addition rate of a polybasic acid and its anhydride.

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 is used. Can do.

In the present invention, after adding at least one of the polybasic acid and the anhydride (c) in this way, the epoxy group-containing compound (d) may be added to a part of the generated carboxyl group. . In this case, as the epoxy group-containing compound (d), in order to improve photosensitivity, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, glycidyl ether compound having a polymerizable unsaturated group, etc. In order to add an epoxy group-containing unsaturated compound or to improve developability, a glycidyl ether compound having no polymerizable unsaturated group can be added, 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 (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol). EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

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

(5) Physical Properties of Alkali-Soluble Resin (A), etc. The weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A) used in the present invention is usually 1500 or more, preferably Is 2000 or more, usually 50000 or less, preferably 30000 or less, more preferably 10,000 or less. If the weight average molecular weight of the alkali-soluble resin (A) is too small, the sensitivity is inferior, and if it is too large, the solubility in the developer is insufficient, which is not preferable.

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, curability is insufficient and the surface properties of the coating film tend to deteriorate.

The condensation reaction of the compound represented by the general formula (1-a-2) and the phenol compound, and the compound represented by the general formula (1-a-1) obtained by the condensation reaction and the epihalohydrin The synthesis reaction of the alkali-soluble resin (A) such as reaction, addition reaction with at least one of the unsaturated group-containing carboxylic acid (b) and the polybasic acid and its anhydride (c) can be performed by a known method. For example, it can be performed by the method described in Japanese Patent Application Laid-Open No. 2005-55814.

<Alkali-soluble resin (A ^' )>
As the binder resin in the present invention, particularly preferred other examples of things, ^'epoxy compound represented by (a following general formula ^(1-a)' and), the reaction product of an unsaturated group-containing carboxylic acid (b ^') And an alkali-soluble resin (A ^′ ) obtained by reacting with at least one of a polybasic acid and its anhydride (c ^′ ).

[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 represents an alkylene group. x and y each independently represents an integer of 0 or more. ]

(1) In formula (1-a ^') an epoxy compound represented by ^(a')
First, the epoxy compound (a ^′ ) represented by the general formula (1-a ^′ ) (hereinafter sometimes referred to as “(a ^′ ) component”) 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 the halogen atom includes Cl, Br, F and the like. R ³¹ and R ³² are particularly preferably each independently an alkyl group having 1 to 5 carbon atoms.

Although details of the mechanism of action of the alkyl groups and halogen atoms of R ³¹ and R ³² are not clear, it is assumed that they affect the three-dimensional structure of the molecule and control the solubility in the developer. Is done.
Therefore, from the above viewpoint, p and q in the general formula (1-a ^′ ) each independently represents 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,

Or

The o-position is preferred.

R ³¹ and R ³² may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.

^Examples of the alkylene group for R ³³ and R ³⁴ include an alkylene group having 1 to 10 carbon atoms, and it is particularly preferable that they are each independently an ethylene group or a propylene group.

X and y each independently represents an integer of 0 or more, but is usually 0 to 6, preferably 0 to 3. In general, the larger x and y, the higher the solubility, but if it is too large, the sensitivity may decrease.

R ³³ and R ³⁴ may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.

The molecular weight of these components (a ^′ ) is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC). . When the molecular weight is at least the lower limit value, the film-forming property is improved, and when the molecular weight is at most the upper limit value, gelation during the addition reaction of the unsaturated group-containing carboxylic acid (b ^′ ) described later is suppressed.

(2) Unsaturated carboxylic acid (b ^' )
Examples of the unsaturated group-containing carboxylic acid (b ^′ ) (hereinafter sometimes referred to as “(b ^′ ) component”) include those in <Alkali-soluble resin (A ″), Alkali-soluble resin (A1 ″)>. The same compounds as those mentioned as the saturated group-containing carboxylic acid (b ″) can be used. Of these, (meth) acrylic acid is preferred among α, β-unsaturated carboxylic acids, and acrylic acid is particularly preferred because of its high reactivity. Of the α, β-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 component (b ^′ ) used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of component (a ^′ ). .
(B ^' ) By making the usage-amount of a component more than a lower limit, a sufficient quantity of unsaturated groups can be introduce | transduced, and also with at least one of the following polybasic acid and its anhydride (c ^' ) The reaction is also sufficient. Moreover, the point that a large amount of epoxy groups does not remain is also preferable. By making the usage-amount of (b ^' ) component or less into an upper limit, it is preferable at the point which does not remain as an unreacted substance. By satisfying the above range, high photocuring characteristics can be obtained.

(3) Polybasic acid and its anhydride (c ^′ )
As the polybasic acid and its anhydride (c ^′ ), those listed as the polybasic acid and its anhydride (c ^″ ) in <Alkali-soluble resin (A ″), Alkali-soluble resin (A1 ″)> And the like, and tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof are preferable.

The addition rate of at least one of the polybasic acid and its anhydride (c ′) should be such that the final alkali-soluble resin (A ′) has an acid value of 10 to 150 mg-KOH / g. More preferably, it is 20 to 140 mg-KOH / g. By setting the acid value to be equal to or higher than the above lower limit, alkali developability is improved, and by setting the acid value to be equal to or lower than the upper limit, sufficient photocurability is obtained.

In addition, it is good also as what introduce | transduced polyfunctional alcohol (d ^' ), such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure at the time of this addition reaction of (c ^' ) component. Examples of the polyhydric alcohol (d ′) include compounds similar to those described above as the polyhydric alcohol (d ^″ ) in <Alkali-soluble resin (A ″), Alkali-soluble resin (A1 ″)>. The same applies to the preferred compounds and preferred amounts.

What is the synthesis reaction of the alkali-soluble resin (A ^′ ), such as an addition reaction of at least one of the unsaturated group-containing carboxylic acid (b ^′ ) and the polybasic acid and its anhydride (c ^′ ) to the epoxy compound (a ^′ )? Can also be performed by known methods. For example, see the methods described in Japanese Patent Application Laid-Open No. 2005-126585, Japanese Patent Application Laid-Open No. 2005-325331, Japanese Patent Application Laid-Open No. 2006-241224, and the like. Can be done.

The weight average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) of the alkali-soluble resin (A ^') (Mw) is usually 1,000 or more, preferably 1,500 or more, usually 30,000 or less , Preferably 20,000 or less, more preferably 10,000 or less, particularly preferably 8,000 or less. When the weight average molecular weight is not more than the above upper limit value, the developability is good, and when it is not less than the lower limit value, the alkali resistance is good.

<Alkali-soluble resin (A ''')>
Other examples of particularly preferable binder resins in the present invention include an epoxy resin (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 reaction product with at least one of a polybasic acid and its anhydride (c ′ ″).

[In the above general formula (1-a ′ ″), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵² represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms. R ⁵³ and R ⁵⁴ each independently represents a hydrogen atom or a glycidyl group. s represents 1 or 2. t and z represent the proportion 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. Among them, a hydrogen atom or a methyl group is preferable from the viewpoint of photocurability. S represents 1 or 2, and is preferably 1.

R ⁵² represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms. Such a group refers to an unsaturated polycyclic hydrocarbon ring compound having the same skeleton and at least two carbon-carbon double bonds (hereinafter sometimes simply referred to as “unsaturated polycyclic hydrocarbon compound”). It can be formed by using the raw material and carrying out the reaction described below.

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

Among these, a bridged carbocycle is more preferable, and dicyclopentadiene is particularly preferable.

The epoxy resin (a ′ ″) represented by the general formula (1-a ′ ″) is a polyaddition of the unsaturated polycyclic hydrocarbon compound described above and a phenol compound represented by the following general formula. It can be obtained by glycidylation of the hydroxyl group of the reaction product.

[In the above general formula, R ⁵¹ and s are as defined in the general formula (1-a ′ ″). ]

As the epoxy resin (a ′ ″), a compound represented by the following general formula (1-a ′ ″-1) obtained by glycidylation of a polyaddition reaction product of dicyclopentadiene and the above-described phenol compound is used. Particularly preferred.

[In the above general formula (1-a ′ ″-1), R ⁵³ , R ⁵⁴ , t and z have the same definitions as 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 50 to 100 mol of the phenolic hydroxyl group in the phenol resin before glycidylation. %, That is, t and z in the general formula (1-a ′ ″) and the general formula (1-a ′ ″-1) must have a relationship of t ≧ z ≧ 0.5t, preferably It is preferable that 70 to 100 mol% is substituted with a glycidyl group.

The alkali-soluble resin (A ′ ″) is a reaction product of the epoxy resin (a ′ ″) represented by the general formula (1-a ′ ″) and the unsaturated group-containing carboxylic acid (b ′ ″). Is a resin obtained by reacting at least one of a polybasic acid and its anhydride (c ′ ″).

As unsaturated group-containing carboxylic acid (b ′ ″), those listed as unsaturated group-containing carboxylic acid (b ″) in <Alkali-soluble resin (A ″), alkali-soluble resin (A1 ″)> The same compounds can be used, and preferred compounds and the reasons thereof are the same as described above.

The proportion of the unsaturated group-containing carboxylic acid (b ′ ″) added to the epoxy group of the epoxy resin (a ″ ″) is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the unsaturated group-containing carboxylic acid (b ′ ″) is usually 0.8 to 1 with respect to 1 equivalent of the epoxy group of the epoxy resin (a ″ ′). It is preferable to carry out the reaction at a ratio of 0.5 equivalent, particularly 0.9 to 1.1 equivalent.

Polybasic acid and its anhydride (c ′ ″) are also exemplified as polybasic acid and its anhydride (c ″) in <Alkali-soluble resin (A ″), Alkali-soluble resin (A1 ″)>. The same compounds as those described above can be used, and preferred compounds and the reasons thereof are the same as described above.

The addition rate of at least one of the polybasic acid and its anhydride (c ′ ″) is generated when an unsaturated group-containing carboxylic acid (b ′ ″) is added to the epoxy resin (a ′ ″). The hydroxyl group is usually 15 to 100 mol%, preferably 20 to 90 mol%, and the final acid-soluble resin (A ′ ″) has an acid value of 45 to 160 mg-KOH / g. Is preferred. By making this addition rate not more than the above upper limit value, it is possible to prevent a decrease in the remaining film rate during development, and by making it not less than the above lower limit value, good solubility and adhesion to the substrate can be obtained. Can do. In addition, when using a polybasic acid and its anhydride together, the said addition rate represents the total addition rate of a polybasic acid and its anhydride.

Reaction of unsaturated polycyclic hydrocarbon compound and phenolic compound, and glycidylation reaction of hydroxyl group in phenol resin obtained by the reaction, unsaturated group-containing carboxylic acid (b ′ ″), polybasic acid and its Any of the synthesis reactions of the alkali-soluble resin (A ′ ″), such as an addition reaction of at least one of the anhydrides (c ′ ″), can be carried out by a known method, for example, Japanese Patent Application Laid-Open No. 5-214048. It can carry out with reference to the method as described in gazette.

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

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

As the binder resin in the colored photosensitive composition of the present invention, among the above alkali-soluble resins (A), (A ′), (A ″), (A ′ ″), (A1 ″), the shape Alkali-soluble resins (A) and (A ′ ″) are preferable from the viewpoints of control of the level difference and the balance of adhesion to the substrate.

The content of the binder resin is usually 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. It is. By setting the content of the binder resin to the above lower limit value or more, the shape and level difference can be controlled, and the solubility of the unexposed portion in the developer can be ensured. Moreover, by setting it as the said upper limit or less, generation | occurrence | production of the wrinkle by the excessive shrinkage | contraction at the time of thermosetting can be suppressed.

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

As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith. A compound having two or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint that the difference in solubility can be expanded, and the ethylenically unsaturated bond is derived from a (meth) acryloyloxy group. More preferred are (meth) acrylate compounds.

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

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

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

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

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

Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, etc.

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

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

(In 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 1 to 10, particularly 1 to 4. Specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, ( (Meth) acryloyloxyethylene glycol phosphate and the like, and these may be used alone or as a mixture.

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

Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 21H-70B”, etc. manufactured by Asahi Kasei Kogyo Co., Ltd. Biuret type, A compound having 3 or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. A compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, For example, “Duranate ME20-100” manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. One or more hydroxyl groups in one molecule and FOB, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.

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

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

In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Those having 5 or more functional groups are particularly preferred.

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, particularly preferably 12 to 30% by weight, based on the total solid content. If the proportion of the photopolymerizable monomer is too much within this range, the degree of curing tends to decrease as the proportion of the other components decreases, so the voltage holding ratio tends to deteriorate. On the other hand, if the amount is too small, the amount of the alkali resin increases, so that the developability tends to decrease.

[4] Photopolymerization initiator The photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator, and a sensitizing dye added as necessary is used in combination.

The photopolymerization initiator system is a component that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

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

The photopolymerization initiator used in the colored photosensitive composition of the present invention is particularly preferably an oxime ester compound from the viewpoint of good generation efficiency of polymerization active radicals. Among them, the compounds exemplified below are preferably used. Can do.

Examples of the accelerator and the sensitizing dye constituting the photopolymerization initiator component include, for example, various compounds described in International Publication No. 2008/153000, and preferable compounds are also described in International Publication No. 2008/153000. It is the same as the prepared compound.

The content ratio of the photopolymerization initiator system component (mixture of photopolymerization initiator and accelerator) is usually 0.1 to 40% by weight, preferably 0.8% in the total solid content in the colored photosensitive composition of the present invention. 5 to 30% by weight. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

The content of the sensitizing dye 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 0% by weight based on the total solid content in the colored photosensitive composition. 10% by weight.

[5] Dispersant / dispersion aid In the colored photosensitive composition of the present invention, at least one of a pigment dispersant and a dispersion aid is used in combination in order to improve the dispersibility and dispersion stability of the pigment. Is preferred. Among them, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability with time. Here, the polymer dispersant is a polymer having a completely different structure from the pigment for ensuring the dispersion stability of the pigment, and the dispersion aid means a pigment derivative or the like for enhancing the dispersibility of the pigment. .

Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of these dispersants are trade names of EFKA (manufactured by BASF), DisperBYK (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by Geneca), KP (Shin-Etsu Chemical Co., Ltd. Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

These polymer dispersants can be used singly or in combination of two or more.

As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

Specific examples of pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.

These pigment derivatives can be used alone or in combination of two or more.

In the colored photosensitive composition of the present invention, the content of at least one of the dispersant and the dispersion aid is usually 5% by weight to 120% by weight, preferably 5% by weight to 90% by weight, based on the pigment. Hereinafter, more preferably, it is 5 wt% or more and 60 wt% or less, and a particularly preferred range is 5 wt% or more and 40 wt% or less. If the content of the dispersant and the dispersion aid is too small, sufficient dispersibility may not be obtained. If the content is too large, the ratio of other components may be relatively decreased, and the voltage holding ratio may be decreased. In addition, when using a dispersing agent and a dispersing aid together, the said content represents content of the sum total of a dispersing agent and a dispersing aid.
When a pigment derivative is used, the amount used is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, based on the pigment in the colored photosensitive composition. More preferably, it is 0.1 to 5% by weight.

[6] Solvent The colored photosensitive composition of the present invention generally contains the above-described pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, dispersant and dispersion aid, and the solid content of other components described below as a solvent. It is prepared by dissolving or dispersing in.

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

A solvent having a boiling point in the range of 100 to 300 ° C. is preferably selected. A solvent having a boiling point of 120 to 280 ° C. is more preferable.
Examples of such a solvent include various solvents described in International Publication No. 2008/153000.

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

In particular, when forming a black photospacer by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], the same applies to the boiling points hereinafter) is selected. More preferably. Particularly preferred are those having a boiling point of 120 to 170 ° C.
Of the solvents described in the above International Publication No. 2008/153000, glycol alkyl ether acetates are preferred from the viewpoint of good balance of coating properties, surface tension, etc., and relatively high solubility of constituents in the composition. .

In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment is likely to aggregate, and the storage stability such as the viscosity of the colored photosensitive composition tends to increase over time tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 30% by weight, more preferably 5 to 20% by weight.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high-boiling solvent in combination, the colored photosensitive composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Because of such high effects, among the various solvents described in the above-mentioned International Publication No. 2008/153000, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. preferable.

The content of the high boiling point solvent in the solvent is preferably 3% to 50% by weight, more preferably 5% to 40% by weight, and particularly preferably 5% to 30% by weight. The amount of high boiling point solvent by the above-described lower limit, for example, foreign matter defects can be prevented by precipitation and solidification of such a pigment in the slit nozzle tip, also by the above-described upper limit or less, the color to be described later In the filter manufacturing process, it is possible to keep the drying rate of the composition moderate so as not to cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.
The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.

Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

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, more preferably 60% by weight or more. It is. By setting the ratio of the solvent to the above upper limit or less, the colored photosensitive composition can contain a necessary and sufficient amount of solids such as a pigment, a binder resin, and a photopolymerizable monomer. Moreover, by setting it as more than the said lower limit, thickening can be suppressed and favorable applicability | paintability and the film thickness uniformity of a coating film can be obtained.

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

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

[7-1] Photoacid generator The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and there is a crosslinking agent such as a melamine compound by the action of the acid generated upon exposure. As a result, the crosslinking reaction proceeds. Among such photoacid generators, those having a high solubility in a solvent, particularly in a solvent used in a colored photosensitive composition, are preferred. For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide or borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Examples thereof include, but are not limited to, triazine compounds such as bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4,6-bistrichloromethyltriazine.
These photoacid generators may be used alone 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 To the colored photosensitive composition of the present invention, a crosslinking agent can be further added. For example, a melamine or guanamine compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XI).

[Wherein, R ⁶¹ represents a —NR ⁶⁶ R ⁶⁷ group or an aryl group, and when R ⁶¹ is a —NR ⁶⁶ R ⁶⁷ group, one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ And when R ⁶¹ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, and R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁵ The rest of ⁶⁷ , independently of each other, represents a hydrogen atom or a —CH ₂ OR ⁶⁸ group, where 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 a substituent such as an alkyl group, an alkoxy group, or a halogen atom is bonded to the phenyl group or naphthyl group. It may be. The alkyl group and the alkoxy group can each have 1 to 6 carbon atoms. Alkyl group represented by R ⁶⁸ is, among the above, methyl group or ethyl group, especially common that a methyl group.

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

[Wherein, when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ^{65 represents} a —CH ₂ OR ⁶⁸ group. And the remainder of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of one another represents a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or alkyl. ]

In addition, guanamine compounds corresponding to the general formula (XI), that is, compounds in which R ⁶¹ in the general formula (XI) is an aryl group include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl. Benzoguanamine and the like are included.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N- ethyl-dimethylol triazone) or its dimethyl ether thereof, dimethylol trimethylene urea or dimethyl ether thereof, 3,5-bis (hydroxymethyl) perhydro-1,3,5 Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.

In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.

The amount when the crosslinking agent is used 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 improving agent in order to sufficiently adhere fine lines and dots.

As the adhesion improver, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent and the like are preferable. Examples of the compound containing a nitrogen atom include diamines (described in Japanese Patent Application Laid-Open No. 11-184080). And other azoles are preferred. Among them, azoles are preferable, and in particular, imidazoles (adhesion improvers described in JP-A-9-236923, etc.), benzimidazoles, benzotriazoles (adhesion improvement described in JP-A-2000-171968). Agents, etc.) are preferred, and imidazoles and benzimidazoles are most preferred. Of these, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve the adhesion. -Aminoimidazole is preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferred. Various types of silane coupling agents such as epoxy, methacrylic, amino, etc. can be used, and epoxy and isocyanate silane coupling agents are particularly preferred.

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

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

[7-4] Sensitizing dye Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, and Japan. A coumarin dye having a heterocyclic ring described in JP-A-5-289335, a 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335, and JP-A-6-19240. Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japan Japanese Laid-Open Patent Publication No. 52-112682, Japanese Laid-Open Patent Publication No. 58-15503, Japanese Laid-Open Patent Publication No. 60-88005, Japanese Laid-Open Patent Publication No. 59-56403, Japanese Laid-Open Patent Publication No. The dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application Laid-Open No. 4-288818. The pigment | dye which has can be mentioned.

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

When a sensitizing dye is blended, 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 it is less than this, the sensitization effect may not be obtained, and if it is too much, developability may be lowered.

[7-5] Surfactant As the surfactant, one or more of anionic, cationic, nonionic, amphoteric surfactants and the like can be used, but they adversely affect various properties. In view of low possibility, it is preferable to use a nonionic surfactant. In addition, fluorine-based and silicon-based materials are effective in terms of coating properties.

When a surfactant is used, the blending ratio is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.8%, based on the total solid content in the colored photosensitive composition. The range is from 01 to 0.5% by weight, most preferably from 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 expressed. If the addition amount is large, the smoothness and uniformity of the coating film may not be expressed, and other characteristics may be exhibited. It may get worse.

[7-6] Organic Carboxylic Acid, Organic Carboxylic Anhydride The colored photosensitive composition of the present invention contains at least one of an organic carboxylic acid and an organic carboxylic anhydride for the purpose of improving developability and improving background stains. You may go out.

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

Among the above organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, among which malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.

The molecular weight of the organic carboxylic acid is usually 1000 or less and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving background stains may be insufficient. If the molecular weight is too small, the addition amount may decrease or process contamination may occur due to sublimation or volatilization.

Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples of aliphatic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, Tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3- Aliphatic carboxylic acid anhydrides such as dicarboxylic acids are mentioned. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

Among the above organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.

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

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

When these organic carboxylic acids and organic carboxylic acid anhydrides are used, the amount added is usually 0.01% by weight to 5% by weight, preferably 0%, based on the total solid content of the colored photosensitive composition of the present invention. 0.03% to 3% by weight. If the addition amount is too small, a sufficient addition effect may not be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and undissolved peeling pieces may be generated.

[7-7] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include one or two of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. More than seeds are used.

The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the colored photosensitive composition, and if it is more than this, the light shielding property and the sensitivity of the colored photosensitive composition are improved. It may cause a decrease.

[7-8] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Species or two or more are used.

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

[Preparation Method of Colored Photosensitive Composition]
The colored photosensitive composition of the present invention is prepared according to a conventional method. Hereinafter, examples will be described in detail, but the method for preparing the colored photosensitive composition in the present invention is not limited to this method.

From the standpoint of securing the dispersion stability of the pigment, the colored photosensitive composition of the present invention is preferably prepared by preparing a pigment dispersion in advance and mixing other components thereto as described below.

[1] Method for Producing Pigment Dispersion A predetermined amount of each of a pigment, a solvent, a dispersant, and, if necessary, a dispersion aid is weighed, and in the dispersion treatment step, the pigment is dispersed to obtain a liquid pigment dispersion. In the dispersion treatment step, it is possible to use a paint conditioner (paint shaker), a sand grinder, a ball mill, a roll mill, stone mill, a jet mill, a homogenizer or the like. Since the pigment is formed into fine particles by performing this dispersion treatment, the colored photosensitive composition using the pigment dispersion prepared in this way has improved coating characteristics and patterning characteristics such as shape and linearity.

When the dispersion treatment is performed 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 during the dispersion treatment is usually set in the range of 0 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 of the pigment dispersion (pigment, solvent, dispersant, etc.) and the size of the apparatus.
In this case, the standard of dispersion is to control the gloss of the pigment dispersion so that the 20 ° 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. Further, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

When the pigment is subjected to a dispersion treatment, the binder resin or the dispersion aid may be appropriately used in combination. By including the binder resin, it is possible to improve the dispersion stability when producing the pigment dispersion.
In this case, the addition amount of the binder resin is usually 5 to 100% by weight, preferably 10 to 60% by weight, based on the pigment in the pigment dispersion. By making the addition amount of the binder resin more than the above lower limit value, it can have higher dispersion stability and patterning characteristics, and by making it less than the above upper limit value, it is possible to ensure a high pigment concentration and higher light shielding properties. Is preferable.

The solid content concentration of the pigment dispersion is usually 10 to 40% by weight.
Here, “total solid content” refers to all 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 the other components contained in the colored photosensitive composition to the pigment dispersion obtained by the above steps and mixing them. It is prepared by making a uniform solution. In addition, the dispersion process with the liquid which mixed all the components mix | blended as a coloring photosensitive composition simultaneously has a possibility that a highly reactive component may modify | denature because of the heat_generation | fever which arises at the time of dispersion | distribution. Further, since fine dust is often mixed in the liquid in the manufacturing process, it is desirable that the obtained colored photosensitive composition solution is filtered by a filter or the like.

[Black Photo Spacer]
The colored photosensitive composition of the present invention is used in the same applications as known colored photosensitive compositions for color filters. Hereinafter, the colored photosensitive composition of the present invention is used as a black photospacer. This will be described according to a specific example of a method for forming a black photospacer using.

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

[1] Supplying Method 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. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. Among them, according to a die coating method, the reduction of consumption is much coating liquid, and there is no influence of mist adhering upon by a spin coating method, a foreign substance generation is suppressed, a comprehensive It is preferable from the viewpoint.

The coating amount varies depending on the application, but in the case of a black photospacer, for example, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel.

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

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

[2] Drying method The drying after supplying the colored photosensitive composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.

Drying conditions can be appropriately selected according to the type of solvent component and the performance of the dryer used. The drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used. The temperature is selected in the range of 30 seconds to 3 minutes.

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

As a preferred embodiment of the present invention, when black photo spacers having different heights are simultaneously formed by a photolithography method, for example, as described above, a light shielding portion (light transmittance of 0%) and a plurality of openings are used as an average light. An exposure mask having an opening (intermediate transmission opening) having a small average light transmittance relative to an opening having the highest transmittance (complete transmission opening) is used. By this method, a difference in the residual film rate is caused by a difference in average light transmittance between the intermediate transmission opening and the complete transmission opening (generally 5% to 40%), that is, a difference in exposure amount.
For example, a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known. Also known is a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.

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

The optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.

Energy of exposure generally, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 150 mJ / cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

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

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

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

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.

The development processing method is not particularly limited, but is usually performed at a development temperature of 10 ° C. to 50 ° C., preferably 15 ° C. to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development. .

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

The size, shape, etc. of the black photospacer of the present invention are appropriately adjusted according to the specifications of the color filter to which the black photospacer is applied, but the colored photosensitive composition of the present invention is particularly suitable for the spacer and sub-spacer by photolithography. It is useful for forming black photo spacers with different heights at the same time, in which case the height of the spacer is usually 2-7 μm and the sub-spacer is usually 0.2-1.5 μm lower than the spacer Have

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

A liquid crystal cell is formed 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 a liquid crystal is injected into the formed liquid crystal cell to manufacture a liquid crystal display device. it can.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. In the following, “part” represents “part by weight”.

The components of the colored photosensitive composition used in the following examples and comparative examples are as follows.

<Binder resin-1>
“ZCR-1569H” manufactured by Nippon Kayaku Co., Ltd. (MW = 3000 to 4000, acid value = about 100 mg-KOH / g)
The binder resin-1 corresponds to the “alkali-soluble resin (A)” in the present invention.

<Binder resin-2>
“ZCR-1642H” manufactured by Nippon Kayaku Co., Ltd. (MW = 5000-6500, acid value = about 100 mg-KOH / g)
The binder resin-2 corresponds to the “alkali-soluble resin (A)” in the present invention.

<Binder resin-3>
Resins obtained by reacting a reaction product of an epoxy compound having the following structure (11) with acrylic acid with trimethylolpropane (TMP) and biphenyltetracarboxylic dianhydride (BPDA) (MW = 3500 to 4500, acid Value = about 110 mg-KOH / g)

The binder resin-3 can be synthesized according to the following method.
<Synthesis Example 1: Synthesis of Binder Resin-3>
50 g of the epoxy compound having the structure (11) (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were added to a thermometer, a stirrer, and cooling. It puts into the flask which attached the pipe | tube, and is made to react at 90 degreeC, stirring until an acid value is set to 5 mgKOH / g or less. The reaction takes 12 hours to obtain an epoxy acrylate solution.

25 parts by weight of the above epoxy acrylate solution, 0.74 parts by weight of trimethylolpropane (TMP), 3.95 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), 2.7 parts by weight of tetrahydrophthalic anhydride (THPA) Is put in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature is slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, it is diluted with methoxybutyl acetate to prepare a solid content of 50% by weight to obtain binder resin-3.

This binder resin-3 corresponds to the “alkali-soluble resin (A1”) ”in the present invention.

<Dispersant>
"DisperBYK-2000" manufactured by Big Chemie
<Dispersing aid>
“S12000” manufactured by Loop Resor Co., Ltd.
<Surfactant>
“MegaFuck F-475” manufactured by Dainippon Ink & Chemicals, Inc.
<Solvent-1>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-2>
MB: 3-methoxybutanol

<Photopolymerization initiator>
The following compounds.

<Photopolymerizable monomer>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

[Preparation of pigment dispersions 1 to 10]
The pigment, dispersant, dispersion aid, binder resin, and solvent described in Table 1 were mixed at a weight ratio described in Table 1. Here, 80% of the volume of the dispersion container is mixed with zirconia beads (average particle size 0.3 mm), and then filled into a picomil dispersion container and dispersed at the necessary retention time (RT) shown in Table 1. Each pigment dispersion was prepared.

[Examples 1 to 5, Comparative Examples 1 to 6]
The pigment dispersion prepared as described above and the other components shown in Table 2 were blended and stirred in the proportions shown in Table 2 to prepare a colored photosensitive composition.

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

[Evaluation of step (ΔH), adhesion, optical density (OD)]
<Batch formation method of cured products with different heights>
Each colored photosensitive composition was applied onto a glass substrate (“AN100” manufactured by AGC) using a spinner. Next, the coating film was formed by heating and drying on a hot plate at 110 ° C. for 70 seconds.
For the obtained coating film, an exposure mask having a circular transmission pattern having a circular pattern with various diameters of 5 to 50 μm, an intermediate transmission opening having a circular pattern with various diameters of 5 to 50 μm, and a solid part is used. The exposure process was performed. The intermediate transmission opening is a Cr oxide thin film having 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 μm. The light Shako, intensity at a wavelength of 365nm is used ultraviolet is 32 mW / cm ^2, the exposure amount was 6 levels of 40 ~ 90mJ / cm ^2. Moreover, ultraviolet irradiation was performed under air.

Subsequently, a developer composed of an aqueous solution containing 0.05% by weight of potassium hydroxide and 0.08% by weight of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used. After performing the shower development at 15 MPa, the development was stopped with pure water and washed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was 1.5 times as long as the unexposed coating film was dissolved and removed.
By these operations, a pattern from which unnecessary portions were removed was obtained. The board | substrate with which the said pattern was formed was heated at 230 degreeC for 20 minute (s) in oven, the pattern was hardened, and the substantially cylindrical spacer pattern was obtained.

<Evaluation of steps>
The height difference (step ΔH) between the complete transmission opening of the circular pattern with a diameter of 15 μm and the intermediate transmission opening of the circular pattern with a diameter of 35 μm is calculated, and the maximum value at an exposure amount of 40 to 90 mJ / cm ² is obtained. Was evaluated according to the following criteria.
(Evaluation criteria for step ΔH)
0.5 μm or more: ○
0.3 μm or more and less than 0.5 μm: Δ
Less than 0.3 μm: ×

<Evaluation of substrate adhesion>
The pattern remains with good resolution at a completely transmissive aperture of a circular pattern of 5 to 50 μm and an intermediate transmissive aperture of 5 to 50 μm at an exposure amount that maximizes the height difference (ΔH). The minimum opening diameter (μm) is shown in Table 2 as the minimum adhesion. The smaller this value, the better the substrate adhesion. “Remaining with good resolution” means that 24 patterns of the same size are formed and all the patterns are formed normally.

<Evaluation of optical density (OD)>
The optical density (OD) of the solid part was measured with a transmission densitometer (“D 200-II” manufactured by Gretag Macbeth). Furthermore, the film thickness at the measurement location was also measured, and the optical density per unit film thickness (unit OD) was calculated and evaluated according to the following criteria. The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.
(Evaluation criteria for unit OD)
0.8 or more: ○
Less than 0.8: ×

[Voltage holding ratio (VHR) evaluation]
<Production of liquid crystal cell>
An extraction substrate having a width of 2 mm was connected to the center of one side of the 2.5 cm square glass substrate and the electrode substrate A (Ec Sea, glass ITO solid for evaluation) having an ITO film formed on the entire surface of a 5 cm square piece. An electrode substrate B (manufactured by ECH, evaluation glass SZ-B111MIN (B)) on which a 1 cm square ITO film was formed was prepared.

Each colored photosensitive composition was applied on the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked on a hot plate at 90 ° C. for 1.5 minutes to obtain a coating film having a dry film thickness of 2.0 μm. . Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed using 3 kW high-pressure mercury under exposure conditions of 50 mJ / cm ² . Next, a developer composed of 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) was used at 25 ° C. After performing shower development at a water pressure of 0.15 MPa, development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was about 1.5 times the time (break time) during which the non-photosensitive layer was dissolved and removed.

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

On the other hand, a polyimide solution was also applied onto the electrode substrate B, pre-baked at 70 ° C. for 2 minutes on a hot plate, and post-baked at 220 ° C. for 24 minutes to complete the evaluation electrode substrate B.
Thereafter, an epoxy resin sealant containing silica beads having a diameter of 5 μm is applied on the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A for evaluation is placed on the front side (the sealant side) of the electrode substrate B. The application surface was pasted and bonded to complete the empty cell. Heating was performed at 180 ° C. for 2 hours in a hot air circulating furnace.
A liquid crystal (MLC-6608 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.

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

From the results of Table 2, 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 as pigments have light shielding properties. It can be seen that it is useful for simultaneously forming cured products having different heights from the same material while maintaining adhesion and voltage holding ratio.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on January 31, 2012 (Japanese Patent Application No. 2012-018337), the contents of which are incorporated herein by reference.

Claims

A colored photosensitive composition comprising a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, wherein the pigment comprises a pigment shown in (A) below and a pigment shown in (B) object.
(A) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. One selected from the group consisting of CI Pigment Orange 72 (B) C.I. I. Pigment Blue 60
The pigment is C.I. I. Pigment orange 64 and C.I. I. The colored photosensitive composition according to claim 1, comprising Pigment Blue 60.
The pigment is C.I. I. Pigment red 254, C.I. I. Pigment violet 23, and C.I. I. The colored photosensitive composition according to claim 1 or 2, further comprising one selected from the group consisting of CI Pigment Violet 29.
The colored photosensitive composition according to claim 1, wherein the pigment contains a pigment shown in the following (1) or a pigment shown in (2).
(1) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, and C.I. I. Pigment Red 254
(2) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, and C.I. I. Pigment Violet 29
A black photospacer formed 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 5.