KR102078989B1 - Colored photosensitive composition, black photo spacer, and color filter - Google Patents

Abstract

The coloring photosensitive composition containing the pigment, binder resin, a photopolymerizable monomer, and a photoinitiator, The coloring photosensitive composition which the said pigment contains the pigment shown to following (A) and the pigment shown to (B).
(A) one selected from the group consisting of CI pigment orange 43, CI pigment orange 64 and CI pigment orange 72
(B) CI Pigment Blue 60

Description

Colored photosensitive composition, black photo spacer and color filter {COLORED PHOTOSENSITIVE COMPOSITION, BLACK PHOTO SPACER, AND COLOR FILTER}

The present invention relates to colored photosensitive compositions and the like. Specifically, for example, in a color filter such as a liquid crystal display, a colored photosensitive composition which is preferably used for formation of a black photo spacer and the like, and a black photo spacer formed by using the colored photosensitive composition and a color including the black photo spacer It is about a filter.

A liquid crystal display (LCD) utilizes the property in which the arrangement | positioning method of a liquid crystal molecule is switched by on / off of the voltage to a liquid crystal. On the other hand, each member which comprises the cell of LCD is formed using the photosensitive composition represented by photolithography in many cases. Even in the reason that it is easy to form a fine structure, and it is easy to process with respect to the board | substrate for a big screen, the range of application of the photosensitive composition will become wider in the future.

However, in the LCD using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electric properties of the photosensitive composition itself or the impurities contained in the photosensitive composition, thereby causing problems such as display unevenness of the display. In particular, in a color liquid crystal display device, a member closer to the liquid crystal layer, for example, a liquid crystal panel, which is used to keep the distance between two substrates constant, so-called columnar spacers, photo spacers, and the like, have the effect. Is big.

Conventionally, when a spacer having no light shielding property is used in a TFT type LCD, the TFT as a switching element may malfunction due to the light passing through the spacer. In order to prevent this, patent document 1 describes making a spacer light-shielding, for example.

However, in order to make a spacer light-shielding, although it is generally considered to add the coloring agent etc. containing a pigment to a photosensitive composition, as the coloring agent is added, the curability of a spacer layer reduces by the decrease of a clear component, and originates from a pigment There is a risk of impairing properties due to the influence of impurities.

In order to control voltage retention, the method of improving curability, the method of controlling curable resin of a photosensitive composition, a dispersing agent, etc. are proposed.

On the other hand, recently, when manufacturing a spacer by the photolithographic method, the method of collectively forming the spacer from which height differs with the change of a panel structure is proposed. Patent Document 2 discloses that the shape and the step of a spacer having a different desired height can be realized by controlling the exposure amount and the residual film ratio.

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

However, Patent Document 2 relates to a spacer to which no pigment is added. When applied to batch formation of a colored spacer to which a pigment is added, the pigment absorbs light in an ultraviolet region contributing to photopolymerization, so that the light transmittance of the opening is It has been found that it is difficult to achieve characteristics such as the shape of the desired spacers having different heights, the control of the steps, and the adhesion to the substrate in a small pattern with low curability.

This invention is made | formed in view of such a situation. That is, the main subject of this invention is the method of collectively forming black photo spacers from which height differs by the photolithography method, ensuring light shielding property and the voltage retention of a liquid crystal, and being able to control a shape and a step | step, It is providing the coloring photosensitive composition which can form the black photo spacer excellent in the adhesiveness of the.

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

Moreover, another subject of this invention is providing the color filter provided with such a black photo spacer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, it discovered that the said subject can be solved by using a specific pigment as a coloring agent, and came to complete this invention. That is, the summary of this invention is as follows.

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

(A) C.I. Pigment Orange 43, C.I. Pigment Orange 64 and C.I. 1 piece selected from the group consisting of pigment orange 72

(B) C.I. Pigment Blue 60

[2] The pigment is C.I. Pigment Orange 64 and C.I. The coloring photosensitive composition as described in said [1] containing pigment blue 60.

[3] The pigment is C.I. Pigment Red 254, C.I. Pigment Violet 23 and C.I. The coloring photosensitive composition as described in said [1] or [2] which further contains one selected from the group which consists of pigment violet 29.

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

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

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

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

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

According to the present invention, in the method of collectively forming black photo spacers having different heights by the photolithography method, by suitably combining pigment species having different light absorption characteristics, and ensuring a balance between light absorption in the ultraviolet region and the visible region, While maintaining the light shielding properties and the voltage retention of the liquid crystal, high shape adhesion to the substrate can be realized while controlling the shape and the step difference.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described in detail, description of the element | module described below is an example (representative example) of embodiment of this invention, and this invention is limited to these content, unless the summary is exceeded. It doesn't happen.

In addition, in this invention, "(meth) acryl" etc. shall mean "at least one of acryl and methacryl", and "(meth) acrylate" etc. shall be at least among "acrylate and methacrylate." One ", etc., and" (meth) acrylic acid "shall mean" at least one of acrylic acid and methacrylic acid. " "(Meth) acryloyl" is also the same. In addition, "(acid) anhydride", "(anhydrous)…" Acid "means containing both an acid and its anhydride.

In addition, "all solid content" shall mean all the components other than the solvent component mentioned later contained in a coloring photosensitive composition or a pigment dispersion liquid.

In addition, 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.).

In addition, in this invention, unless otherwise indicated, "amine value" shows the amine value of effective solid content conversion, and is a value shown by the weight of the base amount and the equivalent KOH per solid content of a dispersing agent. In addition, a measuring method is mentioned later. In addition, unless otherwise indicated, an "acid value" shows the acid value of effective solid content conversion, and is computed by neutralization titration.

In addition, in this invention, a "monomer" is a meaning corresponding to what is called a high molecular substance, and it is a meaning including a dimer, a trimer, an oligomer, etc. other than the monomer (monomer) of a narrow meaning.

The coloring photosensitive composition of this invention contains a pigment, binder resin, a photopolymerizable monomer, and a photoinitiator, and contains following (A) and (B) as a pigment, Especially in the photolithographic method It is preferably used as a coloring photosensitive composition for forming a batch of black photo spacers having different heights.

(A) C.I. Pigment Orange 43, C.I. Pigment Orange 64 and C.I. 1 piece selected from the group consisting of pigment orange 72

(B) C.I. Pigment Blue 60

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

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

As the exposure mask, there is known a method of using an exposure mask having a light shielding layer that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some of the openings is smaller than the average light transmittance of the other openings. It has a light shielding layer (0% light transmittance) and a plurality of openings, and has an average opening with a small average light transmittance (average of 100% light transmission. Hereinafter, referred to as a "completely transmissive opening") with the highest average light transmittance (average). The light transmittance is more than 0% and less than 100%, Preferably it is more than 5% and less than 50%. Hereinafter, it is a method of using the exposure mask which has a "middle transmission opening part." By this method, for example, in the case of a negative colored coloring photosensitive composition, the difference in the degree of curing of the pattern formed by the difference in the average light transmittance of the intermediate transmission opening and the perfect transmission opening, that is, the exposure dose, is generated. Development and thermal curing processes can form black photo spacers of different heights.

[Coloring Photosensitive Composition]

The constituent material of the coloring photosensitive composition of this invention is demonstrated below.

[1] pigments

A pigment means coloring the coloring photosensitive composition of this invention.

As a pigment, pigments of various colors, 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 the structure, organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene can be used.

In the coloring photosensitive composition of this invention, following (A) and (B) are contained as an essential component as a pigment.

(A) C.I. Pigment Orange 43, C.I. Pigment Orange 64 and C.I. 1 piece selected from the group consisting of pigment orange 72

(B) C.I. Pigment Blue 60

In the coloring photosensitive composition of this invention, there is no restriction | limiting in particular in the pigment to use except having containing said (A) and (B) as an essential component as a pigment, and black by mixing each color, such as red, green, blue, etc. Colorants can be used. Moreover, it can select suitably from a black pigment, another inorganic or organic pigment, and dye, and can use together.

Hereinafter, the specific example of the pigment which can be used is shown by a pigment number.

As a red pigment, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48 , 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: 1, 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, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, Preferably C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment red 177, 179, 209, 224, 254 is mentioned. Among them, C.I. Pigment red 254 (R254) is mentioned.

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

As a green pigment, C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, Preferably C.I. Pigment green 7, 36 is mentioned.

As a yellow pigment, C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 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, 173, 174 , 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, and 208. Among these, Preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment yellow 83, 138, 139, 150, 180 is mentioned.

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

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

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

As an example of the commercial item of carbon black, the following items are mentioned.

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 production: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, 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 company production: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL550R, REGAL400R, BLACK , VULCAN XC72R, ELFTEX-8

Columbian carbon company production: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN760, RAVEN780RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1060U, RAVEN1080U, RAVEN1100URAVEN10, RAVEN1100URAVEN10 RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As an example of the commercial item of titanium black, the following items are mentioned.

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

Ako Kasei Corporation make: Tilack DM, M-50, M-50A, M-AM, V, UV-3, UV-6, F, S, C, X

The coloring photosensitive composition of this invention is a C.I. pigment as a pigment from a viewpoint of light-shielding property, voltage retention of a liquid crystal, control of a shape and a level | step, and adhesiveness with a board | substrate. Pigment Orange 64 and C.I. It is preferable to contain Pigment Blue 60.

The coloring photosensitive composition of this invention is C.I. further as a pigment other than said (A) and (B). Pigment Red 254, C.I. Pigment Violet 23 and C.I. It is preferable to contain one selected from the group consisting of pigment violet 29.

The coloring photosensitive composition of this invention is three kinds shown to any one of following (1)-(3) as a pigment, in order to make the light-shielding property, the voltage retention of a liquid crystal, control of a shape and a step | step, and adhesiveness with a board | substrate more favorable. It is preferable to contain the pigment of, and it is preferable to contain 3 types of pigments shown to (1) or (2) especially from a viewpoint of the voltage retention of a liquid crystal.

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

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

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

The ratio of the pigment in the coloring photosensitive composition of this invention is 5-50 weight% normally with respect to a total solid, Preferably it is 10-45 weight%, More preferably, it is 20-42 weight%. When there are more pigments than this range, the shape, step | step of a spacer, adhesiveness with a board | substrate may deteriorate, or a curable component may reduce, and it may become a cause of the voltage retention deterioration by a pigment etc. eluting to a liquid crystal layer. On the other hand, when less than this range, sufficient light-shielding property as a black photo spacer may not be ensured.

In addition, the ratio of (A) and (B) in a pigment is either too much or too at least, and the light-shielding property by this invention by using these together at least, the voltage retention of a liquid crystal, control of a shape and a step | step, and adhesiveness with a board | substrate Since the improvement effect of may not be fully acquired, 25-70 weight% of (A) is especially 30-60 weight%, especially 35-60 weight% with respect to a total of 100 weight% of (A) and (B). It is preferable to use as.

That is, (A) has relatively small absorption of light in the wavelength vicinity of 330 nm-380 nm, and also absorbs light in the wavelength 400 nm-550 nm vicinity. On the other hand, (B) is similarly small in the absorption of the light of wavelength 330nm-380nm vicinity, and also the absorption of the light of the wavelength 550nm-700nm vicinity is large. Therefore, by using a combination of these two pigments in a good balance, the balance between light absorption in the ultraviolet region and the visible region can be made good, and the light shielding property, the voltage retention of the liquid crystal, the control of the shape and the step, and the adhesiveness with the substrate can be improved. have.

Moreover, although the pigment used by this invention may contain various pigments other than (A) and (B), in order to fully acquire the said effect by combined use of (A) and (B), this invention It is preferable that the ratio of the sum total of (A) and (B) is 50 weight% or more, especially 60-95 weight%, especially 70-90 weight% in 100 weight% of total pigments contained in the coloring photosensitive composition of .

Moreover, in the combination of the pigment used by this invention, it is a C.I. By using Pigment Red 254 (R254), absorption of the visible region can be increased while suppressing light absorption in the ultraviolet region, and the light shielding property, the voltage retention of the liquid crystal, the control of the shape and the step difference, and the adhesion to the substrate can be improved. The effect is exerted. In this case, in 100 weight% of total of (A), (B), and R254, 20-40 weight% of (A), 45-65 weight% of (B), 5-25 weight% of R254 especially It is preferable to use (A) 25-35 weight%, (B) 50-60 weight%, and R254 in the ratio of 10-20 weight%. Although pigments other than these (A), (B) and R254 may be used, the ratio of the sum total of (A), (B), and R254 in all the pigments in a coloring photosensitive composition is 70 weight% or more, Especially 90- It is preferable to use so that it may become 100 weight%.

Moreover, in the combination of the pigment used by this invention, it is a C.I. By using Pigment Violet 23 (V23), absorption of the visible region can be increased while suppressing light absorption in the ultraviolet region, thereby improving light shielding and voltage retention of the liquid crystal, control of the shape and step, and adhesion to the substrate. Can be exerted. In this case, 30-100 weight% of (A), 30-50 weight% of (B), and 10-30 weight% of V23 in 100 weight% of the total of (A), (B), and V23 especially It is preferable to use (A) 35-45 weight%, (B) 35-45 weight%, and V23 in the ratio of 15-25 weight%. Although pigments other than these (A), (B) and V23 may be used, the ratio of the sum total of (A), (B), and V23 in all the pigments in a coloring photosensitive composition is 70 weight% or more, Especially 90- It is preferable to use so that it may become 100 weight%.

Moreover, in the combination of the pigment used by this invention, it is a C.I. By using Pigment Violet 29 (V29), absorption of the visible region can be increased while suppressing light absorption in the ultraviolet region, thereby improving light shielding and voltage retention of the liquid crystal, control of the shape and step, and adhesion to the substrate. Can be exerted. In this case, in 100 weight% of total of (A), (B), and V29, 30-50 weight% of (A), 30-50 weight% of (B), and 10-30 weight% of V29, especially It is preferable to use (A) 35-45 weight%, (B) 35-45 weight%, and V29 in the ratio of 15-25 weight%. Although pigments other than these (A), (B) and V29 may be used, the ratio of the sum total of (A), (B), and V29 in all the pigments in a coloring photosensitive composition is 70 weight% or more, Especially 90- It is preferable to use so that it may become 100 weight%.

Moreover, the pigment used by this invention is (A) and (B), and also C.I. It is preferable to contain Pigment Red 272 (R272). R272 is advantageous for high OD due to its large visible absorption.

[2] binder resins

As binder resin used for the coloring photosensitive composition of this invention, if it is resin of the member used for a color filter, it can be used without a restriction | limiting, For example, an epoxy acrylate type resin, a novolak-type resin, polyvinyl phenol type resin, acrylic resin Although a carboxyl group-containing epoxy resin, a carboxyl group-containing urethane resin, etc. are mentioned, It is preferable to use the epoxy acrylate resin and acrylic resin which have a carboxyl group from a viewpoint of control of a shape and a step | step, and adhesiveness with a board | substrate, and having a carboxyl group It is more preferable to use an epoxy acrylate resin.

The epoxy acrylate resin is an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group added to an epoxy resin (or an epoxy compound), and a polybasic acid or anhydride thereof. It is synthesized by reacting. Such a reaction product does not have an epoxy group substantially and is not limited to an "acrylate" in terms of chemical structure, but an epoxy resin (or an epoxy compound) is a raw material and "acrylate" is a representative example. It is named as:

As an epoxy resin used as a raw material, (o, m, p-) cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, trisphenol methane type epoxy resin, or the following And epoxy resins (or epoxy compounds) represented by General Formulas (1-a) to (1-a '' ') described.

What is especially preferable as binder resin in this invention is demonstrated below.

<Alkali-soluble resin (A ''), alkali-soluble resin (A1 '')>

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

[Formula 1]

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

[Formula 2]

(Wherein in the formula (2a) and (2b), R ¹ to R ⁴ and R ¹³ - R ¹⁵ is O, which may each independently have a substituent but group, having 1 to be a hydrogen atom, an optionally substituted The alkyl group of 12 or the phenyl group which may have a substituent is shown.

In said general formula (3), R <^5> -R <^12> respectively independently represents a hydrogen atom, the C1-C12 alkyl group which may have a substituent, or the phenyl group which may have a substituent. Y represents the bivalent coupling group containing the adamantane structure which may have a substituent.

In General Formulas (2a), (2b) and (3), * represents a binding site to a glycidyloxy group in General Formula (1-a '').]

(1) Epoxy compound (a '') represented by general formula (1-a '')

First, group X in the epoxy compound (a '') (Hereinafter, it may be called "(a") component "represented by the said General formula (1-a") is demonstrated.

When said group X is a structure represented by the said General formula (2a) or (2b), it is preferable that the said General formula (2a) and (2b) have 2 or more and 4 or less of adamantane structures all. In the adamantane structure 1, developing resistance falls and there exists a tendency for inferior resolution.

When the said group X is a structure represented by the said General formula (3), if Y in the said General formula (3) is "the bivalent coupling group containing the adamantyl structure which may have a substituent", it is another Although there is no restriction | limiting in particular, For example, it is preferable that it is a linking group represented by following General formula (4) or (5).

[Formula 3]

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

In particular, the epoxy compound (a '') represented by General Formula (1-a '') is preferably represented by the following General Formula (6) or (7).

[Formula 4]

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

In General formula (6), R <^16> -R <^23> respectively independently represents a hydrogen atom, the C1-C12 alkyl group which may have a substituent, or the phenyl group which may have a substituent.

In general formula (7), R <^24> and R <^25> respectively independently represents the adamantyl group which may have a substituent, the hydrogen atom, the C1-C12 alkyl group which may have a substituent, or the phenyl group which may have a substituent. .]

The formula (2a), (2b), (3), the alkyl group of R ¹ ~ R ²⁵ having 1 to 12 carbon atoms of the D (6) and (7), with preferably an alkyl group having 1 to 10 carbon atoms Can be.

Moreover, as a substituent which these alkyl groups may have, a halogen atom, a hydroxyl group, a C1-C10 alkoxyl group, a C2-C10 alkenyl group, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, a nitro group, etc. are mentioned. Can be.

Further, the formula (2a), (2b), (3), (6), R 1 ~ R substituent which may phenyl group having a ^25, a halogen atom, a hydroxyl group, having 1 to 10 carbon atoms in the (7) An alkoxyl group, a C2-C10 alkenyl group, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, a nitro group, etc. are mentioned.

Moreover, the adamantyl group of R <^1> -R <^4> and R <^13> -R <^{15> in} the said General formula (2a) and (2b), Y in General formula (3), General formula (6 ), Adamantane ring in formula (7), adamantyl group in formula (7), R ²⁴ in formula (7), adamantyl group of R ²⁵ and general formulas (4) and (5) As a substituent which the adamantane ring may have, a halogen atom, a hydroxyl group, a C1-C10 alkoxyl group, a C2-C10 alkenyl group, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, a nitro group, etc. are mentioned. Can be.

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 General Formula (7), R ²⁴ and R ²⁵ are particularly preferably alkyl groups, halogen atoms, alkoxyl groups, alkenyl groups, or phenyl groups.

 It is preferable that the molecular weight of X shown in general formula (1-a ") is 200 or more and 1000 or less. By setting the molecular weight of X to 200 or more, sufficient chemical resistance can be ensured, and by setting it to 1000 or less, good sensitivity can be ensured.

Moreover, it is preferable that it is 210 or more, and, as for the epoxy equivalent of the epoxy compound (a ") represented by general formula (1-a"), it is more preferable that it is 230 or more. Moreover, it is preferable that it is 450 or less, and, as for this epoxy equivalent, it is more preferable that it is 400 or less. By setting the epoxy equivalent of the epoxy compound (a '') to 210 or more, sufficient alkali resistance can be ensured, and by setting it to 450 or less, good sensitivity of the resulting organic binder can be ensured.

An epoxy compound (a ") may be used individually by 1 type, and may be used in combination of 2 or more type.

A commercially available thing may be used for an epoxy compound (a "), and it may synthesize | combine and use it by a well-known method from the following phenol compounds.

[Formula 5]

[R <^1> -R <^15> in the said General formula (9a), (9b) and (10) has the same meaning as the definition in General Formula (2a), (2b) and (3), respectively.]

For example, alkali metals, such as sodium hydroxide and potassium hydroxide, in the dissolution mixture of the compound represented by General formula (9a) or (9b), and epihalohydrin, such as excess epichlorohydrin and epibromohydrin. X in general formula (1-a '') is represented by the said general formula (2a) or (2b) by adding hydroxide beforehand or making it react for 1 to 10 hours at the temperature of 20-120 degreeC, adding The epoxy compound (a '') which is group can be obtained.

Moreover, alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are previously added to the dissolution mixture of the compound represented by General formula (10), and epihalohydrin, such as excess epichlorohydrin and epibromohydrin, or By reacting at the temperature of 20-120 degreeC for 1 to 10 hours, the epoxy compound (a ") whose X in general formula (1-a") is a coupling group represented by the said General formula (3) can be obtained. have.

In reaction which obtains this epoxy compound (a "), you may use this aqueous solution as alkali metal hydroxide. In this case, the aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously discharged under reduced pressure or normal pressure, and the liquid is separated, and the water is removed to epi. The halohydrin may be a method of returning continuously into the reaction system.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzyl ammonium chloride is catalyzed by a dissolution mixture of the compound represented by the general formulas (9a), (9b) or (10) and epihalohydrin. Solid or aqueous solution of alkali metal hydroxide is added to the halohydrin etherate of the compound represented by General formula (9a), (9b), or (10) obtained by adding as a reaction and reacting at 50-150 degreeC for 1 to 5 hours. And the epoxy compound (a ") represented by general formula (1-a") can also be manufactured also by the method of making it react for 1 to 10 hours at the temperature of 20-120 degreeC, and also to dehydrogen halide (close ring).

The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, with respect to 1 equivalent of hydroxyl groups of the compound represented by General Formula (9a), (9b) or (10). to be. Moreover, the usage-amount of alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by General formula (9a), (9b), or (10), Preferably it is 0.9-11 mol.

In the above-mentioned reaction, in order to further advance the reaction smoothly, in addition to 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. When using alcohols, the usage-amount is 2-20 weight% with respect to the quantity of epihalohydrin, Preferably it is 4-15 weight%. Moreover, when using an aprotic polar solvent, the usage-amount is 5-100 weight% with respect to the quantity of epihalohydrin, Preferably it is 10-90 weight%.

The unsaturated group-containing carboxylic acid (b '') (hereinafter may be referred to as "(b '') component") includes unsaturated carboxylic acid having an ethylenically unsaturated group, and specific examples thereof include (meth ) Acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, (meth) acrylic acid in which the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group Monocarboxylic acid; 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyladipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydro Phthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxy Propyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyl Of dibasic acids such as oxybutyl adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutyl maleic acid (Meth) acryloyloxyalkyl ester; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth) acrylic acid; (Meth) acrylic acid dimer etc. are mentioned.

In addition, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropanediacrylate, acrylic acid adduct of glycidyl methacrylate, methacryl of glycidyl methacrylate The compound which added acid anhydride, such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, to the hydroxyl-containing unsaturated compound like an acid adduct is also mentioned.

Especially preferred is (meth) acrylic acid.

These may be used individually by 1 type, and may mix and use 2 or more types.

As a method of reacting the epoxy group in the component (a '') with the component (b ''), a known method can be used. For example, tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride and benzyl may be used as the component (a '') and (b ''). Carboxylic acid can be added to an epoxy compound by making it react for several to several ten hours at reaction temperature of 50-150 degreeC in organic solvent using quaternary ammonium salts, such as triethylammonium chloride, pyridine, triphenylphosphine, as a catalyst.

The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight with respect to the reaction raw material mixture (the sum of the components (a '') and (b '')). Moreover, in order to prevent the superposition | polymerization during reaction, it is preferable to use a polymerization inhibitor (for example, metoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert- butylcatechol, phenothiazine, etc.). And the usage-amount is preferably 0.01-10 weight% with respect to reaction raw material mixture, Especially preferably, it is 0.03-5 weight%.

The ratio which adds (b ") component to the epoxy group of (a") component is 90-100 mol% normally. Since the residual of the epoxy group tends to adversely affect the storage stability, the component (b '') is usually 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the component (a ''). It is preferable to carry out.

(3) polybasic acids and anhydrides thereof (c '')

At least one of a polybasic acid and its anhydride (c ") (Hereinafter, it may be called a" (c ") component" or a "polybasic acid (anhydride).), At least one of a dibasic acid and its anhydride. At least one of "basic acid (anhydride)"), tribasic acid and anhydride thereof (hereinafter referred to as "tribasic acid (anhydride)"), at least one of tetrabasic acid and its anhydride (hereinafter referred to as "4 Basic acids (anhydrides) ”and the like.

As a tetrabasic acid (anhydride) (at least one of tetracarboxylic acid and its anhydride), a well-known thing can be used, For example, a pyromellitic acid, a benzophenone tetracarboxylic acid, a biphenyl tetracarboxylic acid, a biphenyl Tetracarboxylic acids, such as ether tetracarboxylic acid, or these dihydrides, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

As tetrabasic acid (anhydride), biphenyl tetracarboxylic acid or its anhydride is especially preferable among the said exemplary compounds.

Molecular weight increases by a crosslinking reaction by making tetrabasic acid (anhydride) react with the reaction product of (a ") component and (b") component as (c ") component. For this reason, there exists an effect, such as the improvement of adhesiveness with respect to a board | substrate, control of solubility, improvement of a sensitivity, alkali resistance, etc., and is preferable.

As a dibasic acid (anhydride) (at least one of dicarboxylic acid and its anhydride), for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorine Lend acid, methyltetrahydrophthalic acid, these anhydrides, etc. are mentioned. Especially, tetrahydrophthalic acid, succinic acid, or these anhydrides are preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

The solubility is easily controlled by reacting the dibasic acid (anhydride) as the component (c '') with the reactant of the component (a '') and component (b ''), and thus the adhesion to the substrate is improved. Do.

As tribasic acid (anhydride) (at least one of a tricarboxylic acid and its anhydride), trimellitic acid, hexahydro trimellitic acid, or these anhydrides are mentioned. In particular, trimellitic anhydride and hexahydro trimellitic anhydride are preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

By using tribasic acid (anhydride) as the component (c ''), the molecular weight of the alkali-soluble resin (A '') can be increased to introduce branch into the molecule, and the molecular weight and viscosity can be balanced. Moreover, the amount of acid groups introduced into the molecule can be increased, and a balanced resin such as sensitivity and adhesion can be obtained.

It is preferable to use tetrabasic acid (anhydride) especially as a (c ") component. In this case, the addition rate of tetrabasic acid (anhydride) is usually 10 to 100 mol%, preferably 20 to 100 mol% with respect to the hydroxyl group produced when the component (b '') is added to the component (a ''). More preferably, it is 30-100 mol%. By making the addition rate of tetrabasic acid (anhydride) which is (c ") component more than the said lower limit, sufficient solubility of alkali-soluble resin (A") and favorable adhesiveness to a board | substrate can be ensured.

Moreover, it is preferable to replace a part of tetrabasic acid (anhydride) mentioned above by dibasic acid (anhydride) from a viewpoint of viscosity adjustment or solubility adjustment of a coloring photosensitive composition.

When tetrabasic acid (anhydride) and dibasic acid (anhydride) are used together as a component (c ''), the molar ratio is dibasic acid (anhydride): tetrabasic acid (anhydride) = 99: 1-20:80 It is preferable that it is 80: 20-30: 70, and it is more preferable. By making the ratio of tetrabasic acid (anhydride) more than the said lower limit, high film | membrane physical property of the coating film obtained can be obtained, and also making bibasic acid (anhydride) more than the said lower limit, the viscosity rise of the resin solution obtained is suppressed, 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 obtain various balances such as molecular weight, viscosity, sensitivity and adhesion, tetrabasic acid (anhydride) and two base It is preferable to use together at least one of an acid (anhydride) and a tribasic acid (anhydride).

In the case where at least one of tetrabasic acid (anhydride) and dibasic acid (anhydride) and tribasic acid (anhydride) are used together as the component (c ''), the amount of the tribasic acid (anhydride) used is less effective. Since alkali resistance may fall, the usage-amount of a tribasic acid (anhydride) is 5-70 mol% normally with respect to the hydroxyl group produced when adding (b ") component to (a") component, Preferably Preferably it is about 10-40 mol%.

The sum total of the addition rate of (c ") component is 10-100 mol% normally with respect to the hydroxyl group produced when adding (b") component to (a ") component, Preferably it is 20-100 mol%, More preferably, it is 30-100 mol%. By making the addition rate of (c ") component more than the said lower limit, the solubility of alkali-soluble resin (A") and adhesiveness with respect to a board | substrate become more favorable.

In addition, the component (c '') reacts with the hydroxyl group generated when the component (b '') is added to the component (a ''), and the component (b '') is added to the component (a ''). When adding and mixing the polyhydric alcohol (d '') mentioned later to this, you may make it react with respect to any hydroxyl group which exists in this mixture.

After adding (b '') component to (a ") component, or after mixing the polyhydric alcohol (d") mentioned later to this, it is well-known as a method of adding (c ") component. The method can be used.

The reaction temperature is 80-130 degreeC normally, Preferably it is 90-125 degreeC. When reaction temperature exceeds 130 degreeC, superposition | polymerization of one part of unsaturated groups in (b '') component may arise, and it may lead to the rapid increase of molecular weight. Moreover, when it is less than 80 degreeC, reaction does not progress smoothly and there exists a possibility that a (c ") component remains.

(4) polyhydric alcohol (d``)

The binder resin used by this invention is a polyhydric alcohol (d ") (hereinafter, a" (d ") component further to the reaction material which adds (b") component to the above-mentioned (a ") component. Alkali-soluble resin (A1 ") obtained by mixing and mixing the above-mentioned (c") component with respect to any hydroxyl group which exists in these mixtures may be sufficient.

As the component (d ''), for example, one or two selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylol ethane and 1,2,3-propanetriol It is preferable that it is a polyhydric alcohol of more than a species.

By using the (d '') component, the molecular weight of alkali-soluble resin (A1 ") can be increased, a branch can be introduce | transduced into a molecule | numerator, and the molecular weight and viscosity can be balanced. Moreover, the introduction rate of the acid group in a molecule | numerator can be increased, and the balanced organic binder, such as a sensitivity and adhesiveness, can be obtained.

If the amount of the component (d '') is too small, the effect is small. If the amount of the component (d '') is too large, thickening or gelation may occur. Pear, Preferably it is 0.02-0.2 weight times.

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

The acid value of alkali-soluble resin (A ") and (A1") obtained in this way is 10 mg-KOH / g or more normally, Preferably it is 50 mg-KOH / g or more. In order to expand good developability, it is preferable that an acid value is more than the said lower limit, and also it is sufficient to ensure sufficient alkali tolerance of a coloring photosensitive composition (that is, it does not produce the roughening or film | membrane reduction of the pattern surface by alkaline developing solution). It is preferable that it is 200 mg-KOH / g or less, and, as for an acid value, it is more preferable that it is 150 mg-KOH / g or less.

It is preferable that the weight average molecular weight (Mw) of standard polystyrene conversion by the gel permeation chromatography (GPC) measurement of alkali-soluble resin (A ") and (A1") is 1,500 or more, and it is more preferable that it is 2,000 or more. Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less. By making a weight average molecular weight more than the said lower limit, a sensitivity, coating film strength, alkali tolerance, etc. become more favorable. Moreover, when it is below the said upper limit, favorable developability and resoluble property can be obtained.

<Alkali-soluble resin (A)>

Alkali-soluble resin (A) is obtained by making the reaction material of specific epoxy resin (a) and unsaturated group containing carboxylic acid (b) further react with at least one of polybasic acid and its anhydride (c).

(1) epoxy resin (a)

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

[Formula 6]

[In the said general formula (1-a), n represents an average value and shows the number of 0-10. R ⁴¹ 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. In addition, some R <^{41> which} exists in 1 molecule may be same or different, respectively. G represents a glycidyl group]

R ⁴¹ in General Formula (1-a) represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. And from the viewpoint of solubility, R ⁴¹ is particularly preferably a hydrogen atom or a methyl group. In addition, some R ⁴¹ in one molecule may be the same or different.

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

[Formula 7]

(In formula, n and R ⁴¹ represent the same meaning as in general formula (1-a).)

The compound represented by the said General formula (1-a-1) can be obtained by condensation-reacting the compound and phenol which are represented by following General formula (1-a-2), for example in presence of an acid catalyst.

[Formula 8]

(Wherein Z represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R ⁴¹ represents the same meaning as that in General Formula (1-a))

In Z of the said General formula (1-a-2), a halogen atom is a chlorine atom, a bromine atom, etc., and a lower alkoxy group has a C1-C4 alkoxy group, such as a methoxy group and an ethoxy group, as a preferable group, respectively. Can be mentioned.

Phenols are aromatic compounds having one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, and Typical o-, m-, p- isomers, or cyclopentyl phenol, cyclohexyl phenol, cyclohexyl cresol, etc. of alkyl phenols, which are representative examples of elenole, methyl butyl phenol, di-t-butyl phenol, etc. Substituted phenols substituted by the group listed as R <^41> in said general formula (1-a), such as cycloalkyl phenol or phenyl phenol which are mentioned, are mentioned. These phenols can be used individually by 1 type or in combination of 2 or more type.

When performing the said condensation reaction, the usage-amount of phenols becomes like this. Preferably it is 0.5-20 mol, Especially preferably, it is 2-15 mol with respect to 1 mol of compounds represented by general formula (1-a-2).

In the condensation reaction, an acid catalyst is preferably used, and various kinds of acid catalysts can be used, but hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride and the like are preferable. In particular, p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are preferable. Although the usage-amount of these acid catalysts is not specifically limited, It is preferable to use 0.1-30 weight% with respect to the compound represented by general formula (1-a-2).

The condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Toluene, xylene, methyl isobutyl ketone, etc. are mentioned as a specific example at the time of using an organic solvent. As for the usage-amount of the organic solvent, 50-300 weight% is preferable with respect to the total weight of the injected raw material, and 100-250 weight% is especially preferable. 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 | finish of reaction, neutralization treatment or water washing treatment is performed, and pH value of a product is adjusted to 3-7, Preferably it is 5-7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia and sodium dihydrogen phosphate, diethylenetriamine, triethylenetetramine, aniline and phenylene What is necessary is just to use various basic substances, such as organic amines, such as diamine, as a neutralizing agent. Moreover, what is necessary is just to perform a water washing process in accordance with a conventional method. For example, the method of adding the water which melt | dissolved the said neutralizing agent in the reaction mixture, and repeating a liquid extraction operation can be employ | adopted.

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

As a method of obtaining the epoxy resin (a) which concerns on this invention represented by the said General formula (1-a) from the compound represented by the said General formula (1-a-1), a well-known method can be employ | adopted. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are added to a dissolved mixture of a compound represented by the general formula (1-a-1) and epihalohydrin such as excess epichlorohydrin and epibrohydrin. The epoxy resin (a) represented by general formula (1-a) can be obtained by adding beforehand or making it react for 1 to 10 hours at the temperature of 20-120 degreeC.

In the reaction for obtaining the epoxy resin (a), the alkali metal hydroxide may be an aqueous solution, and in that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and continuously under reduced pressure or under normal pressure. Water and epihalohydrin may be distilled and separated, water may be removed, and epihalohydrin may be continuously returned into the reaction system.

Further, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzyl ammonium chloride are added as a catalyst to a dissolution mixture of the compound represented by the general formula (1-a-1) and epihalohydrin, Solid or aqueous solution of an alkali metal hydroxide is added to the halohydrin etherate of the compound represented by general formula (1-a-1) obtained by making it react at 50-150 degreeC for 1 to 5 hours, and also 20-120 degreeC It may be a method of reacting at a temperature for 1 to 10 hours to dehydrohalide (close ring).

The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, with respect to 1 equivalent of the hydroxyl group of the compound represented by General Formula (1-a-1). Moreover, the usage-amount of alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by general formula (1-a-1), Preferably it is 0.9-11 mol.

In addition, in order to advance the reaction smoothly, in addition to 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. When using alcohols, the usage-amount is 2-20 weight% with respect to the quantity of epihalohydrin, Preferably it is 4-15 weight%. Moreover, when using an aprotic polar solvent, the usage-amount is 5-100 weight% with respect to the quantity of epihalohydrin, Preferably it is 10-90 weight%.

After washing the reaction product of such an epoxidation reaction with or without washing with water, for example, epihalohydrin or other additive solvent under conditions of 110 to 250 ° C and a pressure of 1.3 Pa (10 mmHg) or less. The target epoxy resin (a) is obtained by removing the like.

Moreover, in order to set it as the epoxy resin with less hydrolysable halogen, the obtained epoxy resin is melt | dissolved again in solvents, such as toluene and methyl isobutyl ketone, and aqueous solution of alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, is added and reaction is performed. Thus, the ring closure can be assured. In this case, the usage-amount of alkali metal hydroxide becomes like this. Preferably it is 0.01-0.3 mol with respect to 1 equivalent of hydroxyl groups of the compound represented by general formula (1-a-1) used for epoxidation, Especially preferably, it is 0.05-0.2 mol. Reaction temperature is 50-120 degreeC, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and then the solvent, such as toluene and methyl isobutyl ketone, is distilled off under heating pressure reduction, and the epoxy resin (a) represented by the said General formula (1-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-, and p-vinyl. Benzoic acid, monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2-acryloyloxyethyladip Acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxy Propyl succinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acrylo Iloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acrylic Ε-caprolactone, β-propiolactone, γ-buty on royloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid (Anhydrous) succinic acid, (anhydride) phthalic acid, to a monomer to which lactones, such as a rolactone and (delta) -valerolactone, were added, or hydroxyalkyl (meth) acrylate and pentaerythritol tri (meth) acrylate The monomer which added acid (anhydride), such as maleic anhydride, (meth) acrylic-acid dimer, etc. are mentioned.

Among them, (meth) acrylic acid is particularly preferable in terms of sensitivity. These may be used individually by 1 type and may use 2 or more types together.

(3) Reaction of epoxy resin (a) and unsaturated group containing carboxylic acid (b)

A well-known method can be used as a method of making an epoxy group in an epoxy resin (a) react with an unsaturated group containing carboxylic acid (b). For example, tertiary amines, such as triethylamine and benzylmethylamine, dodecyl trimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, etc., for an epoxy resin (a) and an unsaturated group containing carboxylic acid (b), Carboxylic acid can be added to an epoxy resin by making it react for several to several ten hours at reaction temperature of 50-150 degreeC in an organic solvent using quaternary ammonium salts, such as benzyl triethylammonium chloride, pyridine, and triphenylphosphine as a catalyst. .

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 epoxy resin (a) and the unsaturated group-containing carboxylic acid (b)).

Moreover, in order to prevent the superposition | polymerization in reaction, using a polymerization inhibitor (for example, metoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert- butylcatechol, phenothiazine, etc.) Preferably, the amount of use thereof is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight based on the reaction raw material mixture.

The ratio which adds an unsaturated group containing carboxylic acid (b) to the epoxy group of an epoxy resin (a) is 90-100 mol% normally. Since the remainder of the epoxy group adversely affects the storage stability, the unsaturated group-containing carboxylic acid (b) is usually reacted at a ratio of 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin (a). It is desirable to.

(4) polybasic acids and anhydrides thereof (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. , Hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chloric acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicar Dibasic carboxylic acids such as acids or anhydrides thereof; And polybasic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and biphenyltetracarboxylic acid, or anhydrides thereof. Especially, tetrahydro phthalic anhydride or succinic anhydride is mentioned preferably. These may be used individually by 1 type and may use 2 or more types together.

The addition rate of at least one of a polybasic acid and its anhydride (c) is 10-100 mol% normally, Preferably it is 20-100 of the hydroxyl group produced when adding unsaturated group containing carboxylic acid (b) to an epoxy resin (a). 100 mol%, More preferably, it is 30-100 mol%. When this addition rate is too large, the residual film rate at the time of image development may fall, and when too small, it may be insufficient in solubility or adhesiveness with respect to a board | substrate. Moreover, when using polybasic acid and its anhydride together, the said addition rate shows the addition rate of the sum total of polybasic acid and its anhydride.

After adding unsaturated group containing carboxylic acid (b) to the said epoxy resin (a), a well-known method can be used as a method of adding at least one of a polybasic acid and its anhydride (c).

In addition, in this invention, after adding at least one of polybasic acid and its anhydride (c) in this way, you may add an epoxy group containing compound (d) to a part of produced | generated carboxyl group. In this case, as an epoxy group containing compound (d), in order to improve light sensitivity, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, the glycidyl ether compound which has a polymerizable unsaturated group, etc. In order to add an epoxy group containing unsaturated compound or to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group, and may use both together. As a specific example of the glycidyl ether compound which does not have a polymerizable unsaturated group, the glycidyl ether compound which has a phenyl group or an alkyl group (manufactured by Nagase Chemical Co., Ltd., brand name: Denacol EX-111, Denacol EX-121, Dena Call EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192).

Alkali-soluble resin (A) which concerns on this invention is the resin obtained by making the reaction material of the above-mentioned epoxy resin (a) and unsaturated group containing carboxylic acid (b) further react at least one among polybasic acid and its anhydride (c). And resin obtained by adding such epoxy group containing compound (d) to a part of carboxyl groups may be sufficient.

(5) Physical properties of alkali-soluble resin (A), etc.

The weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) of alkali-soluble resin (A) used by this invention is 1500 or more normally, Preferably it is 2000 or more, Usually 50000 or less, Preferably Preferably it is 30000 or less, More preferably, it is 10000 or less. If the weight average molecular weight of this alkali-soluble resin (A) is too small, sensitivity will be inferior, and if too large, it will not be preferable because it will lack the solubility to a developing solution.

Moreover, the acid value (mgKOH / g) of alkali-soluble resin (A) used by this invention is 10 or more normally, Preferably it is 50 or more, Usually 200 or less, Preferably it is 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 property of the coating film tends to be deteriorated.

Moreover, condensation reaction of the compound represented by the said General formula (1-a-2) and phenolic compound, reaction of the compound represented by the said General formula (1-a-1) obtained by the condensation reaction, and epihalohydrin Synthesis reaction of alkali-soluble resin (A), such as addition reaction with at least one of unsaturated group containing carboxylic acid (b) and polybasic acid, and its anhydride (c), can be performed by a well-known method, For example, Japan It can carry out by the method of Unexamined-Japanese-Patent No. 2005-55814.

<Alkali Soluble Resin (A ')>

As another example of what is especially preferable as binder resin in this invention, the reaction product of the epoxy compound (a ') represented by the following general formula (1-a'), and unsaturated group containing carboxylic acid (b ') is a polybasic acid and Alkali-soluble resin (A ') obtained by making it react with at least one among the anhydrides (c') is mentioned.

[Formula 9]

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

(1) Epoxy compound (a ') represented by general formula (1-a')

First, the epoxy compound (a ') (Hereinafter, it may be called "(a') component") represented by the said General formula (1-a ') is demonstrated.

In said general formula (1-a '), as an alkyl group of R <^31> and R <^32> , a C1-C10 alkyl group is preferable and Cl, Br, F etc. are mentioned as a halogen atom. R ³¹ and R ³² each independently represent an alkyl group having 1 to 5 carbon atoms.

Although the details of the functional mechanism of the alkyl group and the halogen atom of R ³¹ and R ³² are not clear, it is assumed that the three-dimensional structure of the molecule is influenced to control the solubility in the developer.

Therefore, from the said viewpoint, although p and q in the said general formula (1-a ') respectively independently represent the integer of 0-4, Preferably it is 1 or 2.

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

[Formula 10]

or

[Formula 11]

The o-position is preferred for.

In addition, although the same group may be sufficient as R <^31> and R <^32> , it is preferable that it is the same group from a manufacturing cost point.

Examples of the alkylene group for R ³³ and R ³⁴ include an alkylene group having 1 to 10 carbon atoms, particularly preferably an ethylene group or a propylene group each independently.

Although x and y respectively independently represent the integer of 0 or more, Usually, it is 0-6, Preferably it is 0-3. Generally, x and y are solubility so that it is large, but when too large, there exists a possibility that a sensitivity may fall.

In addition, although the same group may be sufficient as R <^33> and R <^34> , it is preferable that it is the same group from a cost of manufacture.

The molecular weight of these (a ') components is the weight average molecular weight (Mw) of standard polystyrene conversion by the gel permeation chromatography (GPC) measurement, and is 200-200,000 normally, Preferably it is the range of 300-100,000. By making molecular weight more than a lower limit, film formation property becomes favorable, and also by below an upper limit, the gelation at the time of addition reaction, such as unsaturated group containing carboxylic acid (b ') mentioned later, is suppressed.

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

Examples of the unsaturated group-containing carboxylic acid (b ') (hereinafter may be referred to as "(b') component") include <alkali-soluble resin (A '')> and <alkali-soluble resin (A1 '')>. The compound similar to what was listed as unsaturated group containing carboxylic acid (b ") can be used. Among these, (meth) acrylic acid is preferable in (alpha), (beta)-unsaturated carboxylic acid, and acrylic acid is especially preferable because it is rich in reactivity. Among the α, β-unsaturated carboxylic acid esters having a carboxyl group in the ester moiety, 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethyl maleic acid are preferable.

The amount of the 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, based on 1 equivalent of the epoxy group of the component (a').

By making the usage-amount of (b ') component more than a lower limit, a sufficient amount of unsaturated group can be introduce | transduced and reaction with at least one of the following polybasic acid and its anhydride (c') also becomes enough. Moreover, it is also preferable that a large amount of epoxy groups do not remain. By setting the usage-amount of (b ') component below an upper limit, it is preferable at the point which does not remain as an unreacted material. By satisfy | filling the said range, high photocuring characteristic can be obtained.

(3) polybasic acids and anhydrides thereof (c ')

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

The addition ratio of at least one of the polybasic acid and its anhydride (c ') is preferably such that the acid value of the alkali-soluble resin (A') finally obtained is 10 to 150 mg-KOH / g, and 20 to 140 mg-KOH / g. More preferably. By making an acid value more than the said lower limit, alkali developability becomes favorable, and sufficient photocurability is obtained by below an upper limit.

Moreover, you may add polyfunctional alcohol (d '), such as trimethylol propane, pentaerythritol, and dipentaerythritol, and introduce | transduced a multi-branched structure at the time of addition reaction of this (c') component. Examples of the polyhydric alcohol (d ') include the same compounds as described above as the polyhydric alcohol (d' ') in <alkali-soluble resin (A' ') and alkali-soluble resin (A1' '). , Preferred compounds and preferred amounts of use are also the same.

Synthetic reaction of alkali-soluble resin (A '), such as addition reaction of the unsaturated group containing carboxylic acid (b') and polybasic acid, and its anhydride (c ') with respect to an epoxy compound (a'), is all well-known methods The method can be carried out with reference to the methods described in, for example, JP 2005-126685, JP 2005-325331 A, JP 2006-241224 A, and the like.

The weight average molecular weight (Mw) of standard polystyrene conversion by the gel permeation chromatography (GPC) measurement of alkali-soluble resin (A ') is 1,000 or more normally, Preferably it is 1,500 or more, Usually 30,000 or less, Preferably it is 20,000 Or less, more preferably 10,000 or less, particularly preferably 8,000 or less. Developability becomes favorable by carrying out a weight average molecular weight below the said upper limit, and alkali resistance becomes favorable by carrying out more than a lower limit.

<Alkali Soluble Resin (A '' ')>

As another example of particularly preferable binder resin in the present invention, a reactant of an epoxy resin (a '' ') and an unsaturated group-containing carboxylic acid (b' '') represented by the following general formula (1-a '' '): Alkali-soluble resin (A '") obtained by making it react with at least one of polybasic acid and its anhydride (c'") is mentioned.

[Formula 12]

[In the general formula (1-a '''), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵² represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms, and 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 ratio of each repeating unit, and t≥z≥0.5 t.]

In General Formula (1-a '''), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but among them, from the viewpoint of photocurability, preferably a hydrogen atom or a methyl group. Moreover, although s represents 1 or 2, Preferably it is 1.

R ⁵² represents a C 5-16 divalent polycyclic hydrocarbon group. Such a group is made from an unsaturated polycyclic hydrocarbon ring compound having at least two carbon-carbon double bonds in the same skeleton (hereinafter, may be simply referred to as an "unsaturated polycyclic hydrocarbon compound") and subjected to the reaction described later. It can form by doing.

As an unsaturated polycyclic hydrocarbon ring compound used as a raw material, although the following compounds are mentioned, for example, it is not limited to these.

[Formula 13]

Among these, a crosslinked carbon ring is more preferable and dicyclopentadiene is especially preferable.

The epoxy resin (a '' ') represented by said general formula (1-a' ") glycidylates the hydroxyl group of the polyaddition reaction of the unsaturated polycyclic hydrocarbon compound mentioned above and the phenol type compound represented by the following general formula. Can be obtained.

[Formula 14]

[In the general formula, R ⁵¹ and s have the same meaning as the definition in the general formula (1-a ''').]

As an epoxy resin (a '"), the compound represented by the following general formula (1-a'"-1) formed by glycidylating the dicyclopentadiene and the polyaddition reaction of the said phenolic compound is especially preferable. .

[Formula 15]

[In the general formula (1-a '''-1), R ⁵³ , R ⁵⁴ , t and z have the same meaning as the definition in the general formula (1-a''').]

The introduction ratio of the glycidyl group in the said general formula (1-a '' ') and general formula (1-a' ''-1) is 50-100 in the phenolic hydroxyl group in the said phenol resin before glycidylation. Mole%, ie, t and z in the general formulas (1-a '' ') and (1-a' ''-1) must have a relationship of t? Z? 0.5 t, Preferably, 70-100 mol% is substituted by the glycidyl group.

Alkali-soluble resin (A '' ') is a polybasic acid which reacts the reaction product of the epoxy resin (a' ") represented by the said general formula (1-a" '), and unsaturated group containing carboxylic acid (b' "). And resin obtained by reacting with at least one of the anhydrides (c '' ').

As unsaturated group containing carboxylic acid (b '"), it lists as unsaturated group containing carboxylic acid (b") in <alkali-soluble resin (A "), alkali-soluble resin (A1")>. The same compound as that used can be used, and a preferable compound and its reason are also the same as above.

The ratio which adds an unsaturated group containing carboxylic acid (b '") to the epoxy group of an epoxy resin (a'") is 90-100 mol% normally. Since the residual of the epoxy group adversely affects the storage stability, the unsaturated group-containing carboxylic acid (b '' ') is usually 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, to 1 equivalent of the epoxy group of the epoxy resin (a' ''). It is preferable to carry out the reaction at the ratio of.

As the polybasic acid and its anhydride (c '' '), the same compounds as those listed as the polybasic acid and the anhydride (c' ') in <alkali-soluble resin (A' ') and alkali-soluble resin (A1' ')> These are mentioned, A preferable compound and the reason are also the same as the above.

The addition rate of at least one of a polybasic acid and its anhydride (c '") is 15-15 normally of the hydroxyl group produced when adding unsaturated group containing carboxylic acid (b'") to an epoxy resin (a '"). It is 100 mol%, Preferably it is 20-90 mol%, It is preferable that the acid value of alkali-soluble resin (A '") finally obtained becomes 45-160 mg-KOH / g. By making this addition rate below the said upper limit, the fall of the residual film rate at the time of image development can be prevented, and making it more than the said lower limit can provide favorable solubility and adhesiveness with respect to a board | substrate. In addition, when using polybasic acid and its anhydride together, the said addition rate shows the addition rate of the sum total of a polybasic acid and its anhydride.

Reaction of unsaturated polycyclic hydrocarbon compound with phenolic compound and glycidylation reaction of hydroxyl group in phenol resin obtained by the reaction, unsaturated group-containing carboxylic acid (b '' ') and polybasic acid and anhydride thereof (c' '' Synthesis reaction of alkali-soluble resin (A '' '), such as at least one addition reaction, can be performed by a well-known method, For example, with reference to the method of Unexamined-Japanese-Patent No. 5-214048 It can be carried out.

The weight average molecular weight of alkali-soluble resin (A '") is 1,500-4,000 normally, Preferably it is 2,000-3,500, More preferably, it is 2,500-3,000. When the weight average molecular weight is too small, there may be a problem that the development solubility is too high, and when too large, the problem that the development solubility is too low may occur.

In this invention, these binder resins may be used individually by 1 type, and may use 2 or more types together.

As binder resin in the coloring photosensitive composition of this invention, in the said alkali-soluble resin (A), (A '), (A "), (A'"), (A1 "), Alkali-soluble resins (A) and (A '' ') are preferable from the viewpoint of balance between control and adhesion to the substrate.

Content of binder resin is 5 weight% or more normally, Preferably it is 10 weight% or more with respect to the total solid of the coloring photosensitive composition of this invention, Usually it is 80 weight% or less, Preferably it is 70 weight% or less. By making content of binder resin more than the said lower limit, control of a shape and a level | step difference becomes possible, and the solubility with respect to the developing solution of an unexposed part can also be ensured. Moreover, by making it below the said upper limit, generation | occurrence | production of the wrinkle by the excessive shrinkage at the time of thermosetting can be suppressed.

[3] polymerizable monomers

In this invention, a photoinitiator is used with photopolymerizable monomers, such as an ethylenically unsaturated compound.

As an ethylenically unsaturated compound used here, although the compound which has one or more ethylenically unsaturated bond in a molecule | numerator is meant, the difference of polymerizability, crosslinkability, and the solubility of the developing solution of the exposure part and the non-exposure part accompanying it can be expanded. It is preferable that it is a compound which has two or more ethylenically unsaturated bonds in a molecule | numerator from a viewpoint of etc., Moreover, the (meth) acrylate compound which the ethylenically unsaturated bond originates from a (meth) acryloyloxy group is more preferable. .

In addition, the use of a compound having three or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint of voltage retention.

As a compound which has one or more ethylenically unsaturated bonds in a molecule, For example, Unsaturated carboxylic acid, such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, a citraconic acid, and its alkyl ester , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

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

As ester of an unsaturated carboxylic acid and a polyhydroxy compound, the following compounds are mentioned specifically ,.

The reactant of an unsaturated carboxylic acid and a sugar alcohol; Specifically, the sugar alcohol is ethylene glycol, polyethylene glycol (additional number 2-14), propylene glycol, polypropylene glycol (additional number 2-14), trimethylene glycol, tetramethylene glycol And hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.

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

The reactant of unsaturated carboxylic acid and alcohol amine; Alcohol amine specifically, diethanolamine, triethanolamine, etc. are mentioned.

Specific esters of unsaturated carboxylic acids and polyhydroxy compounds are as follows.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Propaneethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythrate Lithitol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and the same crotonate, isoctoto Nate, Maleate, Itaconate, Citraconate, etc.

Other esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or ethylene oxide adducts thereof. And reactants. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like; A reaction product of the same unsaturated carboxylic acid with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (3) of tris (2-hydroxyethyl) isocyanurate Reaction products of unsaturated carboxylic acids, polyhydric carboxylic acids, and polyhydroxy compounds such as meth) acrylates and tri (meth) acrylates, for example, condensates of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth ) Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin. .

As (meth) acryloyloxy-group containing phosphate, what is represented by following General formula (6), (7), (8) is preferable.

[Formula 16]

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

Here, it is preferable that e and g are 1-10, especially 1-4, As these specific examples, it is (meth) acryloyloxyethyl phosphate and bis [(meth) acryloyloxyethyl] phosphate, for example. And (meth) acryloyloxyethylene glycol phosphate, and the like, each of which may be used alone or as a mixture.

As urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethane tri ( Hydroxy (meth) acrylate compounds such as meth) acrylate, aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyl octane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, Aromatic polyisocyanates, such as alicyclic polyisocyanate, such as 4, 4- methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate, 4, 4- diphenylmethane diisocyanate, and tris (isocyanate phenyl) thiophosphate Complexes such as isocyanates and isocyanurates The reactant with polyisocyanate compounds, such as cyclic polyisocyanate, etc. are mentioned.

As such a thing, the brand names "U-4HA", "UA-306A", "UA-MC340H", "UA-MC340H", "U6LPA" by Shin-Nakamura Chemical Co., Ltd., etc. are mentioned, for example.

Among these, compounds having four or more urethane bonds [-NH-CO-O-] and four or more (meth) acryloyloxy groups in one molecule are preferable, and the compound is, for example, pentaerythritol, Compound obtained by making diisocyanate compounds, such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate, react with the compound which has four or more hydroxyl groups in 1 molecule, such as polyglycerol, or ethylene glycol In the compound which has two or more hydroxyl groups in 1 molecule, such as "Duranate 24A-100" by Asahi Kasei Kogyo Co., Ltd. "Duranate 22A-75PX", "Duranate 21S-75E", "Duranate 18H-" 1 such as burette type such as 70B ", copper" duranate P-301-75E ", copper" duranate E-402-90T ", adduct type such as" duranate E-405-80T " 4 or more, preferably 6 or more isocyanate groups in 1 molecule, such as a compound obtained by making the compound which has three or more isocyanate groups react in a molecule | numerator, or the compound obtained by superposing | polymerizing or copolymerizing isocyanate ethyl (meth) acrylate etc. The compound which has, for example, "Duranate ME20-100" by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) A compound having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as acrylate and dipentaerythritol penta (meth) acrylate, can be obtained by reacting have.

As epoxy (meth) acrylates of a (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound, For example, (meth) acrylic acid or the same hydroxy (meth) acrylate compound, (Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neo Pentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropanepolyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl Aliphatic polyepoxy compounds such as ether, phenol novolac polyepoxy compound, brominated phenol novolac polyepoxy compound, (o-, m-, p-) cresol novolac polyepoxy compound, bispe Aromatic polyepoxy compounds such as A polyepoxy compound, bisphenol F polyepoxy compound, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate And reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds.

Other ethylenically unsaturated compounds, in addition to the above, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate , Thioether bond-containing compounds which improve the crosslinking rate by sulfiding ether bonds of ether bond-containing ethylenically unsaturated compounds with phosphorus penta sulfide and the like to thioether bonds, and for example, Japanese Patent Nos. 3164407 and Japan Polyfunctional (meth) acrylate compound described in Unexamined-Japanese-Patent No. 9-100111 etc., and silica sol of 5-30 nm of particle diameters [For example, isopropanol dispersion organosilica sol ("IPA-ST" by Nissan Chemical company) ), Methyl ethyl ketone dispersion organosilica sol ("MEK-ST" made by Nissan Chemical Co., Ltd.), methyl isobutyl ketone dispersion organosilica sol (Nissan chemical Hardened | cured material by making a silica sol react with a silane coupling agent through ethylsilane unsaturated compound, such as a compound which manufactured "MIBK-ST") etc.], and the compound which couple | bonded using the isocyanate group or the mercapto group containing silane coupling agent. Examples thereof include compounds having improved strength and heat resistance.

In this invention, ester (meth) acrylates or urethane (meth) acrylates are preferable as ethylenically unsaturated compound, Especially, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta Particularly preferred are those having five or more functional groups such as (meth) acrylates.

Each of the above ethylenically unsaturated compounds may be used alone, or two or more thereof may be used in combination.

The ratio of the photopolymerizable monomer in the coloring photosensitive composition of this invention is 1-60 weight% normally with respect to all solid content, Preferably it is 5-40 weight%, Especially preferably, it is 12-30 weight%. If the ratio of the photopolymerizable monomer is too large than this range, the degree of curing decreases as the ratio of other components decreases, so the voltage retention tends to deteriorate. On the other hand, when too small, since the quantity of alkali resin increases, there exists a tendency for developability to fall.

[4] photopolymerization initiators

The photoinitiator is normally used as a mixture with an accelerator (photoinitiator type), and the sensitizing dye etc. which are added as needed are used together.

A photoinitiator type is a component which has a function which absorbs light directly, or sensitizes it, produces a decomposition reaction or a hydrogen drawing reaction, and produces | generates a polymerization active radical.

As a photoinitiator which comprises a photoinitiator type component, the various compounds of international publication 2008/153000 etc. can be used, for example.

As a photoinitiator used for the coloring photosensitive composition of this invention, Especially preferably, an oxime ester type compound is mentioned from the point which the generation efficiency of a polymerization active radical is good, Especially the compound illustrated below can be used preferably. .

[Formula 17]

[Formula 18]

As an example of the accelerator and the sensitizing dye which comprise a photoinitiator type component, the various compounds of international publication 2008/153000 etc. are mentioned, for example, A preferable compound is also the same as the compound of international publication 2008/153000. Do.

The content rate of a photoinitiator type component (mixture of a photoinitiator and an accelerator) is 0.1-40 weight% normally in the total solid in the coloring photosensitive composition of this invention, Preferably it is 0.5-30 weight%. If the content ratio is significantly low, the sensitivity to exposure light may be lowered. On the contrary, if the content ratio is significantly high, the solubility of the unexposed portion in the developing solution may be lowered, causing development failure.

The content rate of the sensitizing dye which occupies in the coloring photosensitive composition of this invention is 0-20 weight% normally in the total solid in a coloring photosensitive composition, Preferably it is 0-15 weight%, More preferably, it is 0-10 weight%.

[5] dispersants and dispersing aids

In order that the coloring photosensitive composition of this invention may improve the dispersibility of a pigment and the improvement of dispersion stability, it is preferable to use together at least one of a pigment dispersing agent and a dispersion adjuvant. Among them, in particular, the use of a polymer dispersant as the pigment dispersant is preferable because of its excellent dispersion stability over time. In addition, a polymer dispersing agent is a polymer completely different from a pigment in order to ensure the dispersion stability of a pigment, and a pigment derivative etc. which improve the dispersibility of a pigment with a dispersion aid.

Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. have. Specific examples of these dispersants include EFKA (manufactured by BASF Corporation), DisperBYK (manufactured by BICKEMICAL COMPANY), disparon (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (manufactured by Geneca Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), poly Flow (made by Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

These polymeric dispersants can be used individually by 1 type or in mixture of 2 or more types.

Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perylone and diketopy. Derivatives, such as a rolopyrrole system and a dioxazine system, are mentioned, Especially, a quinophthalone system is preferable. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and its quaternary salt, phthalimidomethyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group, etc. are directly in the pigment skeleton or an alkyl group, an aryl group, a heterocyclic group, or the like. And the thing bonded together, Preferably it is a sulfonic acid group. Moreover, these substituents may be substituted by two in one pigment skeleton.

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

These pigment derivatives can be used individually by 1 type or in combination of 2 or more type.

In the coloring photosensitive composition of this invention, content of at least one of a dispersing agent and a dispersal auxiliary agent is 5 weight% or more and 120 weight% or less normally with respect to a pigment, Preferably they are 5 weight% or more and 90 weight% or less, More preferably, 5 weight% or more and 60 weight% or less, and especially preferable ranges are 5 weight% or more and 40 weight% or less. If the content of the dispersing agent and the dispersing aid is too small, sufficient dispersibility may not be obtained. If the content of the dispersing agent and the dispersing agent is excessively large, the proportion of other components may be relatively reduced, and the voltage retention may be lowered. In addition, when using a dispersing agent and a dispersal auxiliary agent together, the said content shows content of the sum total of a dispersing agent and a dispersal auxiliary agent.

When using a pigment derivative, the usage-amount is 0.1-30 weight% normally with respect to the pigment in a coloring photosensitive composition, Preferably it is 0.1-20 weight%, More preferably, it is 0.1-10 weight%, More preferably, it is 0.1-5 % By weight.

[6] solvents

Generally, the coloring photosensitive composition of this invention is prepared by melt | dissolving or disperse | distributing solid content of the pigment, binder resin, photopolymerizable monomer, photoinitiator, dispersing agent, and dispersing adjuvant which are mentioned above, and the other component mentioned later in a solvent.

In the coloring photosensitive composition of this invention, a solvent has a function which melt | dissolves or disperse | distributes a pigment, binder resin, a photopolymerizable monomer, a photoinitiator, etc., and adjusts a viscosity.

As a solvent, it is preferable to select a thing whose boiling point is 100-300 degreeC. More preferably, it is a solvent which has a boiling point of 120-280 degreeC.

As such a solvent, the various solvents described in international publication 2008/153000 etc. are mentioned, for example.

These solvents may be used individually by 1 type, and may use 2 or more types together.

In particular, when forming a black photo spacer by the photolithography method, it is more preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. (under pressure 1013.25 [hPa] conditions. desirable. Especially preferably, it has a boiling point of 120-170 degreeC.

Among the solvents described in International Publication No. 2008/153000 and the like, glycol alkyl ether acetates are preferred in view of good balance of coating properties, surface tension, and the like and high solubility of the constituent components in the composition.

Moreover, although glycol alkyl ether acetates may be used independently, you may use another solvent together. As a solvent used together, especially preferable are glycol monoalkyl ethers. Especially, propylene glycol monomethyl ether is preferable at the point of the solubility of the component in a composition. Moreover, since glycol polar alkyl ethers have a high polarity and the addition amount is too large, the pigment tends to aggregate, and since the storage stability such as the viscosity of the colored photosensitive composition increases over time, there is a tendency to decrease the glycol monoalkyl ether in the solvent. 5 weight%-30 weight% are preferable, and, as for the ratio of ethers, 5 weight%-20 weight% are more preferable.

Moreover, it is also preferable to use together the organic solvent (henceforth a "high boiling point solvent") which has a boiling point of 150 degreeC or more. By using such a high boiling point solvent together, a colored photosensitive composition does not dry well, but there exists an effect which prevents the uniform dispersion state of the pigment in a composition from being destroyed by rapid drying. That is, there exists an effect which prevents generation | occurrence | production of the foreign material defect by precipitation and solidification, such as a color material, at the tip of a slit nozzle, for example. In view of such a high effect, among the various solvents described in the above-mentioned International Publication No. 2008/153000, in particular, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate and diethylene glycol mono Ethyl ether acetate is preferred.

3 weight%-50 weight% are preferable, as for the content rate of the high boiling point solvent in a solvent, 5 weight%-40 weight% are more preferable, 5 weight%-30 weight% are especially preferable. By carrying out quantity of a high boiling point solvent more than the said lower limit, the foreign material defect generation | occurrence | production can be prevented by precipitation and solidification, such as a pigment in a slit nozzle tip, for example, and the color filter manufacture mentioned later by making it below the said upper limit carries out In the process, it is possible to appropriately maintain the drying rate of the composition so as not to cause problems such as tact failure of the vacuum drying process and traces of pins of the prebaking.

Moreover, glycol alkyl ether acetates may be sufficient as the high boiling point solvent of boiling point 150 degreeC or more, and glycol alkyl ether may be sufficient in this case, In this case, you do not need to contain the high boiling point solvent of boiling point 150 degreeC or more separately.

As a preferable high boiling point solvent, For example, in the various solvent mentioned above, 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 diacetate, triacetin and the like.

Although the content of the solvent in the whole coloring photosensitive composition of this invention does not have a restriction | limiting in particular, Usually, it is 99 weight% or less, Usually it is 50 weight% or more, Preferably it is 55 weight% or more, More preferably, it is 60 weight% or more. By carrying out the ratio of a solvent below the said upper limit, solid content, such as a pigment, binder resin, a photopolymerizable monomer, can be contained in a coloring photosensitive composition in an amount sufficient as needed. Moreover, by using more than the said lower limit, thickening can be suppressed and favorable coatability and the film thickness uniformity of a coating film can be obtained.

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

[7] components, other

In addition to the above components, the colored photosensitive resin composition of the present invention may further contain a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improving agent, a plasticizer, a storage stabilizer, a surface protecting agent, an organic carboxylic acid, and an organic carboxyl. It may contain an acid anhydride, a developing improver, a thermal polymerization inhibitor, and the like.

[7-1] mine generators

A photoacid generator is a compound which can generate | occur | produce an acid by ultraviolet-ray, and a crosslinking reaction advances because there exists a crosslinking agent, such as a melamine compound, by the effect | action of the acid generate | occur | produced when exposing, for example. Among these photoacid generators, those having high solubility in solvents, particularly those in solvents used in colored photosensitive compositions, are preferable, and for example, diphenyl iodonium, ditolyl iodonium, phenyl (p-anisyl) iodine Nium, bis (m-nitrophenyl) iodium, bis (p-tert-butylphenyl) iodium, bis (p-chlorophenyl) iodium, bis (n-dodecyl) iodium, p-isobutylphenyl ( chlorides, bromides, or boron salts, hexafluoro of diaryl iodonium such as p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium such as triphenylsulfonium Sulfonium organic boron complexes such as phosphate salt, hexafluoroarsenate salt, aromatic sulfonate salt, tetrakis (pentafluorophenyl) borate salt, diphenylphenacylsulfonium (n-butyl) triphenylborate, and the like, Or 2-methyl-4,6-bistrichloromethyltriazine, 2 Triazine compounds, such as-(4-methoxyphenyl) -4,6-bistrichloromethyl triazine, etc. are mentioned, It is not limited to this.

These photoacid generators may be used individually by 1 type, and may use 2 or more types together.

When using a photoacid generator, 0-20 weight% is preferable with respect to the total solid of a coloring photosensitive composition, Especially preferably, it is 2-15 weight%.

[7-2] crosslinking agent

A crosslinking agent can be further added to the coloring photosensitive composition of this invention, For example, a melamine or guanamine type compound can be used. As these crosslinking agents, the melamine or guanamine type compound represented by the following general formula (XI) is mentioned, for example.

[Formula 19]

In which R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or aryl, 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 the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are mutually Independently a hydrogen atom or a —CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents a hydrogen atom or an alkyl group.)

Here, an aryl group is typically a phenyl group, 1-naphthyl group, or 2-naphthyl group, and substituents, such as an alkyl group, an alkoxy group, and a halogen atom, may be couple | bonded with these phenyl groups and naphthyl groups. The alkyl group and the alkoxy group may each be 1 to 6 carbon atoms. It is common that the alkyl group represented by R ⁶⁸ is a methyl group or an ethyl group, especially a methyl group among the above.

Melamine compounds corresponding to general formula (XI), that is, compounds of the following general formula (XI-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine and pentamethoxymethyl Melamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine and the like.

[Formula 20]

(Wherein 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, 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 an alkyl group.)

Moreover, in the guanamine type compound corresponding to general formula (XI), ie, the compound whose R <^61> in general formula (XI) is an aryl group, tetramethylol benzoguanamine, tetramethoxymethylbenzoguanamine, and trimethoxymethylbenzo Guanamine, tetraethoxymethylbenzoguanamine and the like.

Moreover, you may use the crosslinking agent which has a methylol group or a methylol alkyl ether group. Examples thereof are listed below.

2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro -1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether body, dimethylol trimethyleneurea or its dimethyl ether body, 3,5-bis (hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (common name dimethyloluron) or its dimethyl ether body, tetramethylolglyoxaldiurene or its tetramethyl ether body.

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

As for the quantity at the time of using a crosslinking agent, 0.1-15 weight% is preferable with respect to the total solid of a coloring photosensitive composition, Especially preferably, it is 0.5-10 weight%.

[7-3] Adhesion Enhancers

The colored photosensitive composition of the present invention may contain an adhesion promoter in order to sufficiently adhere thin lines and dots.

As an adhesion promoter, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent, and the like are preferable, and as the compound containing a nitrogen atom, for example, diamines (described in Japanese Patent Application Laid-Open No. 11-184080). Adhesion enhancers, etc.) and azoles are preferable. Among them, azoles are preferable, and in particular, imidazoles (adhesion enhancers described in JP-A-9-236923, others), benzoimidazoles, and benzotriazoles (adhesions described in JP-A-2000-171968). Improver, etc.) are preferable, and imidazole and benzoimidazole are the most preferable. Among them, 2-hydroxybenzoimidazole, 2-hydroxyethylbenzoimidazole, benzoimidazole, 2-hydroxyimidazole, imidazole, and the like in that blackening hardly occurs and adhesiveness can be greatly improved. Mercaptoimidazole and 2-aminoimidazole are preferred, and 2-hydroxybenzoimidazole, benzoimidazole, 2-hydroxyimidazole and imidazole are particularly preferred. As a kind of silane coupling agent, various things, such as an epoxy type, a methacryl type, and an amino type, can be used, Especially an epoxy type and an isocyanate type silane coupling agent are preferable.

These can be used individually by 1 type or in combination of 2 or more type.

When mix | blending these adhesion promoters, although the compounding ratio changes also with the kind of adhesion promoter to be used, it is preferable to set it as 0.01-5 weight%, especially 0.05-3 weight% with respect to the total solid of a coloring photosensitive composition. . If there is less than this, sufficient adhesive improvement effect may not be obtained, and when too large, developability may fall.

[7-4] sensitizing dyes

As a sensitizing dye, the xanthene dye of Unexamined-Japanese-Patent No. 4-221958, Unexamined-Japanese-Patent No. 4-219756, Unexamined-Japanese-Patent No. 3-239703, and 5-289335, for example. The coumarin pigment | dye which has a hetero ring of description, 3-ketokumarin compound of Unexamined-Japanese-Patent No. 3-239703, 5-289335, and pyrromethene of Unexamined-Japanese-Patent No. 6-19240. Dyestuffs, In addition, Unexamined-Japanese-Patent No. 47-2528, Unexamined-Japanese-Patent No. 54-155292, Unexamined-Japanese-Patent No. 45-37377, Unexamined-Japanese-Patent No. 48-84183, Unexamined-Japanese-Patent No. 52 -112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-open No. 60-88005, Japanese Patent Application Laid-open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57 -168088, Japanese Patent Application Laid-open No. Hei 5-107761, Japanese Patent Application Laid-open No. Hei 5-210240, Japan The pigment | dye which has the dialkyl aminobenzene skeleton of Unexamined-Japanese-Patent No. 4-288818, etc. are mentioned.

These can be used individually by 1 type or in combination of 2 or more type.

When mix | blending a sensitizing dye, the content rate of the sensitizing dye in the total solid in a coloring photosensitive composition is 0.01 to 5 weight% normally, Preferably it is 0.05 to 3 weight%. If there is less than this, a sensitization effect may not come out, and when too much, developability may fall.

[7-5] Surfactants

As the surfactant, one kind or two or more kinds of various kinds such as anionic, cationic, nonionic, and amphoteric surfactants can be used. However, nonionic surfactants are used because they are unlikely to adversely affect all properties. It is desirable to. In addition, fluorine-based or silicone-based ones are effective in terms of applicability.

When using surfactant, as the compounding ratio, it is 0.001-10 weight% normally with respect to the total solid in a coloring photosensitive composition, Preferably it is 0.005-1 weight%, More preferably, it is 0.01-0.5 weight%, Most preferably Is 0.03 to 0.3% by weight of the range. If the amount of the surfactant added is less than the above range, the smoothness and uniformity of the coating film may not be expressed, and if the amount is large, the smoothness and uniformity of the coating film may not be expressed, and other characteristics may deteriorate. have.

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

The coloring photosensitive composition of this invention may contain at least one among organic carboxylic acid and organic carboxylic anhydride for the purpose of the improvement of developability, and the contamination of a board | substrate.

Aliphatic carboxylic acid and aromatic carboxylic acid are mentioned as organic carboxylic acid.

Specific examples of aliphatic carboxylic acids include mono acids 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, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid And dicarboxylic acids such as tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, tricarvalic acid, aconitic acid and camphoronic acid Tricarboxylic acid etc. are mentioned.

Moreover, as aromatic carboxylic acid, specifically, benzoic acid, toluic acid, cuminic acid, hemelic acid, mesitylene acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid, pyromellitic acid Carboxyl groups bonded directly to phenyl groups, such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamonic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, kumaric acid and umbelic acid The carboxylic acid etc. which the carboxyl group couple | bonded through the carbon bond from an acid and a phenyl group are mentioned.

In the said organic carboxylic acid, monocarboxylic acid and dicarboxylic acid are preferable, Especially, malonic acid, glutaric acid, and glycolic acid are more preferable, Malonic acid is especially preferable.

The molecular weight of the said organic carboxylic acid is 1000 or less normally, and is 50 or more normally. When the molecular weight of the said organic carboxylic acid is too large, the contamination improvement effect of a board | substrate may become inadequate, and when too small, there exists a possibility of reducing the addition amount and process contamination by sublimation, volatilization, etc.

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

In the said organic carboxylic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, a citraconic anhydride is preferable, and maleic anhydride is more preferable.

The molecular weight of the said organic carboxylic anhydride is 800 or less normally, Preferably it is 600 or less, More preferably, it is 500 or less, and is usually 50 or more. When the molecular weight of the said organic carboxylic anhydride is too large, the contamination improvement effect of a board | substrate may become inadequate, and when too small, there exists a possibility of reducing the addition amount and process contamination by sublimation, volatilization, etc.

These organic carboxylic acids and organic carboxylic anhydrides may be used individually by 1 type, respectively, and may mix and use 2 or more types.

When using these organic carboxylic acid and organic carboxylic anhydride, the addition amount is 0.01 weight%-5 weight% normally in the total solid of the coloring photosensitive composition of this invention, respectively, Preferably it is 0.03 weight%-3 weight each % to be. When the addition amount is too small, sufficient addition effect may not be obtained, and when too large, surface smoothness and sensitivity may deteriorate, and unsealed peeling piece may generate | occur | produce.

[7-7] thermal polymerization inhibitors

As the thermal polymerization inhibitor, for example, one kind or two or more kinds such as hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol and β-naphthol are used. .

It is preferable that it is the range of 0 to 2 weight% with respect to the total solid in a coloring photosensitive composition, and when there is more, the compounding ratio of a thermal polymerization inhibitor may cause the light-shielding property and the sensitivity fall of a coloring photosensitive composition.

[7-8] plasticizers

As a plasticizer, For example, 1 type, such as a dioctyl phthalate, a dodecyl phthalate, a triethylene glycol dicaprylate, a dimethyl glycol phthalate, a tricresyl phosphate, a dioctyl adipate, a dibutyl sebacate, a triacetyl glycerine, or 2 or more types are used.

It is preferable that the compounding ratio of these plasticizers is 0 to 5 weight% with respect to the total solid in a coloring photosensitive composition, and when more than this, the hardening point of a black photo spacer will fall.

[Preparation method of colored photosensitive composition]

The coloring photosensitive composition of this invention is prepared according to a conventional method. Although it demonstrates concretely, for example below, the preparation method of the coloring photosensitive composition in this invention is not limited to the said method.

From the standpoint of ensuring the dispersion stability of the pigment, the coloring photosensitive composition of the present invention is preferably prepared with a pigment dispersion in advance, and a preparation method of mixing other components therein is preferable.

[1] production of pigment dispersions

A predetermined amount of a pigment, a solvent, a dispersant, and a dispersion aid are weighed, respectively, if necessary, and the pigment is dispersed in a dispersion treatment step to form a liquid pigment dispersion. In this dispersion treatment step, a paint conditioner (paint shaker), sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like can be used. Since the pigment becomes fine particles by performing this dispersion process, the coloring photosensitive composition using the pigment dispersion liquid prepared in this way improves application | coating characteristic, and patterning characteristics, such as a shape and linearity.

When dispersing using a sand grinder or paint shaker, glass beads or zirconia beads having a diameter of 0.1 to 8 mm are preferably used. The temperature at the time of dispersion treatment is set in the range of 0 degreeC-100 degreeC normally, Preferably it is the range of room temperature-80 degreeC. In addition, since a suitable time changes with a composition (a pigment, a solvent, a dispersing agent, etc.) of a pigment dispersion liquid, the magnitude | size of an apparatus, etc., it is necessary to adjust dispersion time suitably.

In this case, it is a reference | standard of dispersion to control the glossiness of a pigment dispersion liquid so that 20 degree specular glossiness in JIS Z8741 (1997) may become the range of 100-200. When the glossiness of the pigment dispersion is low, the dispersion treatment is not sufficient, and coarse pigment particles are often left, and may be insufficient in terms of developability, adhesiveness, resolution, and the like. In addition, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, and thus dispersion stability is likely to be impaired.

When disperse | distributing a pigment, you may use together said binder resin, a dispersion adjuvant, etc. suitably. By containing binder resin, the dispersion stability at the time of manufacturing a pigment dispersion liquid can be improved.

In this case, the addition amount of binder resin is 5 to 100 weight% normally with respect to the pigment in a pigment dispersion liquid, It is preferable to set it as 10 to 60 weight% normally. By setting the amount of the binder resin to be equal to or greater than the lower limit, it is possible to have higher dispersion stability and patterning characteristics, and to be equal to or lower than the upper limit so that a high pigment concentration can be ensured and higher light-shielding properties are obtained.

In addition, solid content concentration of a pigment dispersion liquid is 10 to 40 weight% normally.

Here, "total solid content" refers to all the components of pigment dispersion liquids other than a solvent.

[2] a method of producing a colored photosensitive composition

The coloring photosensitive composition of this invention is prepared by adding and mixing the other component which a coloring photosensitive composition contains to the pigment dispersion liquid obtained by the said process, and making it into a uniform solution. In addition, in the dispersion | distribution process in the liquid which mixed all the components mix | blended as a coloring photosensitive composition simultaneously, there exists a possibility that the highly reactive component may denature because of the heat generation which arises at the time of dispersion. Moreover, in a manufacturing process, since the fine dust often mixes in a liquid, it is preferable to filter the obtained colored photosensitive composition solution with a filter etc.

[Black Photo Spacer]

Although the coloring photosensitive composition of this invention is used for the same use as the coloring photosensitive composition for well-known color filters, Hereinafter, the specific example of the formation method of the black photo spacer using the coloring photosensitive composition of this invention about the case where it is used as a black photo spacer. Explain accordingly.

Usually, a coloring photosensitive composition solution is supplied to a film form or a pattern form by methods, such as application | coating, on the board | substrate on which the black photo spacer is to be formed, and a solvent is dried. Subsequently, pattern formation is performed by methods, such as the photolithography method which performs exposure development. Then, a black photo spacer is formed on the board | substrate by performing further exposure and a thermosetting process as needed.

[1] supply methods to substrates

The coloring photosensitive composition of this invention is normally supplied on a board | substrate in the state melt | dissolved or dispersed in the solvent. As a supply method, it can carry out by a conventionally well-known method, for example, the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, the spray coat method, etc. Moreover, you may supply in a pattern form by the inject method, the printing method, etc. Among them, the die coating method is preferable from a comprehensive viewpoint, such that the amount of the coating liquid is significantly reduced, and there is no influence of mist or the like adhered when the spin coating method is used, and foreign matter generation is suppressed.

Although the application amount varies depending on the application, for example, in the case of a black photo spacer, as a dry film thickness, it is 0.5 micrometer-10 micrometers normally, Preferably 1 micrometer-9 micrometers, Especially preferably, the range of 1 micrometer-7 micrometers to be. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform throughout the substrate. If the deviation is large, nonuniform defects occur in the liquid crystal panel.

However, when the colored photosensitive composition of this invention forms the black photo spacer from which height differs collectively by the photolithographic method, the height of the finally formed black photo spacer will differ.

Moreover, well-known board | substrates, such as a glass substrate, can be used as a board | substrate. Moreover, it is preferable that a board | substrate surface is planar.

[2] drying methods

Drying after supplying the coloring photosensitive composition solution on a board | substrate is preferable by the drying method using a hotplate, an IR oven, and a convection oven. Moreover, you may combine the reduced pressure drying method which performs drying in a pressure reduction chamber, without raising a temperature.

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

[3] exposure methods

Exposure is performed by superimposing a negative mask pattern on the coating film of a coloring photosensitive composition, and irradiating the light source of an ultraviolet-ray or a visible ray through this mask pattern. When performing exposure using an exposure mask, the exposure mask is approached to the coating film of a coloring photosensitive composition, or the exposure mask is arrange | positioned in the position away from the coating film of a coloring photosensitive composition, and exposure through the exposure mask is carried out. It is also possible to use a method of projecting light. Moreover, you may use the scanning exposure system by the laser beam which does not use a mask pattern. At this time, if necessary, in order to prevent the deterioration of the sensitivity of the photopolymerizable layer due to oxygen, it is carried out in a deoxygen atmosphere, or an exposure is performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. You may also

In the case of simultaneously forming black photo spacers having different heights by the photolithography method as a preferred embodiment of the present invention, for example, as described above, the average light transmittance as the light shielding portion (0% light transmittance) and the plurality of openings An exposure mask having an opening (medium transmission opening) having a small average light transmittance with respect to the highest opening (complete transmission opening) is used. By this method, the difference in the residual film rate is generated in accordance with the difference between the average light transmittance (typically 5% to 40%) of the intermediate transmission opening and the perfect transmission opening, that is, the exposure amount.

For example, a method of manufacturing the intermediate transmissive opening with a matrix light shielding pattern having a fine polygonal light shielding unit is known. As absorbers, there are known a method of controlling light transmittance by a film made of a material such as chromium, molybdenum, tungsten, or silicon and controlling the light transmittance.

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

As the optical filter, for example, a thin film may be a type that can control the light transmittance at an exposure wavelength. As the material in that case, for example, Cr compounds (oxides, nitrides, oxynitrides, fluorides, etc. of Cr), MoSi, Si, W, Al, etc. are mentioned.

As an exposure amount, it is 1 mJ / cm <2> or more normally, Preferably it is 5 mJ / cm <2> or more, More preferably, it is 10 mJ / cm <2> or more, Usually 300 mJ / cm <2> or less, Preferably 200 mJ / cm <2> or less, More preferably Preferably 150 mJ / cm 2 or less.

In the case of the proximity exposure system, 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, it is 300 micrometers or less.

[4] developing methods

After performing the said exposure, an image pattern can be formed on a board | substrate by the image development using the aqueous solution of an alkaline compound, or an organic solvent. The aqueous solution may further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

As an alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, Inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine, mono-di- or triethylamine, mono- or Organic alkaline compounds such as diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH) and choline. 2 or more types of mixtures may be sufficient as these alkaline compounds.

As said surfactant, For example, Nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester; Anionic surfactants, such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate, and sulfosuccinic acid ester salt; Amphoteric surfactant, such as alkylbetaines and amino acids, are mentioned.

As an organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. are mentioned, for example. The organic solvent can be used alone or in combination with an aqueous solution.

Although there is no restriction | limiting in particular about the method of image development processing, Usually, it is implemented by methods, such as immersion image development, spray image development, brush image development, ultrasonic image development, at developing temperature of 10 degreeC-50 degreeC, Preferably 15 degreeC-45 degreeC. .

[5] further exposure and thermosetting

If necessary, the substrate after development may be subjected to additional exposure by the same method as the above exposure method, or may be subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are selected 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.

Although the size, shape, etc. of the black photo spacer of this invention are adjusted suitably according to the specification of the color filter which applies this, etc., the coloring photosensitive composition of this invention has the black photo from which the height of a spacer and a sub spacer differs especially by the photolithographic method. It is useful for forming the spacers at the same time, in which case the height of the spacer is usually 2 to 7 mu m, and the sub spacer has a height that is usually 0.2 to 1.5 mu m lower than the spacer.

[Color filter]

The color filter of this invention is equipped with the black photo spacer of this invention as mentioned above, For example, on a glass substrate as a transparent substrate, a black matrix, a red, green, blue pixel coloring layer, and an overcoat layer are It is laminated | stacked and manufactured by forming an oriented film after forming a black photo spacer.

The color filter of this invention which has such a black photo spacer of this invention, and a liquid crystal drive side board | substrate are bonded together, a liquid crystal cell is formed, a liquid crystal is inject | poured into the formed liquid crystal cell, and a liquid crystal display device can be manufactured.

Example

Next, although an Example and a comparative example are given and this embodiment is demonstrated more concretely, this embodiment is not limited to a following example, unless the summary is exceeded. In addition, "part" shows a "weight part" below.

The structural component of the coloring photosensitive composition used by the following example and the comparative example is as follows.

<Binder Resin-1>

Nippon Kayaku Co., Ltd. product "ZCR-1569H" (MW = 3000-4000, acid value = approximately 100 mg-KOH / g)

In addition, this binder resin-1 is corresponded to "alkali-soluble resin (A)" in this invention.

<Binder Resin-2>

Nippon Kayaku Co., Ltd. product "ZCR-1642H" (MW = 5000-6500, acid value = approximately 100 mg-KOH / g)

In addition, this binder resin-2 is corresponded to "alkali-soluble resin (A)" in this invention.

<Binder Resin-3>

Resin obtained by reacting the reaction product of the epoxy compound of the following structure (11) with acrylic acid with trimethylolpropane (TMP) and biphenyl tetracarboxylic dianhydride (BPDA) (MW = 3500-4500, acid value = about 110 mg-). KOH / g)

[Formula 21]

In addition, binder resin-3 can be synthesize | combined according to the following method.

Synthesis Example 1: Synthesis of Binder Resin-3

50 g of the epoxy compound (epoxy equivalent 264) of the structure (11), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine and 0.032 g of paramethoxyphenol were equipped with a thermometer, a stirrer and a cooling tube. The mixture is stirred in a flask and reacted at 90 ° C. until the acid value is 5 mgKOH / g or less. The reaction requires 12 hours and an epoxy acrylate solution is obtained.

25 parts by weight of the 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), thermometer, stirrer, cooling The reaction mixture was slowly heated to 105 ° C. while stirring in a flask equipped with a tube.

When the resin solution becomes transparent, the mixture is diluted with methoxybutyl acetate and prepared to have a solid content of 50% by weight to obtain binder resin-3.

In addition, this binder resin-3 is corresponded to "alkali-soluble resin (A1") in this invention.

<Dispersant>

BIC Chem Corporation `` DisperBYK-2000 ''

<Dispersion aid>

Lubrizol company `` S12000 ''

<Surfactant>

`` Mega pack F-475 '' made by Dainippon ink chemistry company

<Solvent-1>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-2>

MB: 3-methoxybutanol

<Photoinitiator>

The following compound.

[Formula 22]

<Photopolymerizable Monomer>

DPHA: Nippon Kayaku Co., Ltd. product dipentaerythritol hexaacrylate

<Pigment Dispersion-Preparation of 1 to 10>

The pigment, dispersant, dispersion aid, binder resin, and solvent shown in Table 1 were mixed in the weight ratio shown in Table 1. After mixing 80% of the zirconia beads (average particle size 0.3 mm) of the volume of the dispersion vessel therein, the pycomyl dispersion vessel was filled, dispersed in the necessary retention time (RT) shown in Table 1, and each pigment dispersion liquid was dispersed. It prepared.

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

The pigment dispersion liquid prepared as mentioned above and each other component shown in Table 2 were mix | blended and stirred in the ratio shown in Table 2, and the coloring photosensitive composition was prepared.

Each evaluation was performed as follows using this coloring photosensitive composition, and the result was shown in Table 2.

[Evaluation of Step (ΔH), Adhesiveness, and Optical Concentration (OD)]

<Batch formation method of hardened | cured material from a different height>

Each colored photosensitive composition was apply | coated using the spinner on the glass substrate ("AN100" by AGC company). Subsequently, it heat-dried on the hotplate at 110 degreeC for 70 second, and formed the coating film.

The obtained coating film was subjected to exposure treatment using an exposure mask having a completely transmissive opening of a circular pattern of various diameters of 5 to 50 μm, an intermediate transmissive opening of a circular pattern of various diameters of 5 to 50 μm, and a non-printing portion. Was carried out. The intermediate transmissive opening is a thin film of Cr oxide and has a light transmittance of 10 ± 2% at a wavelength of 365 nm. The exposure gap (distance between the mask and the application surface) was 250 µm. As light irradiation, the ultraviolet-ray whose intensity | strength in wavelength 365nm is 32 mW / cm <2> was used, and the exposure amount was made into 6 levels of 40-90 mJ / cm <2>. In addition, ultraviolet irradiation was performed in air.

Subsequently, the shower phenomenon of the water pressure of 0.15 MPa is used at 25 degreeC using the developing solution which consists of aqueous solution containing 0.05 weight% potassium hydroxide and 0.08 weight% nonionic surfactant ("A-60" by Kao Corporation). After the reaction was carried out, development was stopped with pure water and washed with water spray. The shower image development time was adjusted for 10 to 120 second, and was made into 1.5 times the time which the unexposed coating film melts and removes.

The pattern from which the unnecessary part was removed by these operations was obtained. The board | substrate with which the said pattern was formed was heated in 230 degreeC at 230 degreeC for 20 minutes, hardening a pattern, and obtaining the substantially cylindrical spacer pattern.

<Evaluation of step>

Calculating the difference (difference (ΔH)) of the height of the completely permeable opening of the circular pattern having a diameter of 15 μm and the intermediate permeable opening of the circular pattern having a diameter of 35 μm, and obtaining the maximum value at an exposure dose of 40 to 90 mJ / cm 2; Together, the value of ΔH was evaluated based on the following criteria.

(Evaluation Criteria of Step DELTA H)

0.5 μm or more ： ○

0.3 micrometer or more and less than 0.5 micrometer: △

Less than 0.3 μm ： ×

<Evaluation of substrate adhesiveness>

Minimum aperture diameter (μm) in which the pattern remains well resolvable in the fully transmissive opening of a circular pattern of 5 to 50 μm and similarly in the intermediate transmissive opening of 5 to 50 μm at the exposure amount at which the height difference ΔH becomes the maximum. ) Is shown in Table 2 as minimum adhesion. The smaller this value is, the better the substrate adhesion is. In addition, the good resolution means that 24 patterns of the same size are formed and all the patterns are normally formed.

<Evaluation of Optical Concentration (OD)>

The optical density (OD) of the non-printed portion was measured by a transmission densitometer ("D 200-II" manufactured by Gretagmark-Bess). Moreover, the film thickness of the measurement point was also measured, and the optical density (unit OD) per unit film thickness was computed, and the following references | standards evaluated. In addition, an OD value is a numerical value which shows the light-shielding ability, and it shows that it is high light-shielding property, so that a numerical value is large.

(Evaluation Criteria of Unit OD)

0.8 or more ： ○

Less than 0.8: X

[Voltage Retention Rate (VHR) Evaluation]

<Production of Liquid Crystal Cells>

2 mm wide extraction electrode in the electrode substrate A (glass ITO beta for EHC manufacture and evaluation) in which the ITO film | membrane was formed in the whole surface of the piece of 5 cm in width and the center of one side of the copper glass substrate of 2.5 cm in width and length. The electrode substrate B (glass SZ-B111MIN (B) for EHC manufacture, evaluation) which formed this connected 1 cm wide ITO film | membrane was prepared.

Each colored photosensitive composition was apply | coated on the electrode substrate A, and after vacuum drying for 1 minute, it prebaked at 90 degreeC for 1.5 minute on the hotplate, and obtained the coating film of 2.0 micrometers of dry film thicknesses. Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed under exposure conditions of 50 mJ / cm 2 using 3 kW high-pressure mercury lamps, respectively. Subsequently, using a developing solution composed of about 0.06% by weight of potassium hydroxide and about 0.14% by weight of a nonionic surfactant ("A-60" manufactured by Kao Co., Ltd.), a water pressure of 0.15 MPa was obtained at 25 ° C. After the shower development was carried out, the development was stopped with pure water and rinsed with water spray. The shower image development time was adjusted for 10 to 120 second, and was made into about 1.5 times the time (break time) in which a non-photosensitive layer melt | dissolves and removes.

The electrode substrate thus formed was post-baked at 230 ° C. for 20 minutes to obtain an electrode substrate on which resist was applied (resist substrate). Then, the polyimide solution was apply | coated to the resist board | substrate, prebaked at 70 degreeC for 2 minutes on the hotplate, and postbaked at 220 degreeC for 24 minutes. The resist substrate thus obtained was cut into a substrate having a length and width of 2.5 cm to complete the electrode substrate A for evaluation.

On the other hand, the polyimide solution was apply | coated also on the electrode substrate B, it prebaked at 70 degreeC for 2 minutes on a hotplate, and post-baked at 220 degreeC for 24 minutes, and the electrode substrate B for evaluation was completed.

Then, after apply | coating the epoxy resin sealing compound containing 5 micrometers diameter silica beads using the dispenser on the outer periphery of the electrode substrate B, the electrode substrate A for evaluation is carried out to the front side (sealing agent side) of the electrode substrate B. Adhesion was carried out while pressing the coated surface to complete an empty cell. It heated in 180 degreeC in hot-air circulation path for 2 hours.

The liquid crystal (MLC-6608 made by Merck Japan) was injected into the empty cell obtained in this way, the peripheral part was sealed with UV hardening type sealing compound, and the liquid crystal cell for voltage retention measurements was completed.

<Evaluation of Voltage Retention Rate (VHR)>

After the annealing treatment (heating at 105 ° C. for 2.5 hours in a hot air circulation path), the liquid crystal cell was applied to evaluation electrode substrates A and B under conditions of voltage 5 V, 0.6 Hz, and frame time of 1667 msec. It measured with "VHR-6254 type" by Toyo Technica.

From the result of Table 2, the coloring photosensitive composition of this invention which contains Or64 and B60 as an essential component as a pigment, and the coloring photosensitive composition of this invention which contains Or72 and B60 as an essential component as a pigment are light-shielding, adhesiveness, and voltage retention. It can be seen that it is useful to simultaneously form cured products having different heights from the same material, while maintaining.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is based on the JP Patent application (patent application 2012-018337) of an application on January 31, 2012, The content is taken in here as a reference.

Claims (5)

As a pigment dispersion liquid containing a pigment, a solvent, and a dispersing agent, the said pigment contains the pigment shown to following (A) and the pigment shown to (B),
Pigment dispersion liquid for coloring photosensitive compositions.
(A) one selected from the group consisting of CI pigment orange 43, CI pigment orange 64 and CI pigment orange 72
(B) CI Pigment Blue 60 The method of claim 1,
A pigment dispersion wherein said pigment contains CI Pigment Orange 64 and CI Pigment Blue 60. The method of claim 1,
The pigment dispersion liquid which the said pigment further contains 1 chosen from the group which consists of CI pigment red 254, CI pigment violet 23, and CI pigment violet 29. The method of claim 1,
The pigment dispersion liquid which the said pigment contains the pigment shown to following (1), or the pigment shown to (2).
(1) CI Pigment Orange 64, CI Pigment Blue 60 and CI Pigment Red 254
(2) CI Pigment Orange 64, CI Pigment Blue 60 and CI Pigment Violet 29 The method according to any one of claims 1 to 4,
Pigment dispersion for color photosensitive compositions used to form black photo spacers.