KR20180113222A - Photosensitive coloring composition, cured product, coloring spacer, image display device - Google Patents

Abstract

Provided is a photosensitive coloring composition having less light leakage near a wavelength of 700 nm, excellent transmittance near a wavelength of 900 nm, and excellent electrical reliability after ultraviolet irradiation. The photosensitive coloring composition of the present invention is a photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, (A) at least one compound selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound: (A3) a content ratio of the organic black pigment (a1) relative to 100 parts by mass of the carbon black is 150 (a2) Mass part or more.
[Chemical Formula 1]

Description

Photosensitive coloring composition, cured product, coloring spacer, image display device

The present invention relates to a photosensitive coloring composition and the like. More specifically, the present invention relates to a photosensitive coloring composition which is preferably used for forming coloring spacers and the like in an image display apparatus such as a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, a colored spacer formed by the cured product, And an image display device having the coloring spacer.

Japanese Patent Application No. 2017-026369 filed on February 15, 2017, and Japanese Patent Application No. 2017-166318 filed on August 31, 2017, Japanese Patent Application No. 2017-166318, claims, drawings and summary Some or all of the contents disclosed in the entire contents and the documents cited in this specification are hereby incorporated herein by reference.

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

However, the LCD manufactured by using the photosensitive composition is not maintained with the voltage applied to the liquid crystal due to the electric characteristics of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, thereby causing problems such as display unevenness of the display . Particularly, in a so-called columnar spacer, a photo spacer, or the like, which is used to keep a gap between two substrates closer to the liquid crystal layer in a color liquid crystal display, for example, a liquid crystal panel The effect is large.

Conventionally, when a spacer having no light shielding property is used for a TFT-type LCD, a TFT serving as a switching element may malfunction due to light transmitted through a spacer. In order to prevent this, a method of using spacers (colored spacers) having light shielding properties has been studied.

On the other hand, in recent years, a method of collectively forming colored spacers having different heights by a photolithography method has been proposed along with a change in the structure of the panel. For example, Patent Document 1 discloses that by using a specific black pigment species, it is possible to realize a light-shielding property, a dispersibility, a plate-making property, and a sufficiently low relative permittivity.

Patent Document 2 discloses a colored photosensitive resin composition which is excellent in elastic recovery rate, resolution, and chemical resistance and satisfies the characteristics of a black matrix by using a plurality of organic colored pigments in the pigment.

International Publication No. 2015/046178 Korean Patent Publication No. 10-2014-0096423

Along with the recent change in the panel structure, in the colored spacer, the transmittance near the wavelength 900 nm is secured so as not to cause light leakage even in the vicinity of the wavelength 700 nm and to recognize the mark for mask alignment at the time of exposure .

On the other hand, in order to improve the liquid crystal alignment property, a method of irradiating ultraviolet rays after manufacturing a liquid crystal cell has been expanded. When ultraviolet ray irradiation is performed, a part of the pigment or its treating agent tends to be decomposed to generate impurities. However, even in this case, it is required to maintain sufficient electrical reliability.

As a result of studies on the photosensitive coloring composition described in Patent Document 1, the inventors of the present invention have found that it is difficult to achieve both suppression of light leakage near a wavelength of 700 nm and securing of light transmittance near a wavelength of 900 nm.

As a result of studies on the photosensitive coloring composition described in Patent Document 2, it has been difficult to secure electrical reliability particularly after ultraviolet ray irradiation.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a photosensitive coloring composition having less light leakage near a wavelength of 700 nm, excellent light transmittance near 900 nm and excellent electrical reliability after ultraviolet irradiation do.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that a specific organic black pigment, CI Pigment Blue 60 and carbon black are used in the photosensitive coloring composition and the content ratio of a specific organic black pigment to carbon black To a specific range, the present inventors have found out that the above problems can be solved, and have reached the present invention.

That is, the present invention has the following structures [1] to [12].

[1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f)

Wherein the (a) colorant comprises (a1) at least one compound selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound and a salt of a geometric isomer of the compound (A2) CI Pigment Blue 60, and (a3) carbon black,

Wherein the content of the organic black pigment (a1) in the (a3) 100 parts by mass of the carbon black is 150 parts by mass or more.

[Chemical Formula 1]

(In the formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;

^{R 2, R 3, R 4} , R 5, R 7, R 8, R 9 and R ¹⁰ is a halogen atom, R ^11, COOH, COOR ^11, COO hydrogen atoms, each independently ^-, CONH _2, CONHR ^{11, CONR 11 R 12, CN, OH} , OR 11, COCR 11, OOCNH 2, OOCNHR 11, OOCNR 11 R 12, NO 2, NH 2, NHR 11, NR 11 R 12, NHCOR 12, NR 11 COR 12, N = ^{_{CH 2, N = CHR 11,}} N = CR 11 R 12, SH, SR 11, SOR 11, SO 2 R 11, SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ¹² and;

At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Or they may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR < ¹¹ > bridges;

R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms )

[2] The photosensitive coloring composition according to [1], wherein the content of (a1) the organic black pigment in the (a3) 100 parts by mass of the carbon black is 200 parts by mass or more.

[3] The photosensitive colored composition according to [1] or [2], wherein the content of the organic black pigment (a1) is 210 parts by mass or more based on 100 parts by mass of the carbon black (a3).

[4] The photosensitive colored composition according to any one of [1] to [3], wherein the (a3) content of the C. I. Pigment Blue 60 (a2) relative to 100 parts by mass of the carbon black is 200 parts by mass or more.

[5] The photosensitive colored composition according to any one of [1] to [4], wherein the total content of the organic pigments in the (a3) 100 parts by mass of the carbon black is 550 parts by mass or more.

[6] The photosensitive colored composition according to any one of [1] to [5], wherein the content of the colorant (a) in the total solid content is 10% by mass or more.

[7] The photosensitive coloring composition according to any one of [1] to [6], wherein the content of the colorant (a) in the total solid content is 45% by mass or less.

[8] The photosensitive colored composition according to any one of [1] to [7], wherein the alkali-soluble resin (b) comprises (b1) an epoxy (meth) acrylate resin.

[9] The photosensitive coloring composition according to any one of [1] to [8], wherein the cured coating film has an optical density per 1 μm of the film thickness of 1.0 or more.

[10] A cured product obtained by curing the photosensitive colored composition according to any one of [1] to [9].

[11] A colored spacer formed from the cured product according to [10].

[12] An image display apparatus comprising the coloring spacer according to [11].

According to the present invention, it is possible to provide a photosensitive coloring composition, a cured product, and a colored spacer excellent in electrical reliability after irradiation with ultraviolet rays, having less light leakage near a wavelength of 700 nm, excellent transmittance of light at a wavelength of 900 nm, An image display apparatus having such a coloring spacer can be provided.

1 is a schematic view of an upper surface of an electrode substrate B used in the embodiment.
2 is a schematic view of a side surface of a liquid crystal cell for measurement used in the embodiment.
3 is a schematic diagram of a waveform of an applied voltage in one cycle in ion density measurement and a schematic diagram of a waveform of a measured current.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications may be made within the scope of the present invention.

In the present invention, "(meth) acryl" means "acrylic and / or methacrylic", and "(meth) acrylate" and "(meth) acryloyl"

The term "(co) polymer" means both of a homopolymer (homopolymer) and a copolymer (copolymer), and the term "(co) polymer" Quot; acid " means containing both an acid and an anhydride thereof. In the present invention, "acrylic resin" means a (co) polymer containing (meth) acrylic acid or a (co) polymer containing a (meth) acrylic ester having a carboxyl group.

In the present invention, the term " monomer " refers to a so-called polymer material (polymer), and includes not only the monomer (monomer) but also the dimer, trimer and oligomer.

In the present invention, the term " total solid content " means all components other than the solvent contained in the photosensitive coloring composition or in the ink described below.

In the present invention, the "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (Gel Permeation Chromatography).

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

Regarding the pigment, " C.I. I. " means a color index.

In the present specification, the percentages and parts denoted by " mass " have the same meaning as the percentages and parts denoted by " weight ".

[Photosensitive coloring composition]

In the photosensitive coloring composition of the present invention,

(a) a colorant

(b) an alkali-soluble resin

(c) a photopolymerization initiator

(d) Ethylenically unsaturated compound

(e) Solvent

(f) a dispersant as an essential component and, if necessary, further additives such as a silane coupling agent and the like adhesion improver, a coating property improving agent, a development improving agent, an ultraviolet absorber, an antioxidant, a surfactant, , And usually, each compounding ingredient is used in a state dissolved or dispersed in a solvent.

The photosensitive coloring composition of the present invention is characterized in that (a) the coloring agent comprises (a1) a group consisting of a compound represented by the general formula (I) described later, a geometric isomer of the compound, a salt of the compound and a salt of a geometric isomer of the compound (A2) CI Pigment Blue 60, and (a3) carbon black, wherein (a3) the organic black pigment (a1) based on 100 parts by mass of the carbon black, Is not less than 150 parts by mass. Hereinafter, each component will be described in detail.

< (a) Colorant >

The colorant (a) in the photosensitive coloring composition of the present invention contains the following (a1), (a2) and (a3) as essential components.

(a1) an organic black pigment containing at least one member selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound

(a2) C. I. Pigment Blue 60

(a3) carbon black

Among these pigments, (a1) and (a2) are organic pigments, and (a3) is an inorganic pigment.

< (a1) Organic black pigment >

As described above, the colorant (a) contained in the photosensitive coloring composition of the present invention comprises (a1) a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound and a geometric isomer (Hereinafter sometimes to be abbreviated as &quot; (a1) organic black pigment &quot;) as an essential component. (a1) It is considered that by containing the organic black pigment, it is easy to secure the light shielding property, to suppress the decrease of the voltage holding ratio of the liquid crystal, to suppress the absorption of ultraviolet rays, and to control the shape and the level difference.

(2)

In the formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;

^{R 2, R 3, R 4} , R 5, R 7, R 8, R 9 and R ¹⁰ is a halogen atom, R ^11, COOH, COOR ^11, COO hydrogen atoms, each independently ^-, CONH _2, CONHR ^{11, CONR 11 R 12, CN, OH} , OR 11, COCR 11, OOCNH 2, OOCNHR 11, OOCNR 11 R 12, NO 2, NH 2, NHR 11, NR 11 R 12, NHCOR 12, NR 11 COR 12, N = ^{_{CH 2, N = CHR 11,}} N = CR 11 R 12, SH, SR 11, SOR 11, SO 2 R 11, SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ¹² and;

At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Or they may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR &lt; ¹¹ &gt; bridges;

R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms .

The compound represented by the general formula (I) or the geometric isomer of the compound has the following core structure (however, the substituent in the structural formula is omitted), and the trans-trans isomer is probably the most stable.

(3)

When the compound represented by the general formula (I) is not anionic, its charge can be converted to any known suitable cation such as a metal, an organic, an inorganic or a metal organic cation, particularly an alkali metal, an alkaline earth metal, , Quaternary ammonium such as primary ammonium, secondary ammonium or trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salt compensated by an organometallic complex. When the geometric isomer of the compound represented by the general formula (I) is not anionic, the same salt is preferred.

In the substituent groups of the formula (I) and their definitions, the shielding ratio tends to be high. This is because it is considered that the following substituents do not absorb and do not affect the color of the pigment.

R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, more preferably a hydrogen atom.

R ³ and R ⁸ are each independently preferably a hydrogen atom, NO _2, OCH _3, OC ₂ H _5, a bromine atom, a chlorine _{atom, CH 3, C 2 H 5} , N (CH 3) 2, N (CH ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.

Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is composed of the same substituent , More preferably R ¹ is the same substituent as R ⁶ , R ² is the same substituent as R ⁷ , R ³ is the same substituent as R ⁸ , R ⁴ is the same substituent as R ^9, and R ⁵ is R ¹⁰ .

Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n- octyl group, 1,1,3,3- An ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms includes, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a toluyl group, a norbornyl group, A norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group,

Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, Methyl-3-butene-2-yl group, 3-methyl-2-thiol group, A buten-1-yl group, a 1,4-pentadiene-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group.

The cycloalkenyl group having 3 to 12 carbon atoms includes, for example, a 2-cyclobutene-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexene- Cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4 (10) -toyen-10-yl group, 2-norbornen- En-1-yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphhenyl group.

The alkynyl group having 2 to 12 carbon atoms includes, for example, a 1-propyn-3-yl group, a 1-butyne-4-yl group, Pentadien-5-yl group, a 1-hexyl-6-yl group, a cis-3-methyl- Octyne-8-yl group, 1-nonyne-9-yl group, 1-decyne- Yl group or a 1-dodecyn-12-yl group.

The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

When the organic black pigment (a1) contains at least one member selected from the group consisting of the compound represented by the general formula (I), the geometric isomer of the compound, the salt of the compound, and the salt of the geometric isomer of the compound However, they may contain a plurality of them. The organic black pigment (a1) is preferably at least one compound selected from the group consisting of a compound represented by the general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound from the viewpoints of light- , And the like.

The organic black pigment (a1) is preferably a compound represented by the following formula (I-1) and / or a geometric isomer of the compound, more preferably a compound represented by the following formula (I-1).

[Chemical Formula 4]

Specific examples of such organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.

The organic black pigment is preferably dispersed and used by a dispersant, a solvent and a method described later. The presence of a sulfonic acid derivative (sulfonic acid substituent) of the compound represented by the above general formula (I), particularly, a sulfonic acid derivative of the compound represented by the above general formula (I-1) at the time of dispersion improves dispersibility and storage stability , It is preferable that the organic black pigment (a1) further contains these sulfonic acid derivatives. As the sulfonic acid derivative, for example, at least one selected from the group consisting of R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (I) SO &lt; ₃ &gt; H.

In order to adjust the chromaticity, it is preferable that the organic black pigment (a1) further contains a compound represented by the following general formula (I-2) and / or a geometric isomer of the above compound.

[Chemical Formula 5]

< (a2) C. I. Pigment Blue 60 >

The colorant (a) contained in the photosensitive coloring composition of the present invention contains (a2) C. I. Pigment Blue 60 as an essential component.

Since the organic black pigment (a1) has a high transmittance in the vicinity of 650 to 750 nm and insufficient light shielding property in its wavelength region, (a2) CI Pigment Blue 60 has an absorption band in its wavelength region, ) CI Pigment Blue 60 is used in combination, it is considered that the transmittance in the wavelength region can be lowered.

(A2) CI Pigment Blue 60 has a high transmittance in the vicinity of 300 to 400 nm with respect to other blue pigments such as CI Pigment Blue 15: 6, suppressing the absorption of ultraviolet rays and controlling the shape and level difference of colored spacers easy to do. In addition, since the elution of impurities is small, the voltage holding ratio is high and the ion density is low. Particularly, since absorption of ultraviolet rays is small, decomposition by ultraviolet irradiation and elution of impurities are considered to be small, and even after irradiation with ultraviolet rays for improving liquid crystal alignability, reduction in voltage retention rate and ion density is small and electrical reliability is excellent.

<(a3) Carbon Black>

The colorant (a) contained in the photosensitive coloring composition of the present invention contains (a3) carbon black as an essential component.

(a3) Since the carbon black has an absorption spectrum over the entire wavelength at the entire wavelength of the visible region and has a low transmittance, (a1) an organic black pigment, (a2) CI Pigment Blue 60, (a3) , It is considered that it is possible to suppress the light leakage and to reduce the content ratio of the coloring agent to the total solid content and thereby to secure a high electrical reliability .

Examples of the carbon black include the following carbon blacks.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 , # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, , OIL11B, OIL30B, OIL31B

Printex 3, Printex 3OP, Printex 30, Printex 30, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex (registered trademark) U, Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Monarch 180, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark), REGAL 99R, REGAL 415, REGAL 415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8

(Registered trademark) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 15, RAVEN 15, RAVEN 15, RAVEN 14, RAVEN 14, RAVEN 14, RAVEN 14, RAVEN 14, RAVEN 14, RAVEN 10, RAVEN 880, , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

The pH of the surface of the carbon black used in the present invention is not particularly limited, but is preferably 9 or less, more preferably 7 or less, further preferably 5 or less, and particularly preferably 4 or less. When the amount is less than the upper limit, the dispersant tends to adhere and the dispersibility tends to be good. The lower the pH of the surface of the carbon black is, the more preferable it is usually 2 or more.

The pH of the surface of the carbon black is measured by dispersing the powder of the carbon black in water and conducting a pH measurement of the aqueous solution against the dispersion.

The average particle diameter of the carbon black is preferably 8 nm or more, more preferably 17 nm or more, further preferably 21 nm or more, further preferably 100 nm or less, more preferably 65 nm or less, and 40 nm or less Still more preferably 32 nm or less. When the amount is less than the above upper limit value, dispersion stability and storage stability tends to be good, and when it is more than the lower limit value, the light shielding property tends to be good.

The average particle diameter of the carbon black in the present invention means the number average particle diameter. In general, the average particle diameter of carbon black is obtained by photographing a photograph taken at several tens of magnifications by electron microscope observation, and by particle image analysis in which particles of these photographs are measured by an image processing apparatus to about 2,000 to 3,000 pieces.

The carbon black coated with a resin may be used. The use of carbon black coated with a resin has the effect of improving the adhesion to a glass substrate and the volume resistance value. As the carbon black coated with resin, for example, carbon black described in JP-A-09-71733 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and permittivity.

It is preferable that the total content of Na and Ca is 100 ppm or less as the carbon black to be provided for the coating treatment by the resin. Carbon black is usually mixed with Na, Ca, K, Mg, Al, or the like mixed in from raw oil, lead oxide (or gas), reaction stop water, granulated water, Fe and so on. Among these, Na and Ca are generally contained in several hundreds ppm or more, respectively. However, by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electric short-circuiting can be prevented.

As a method for reducing the content of the ash containing Na or Ca, there are a method of selecting as the raw material oil, fuel oil (or gas), and reaction stop water at the time of producing carbon black as few as possible, This is possible by minimizing the addition amount of the alkali substance to be adjusted. Another method is to wash the carbon black produced from the furnace with water or hydrochloric acid to dissolve Na or Ca and remove the carbon black.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or aqueous hydrogen peroxide and then a soft solvent is added to the water, the carbon black migrates to the solvent side and is completely separated from the water, and most Na Ca is dissolved and removed in water or acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it is possible to use a raw material in a carbon black manufacturing process alone or in a water or acid dissolving method alone. However, The total amount can be made 100 ppm or less.

The resin-coated carbon black is preferably an acidic carbon black having a pH of 6 or less. The dispersion diameter (Agglomerate diameter) in water becomes small, so that it is possible to cover up to the fine unit. And an average particle diameter of 40 nm or less and a dibutyl phthalate (DBP) absorption amount of 140 ml / 100 g or less. Within the above range, a coating film having good light shielding property tends to be obtained.

The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the amount of the carbon black and the resin, the resin is mixed with a solvent such as cyclohexanone, toluene or xylene, A suspension obtained by mixing the resin solution dissolved with carbon black and water is mixed and stirred to separate the carbon black and water, and then the water is removed and heated and kneaded. The composition obtained is shaped into a sheet, pulverized and then dried Way ; 2. A method of granulating carbon black and a resin by mixing and stirring the resin solution and suspension prepared in the same manner as above to separate and heat the obtained granular material to remove remaining solvent and water; 3. Carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-mentioned solvent, carbon black is added, mixed and dried, and the solvent is removed to obtain carboxylic acid-impregnated carbon black, Followed by dry blending; 4. A suspension containing a reactive group-containing monomer component constituting the resin to be coated and water is stirred at a high speed to prepare a suspension. After polymerization and cooling to obtain a reactive group-containing resin from the polymer suspension, carbon black is added thereto, A method of reacting black with a reactive group (grafting carbon black), cooling, and pulverizing can be adopted.

The kind of the resin to be coated is not particularly limited, but a synthetic resin is common, and a resin having a benzene ring in its structure has the same action as an amphoteric surfactant, and is preferable in terms of dispersibility and dispersion stability.

Specific examples of the synthetic resin include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, grit resin, epoxy resin and alkylbenzene resin, and thermosetting resins such as polystyrene, polycarbonate, polyethylene terephthalate Examples of the thermoplastic resin composition of the present invention include thermoplastic resins such as polybutylene terephthalate, phthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, Resin can be used. The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the amount is above the lower limit value, there is a tendency that the coating can be made sufficient. On the other hand, when the amount is less than the upper limit, adhesion between the resins is prevented, and the dispersibility tends to be good.

Carbon black obtained by coating with a resin in this way can be used as a coloring agent for a coloring spacer according to a conventional method, and a color filter having the coloring spacer as a component can be produced by a conventional method. When such carbon black is used, there is a tendency that a color spacer having a high light-shielding ratio and a low surface reflectance can be formed at low cost. It is also presumed that the carbon black surface has a function of confining Ca or Na in the carbon black by coating the surface with a resin.

&Lt; Other coloring agents >

The colorant (a) contained in the photosensitive coloring composition of the present invention may contain other coloring agents such as other pigments and other dyes in addition to the pigments of (a1), (a2) and (a3). The color of the other colorants is not particularly limited, and colorants of the respective colors such as red, orange, blue, purple, green, and yellow can be used. In addition, black pigments other than the above-mentioned (a1) and (a3) may be used. As other coloring agents, it is preferable to use an organic pigment from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal, suppressing absorption of ultraviolet rays, and facilitating control of the shape and level difference of the colored spacer.

The chemical structure of the other pigments is not particularly limited. However, in addition to organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazine pigments, indanthrene pigments, Pigments and the like can also be used. Specific examples of the organic pigments that can be used hereinafter are represented by pigment numbers.

As the red pigment, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38 50: 1, 52: 1, 52: 2, 53, 53: 1, 48: 3, 48: 4, 49, 49: 63: 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 53: 2, 53: 3, 57, 57: , 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, , 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, , 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, . Of these, CI Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, 272 Preferred are CI Pigment Red 177, 209, 224, 254, 272, particularly preferably CI Pigment Red 177, 254, 272. In the case of curing with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. From this viewpoint, C. I. Pigment Red 254, 272 is more preferable.

Examples of orange color pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, In addition, CI Pigment Orange 13, 43, 64 and 72 are preferable from the viewpoints of dispersibility and light shielding property. When curing with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet ray absorption rate. CI Pigment Orange 64 is more preferable, and CI Pigment Orange 64 is more preferable.

The blue pigments include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, , 28, 29, 33, 35, 36, 56, 56: 1, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, . Among these, CI Pigment Blue 15: 6 and 16 are preferable from the viewpoints of dispersibility and light shielding.

CI 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, Among these, CI Pigment Violet 19, CI 23 and CI 29, and more preferably CI Pigment Violet 23 and 29 are preferable from the viewpoint of light shielding.

CI Pigment Violet 23 and 29 are preferable from the viewpoints of dispersibility and light shielding property. In the case of curing with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. From this viewpoint, CI Pigment Violet 23 29 is more preferable. Also, from the viewpoint of light shielding property, C.I. Pigment Violet 29 is preferable.

Examples of the organic coloring pigments that can be used in addition to the red pigment, the orange pigment, the blue pigment, and the purple pigment include green pigments and yellow pigments.

As the green pigment, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, . Among these, CI Pigment Green 7 and CI 36 are preferably used.

Examples of the yellow pigments include CI 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, , 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: , 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, , 200, 202, 203, 204, 205, 206, 207, 208. Of these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185, and more preferably CI Pigment Yellow 83, 138, 139 , 150, and 180, respectively.

Among these, an orange color pigment and / or a purple pigment are preferable from the viewpoint of light shielding property and reliability, and a purple pigment is more preferable from the viewpoint of light shielding property, and C. I. Pigment Violet 29 is more preferable.

Examples of the black pigments other than (a1) and (a3) include acetylene black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black and perylene black.

Examples of other dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Dispersed Red 58 CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, and the like.

Examples of the anthraquinone dyes include CI BAT BLUE 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse Blue 60, and the like.

In addition, examples of the phthalocyanine dyes include CI Pad Blue 5, quinoneimine dyes such as CI Basic Blue 3 and CI Basic Blue 9, quinoline dyes such as CI Solvent Yellow, 33, CI Acid Yellow 3 and CI Disperse Yellow 64, and nitro-based dyes, for example, CI Acid Yellow 1, CI Acid Orange 3 and CI Disperse Yellow 42.

The above-mentioned (a1), (a2), (a3) and other pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less Do. Here, the reference of the average particle size is the number of pigment particles.

The average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size measurement was carried out for a sufficiently diluted photosensitive coloring composition (usually diluted to a pigment concentration of about 0.005 to about 0.2 mass%, and if there is a recommended concentration by a measuring instrument, the concentration depends on the concentration) .

<(b) Alkali-soluble resin>

The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, Resins, novolac-based resins, and polyvinylphenol-based resins. Of these,

(b1) an epoxy (meth) acrylate resin

(b2) Acrylic copolymer resin

Is preferably used from the viewpoint of excellent formability. These may be used singly or in combination of plural kinds.

<(b1) Epoxy (meth) acrylate resin>

(b1) The epoxy (meth) acrylate resin is obtained by reacting an epoxy compound (epoxy resin) with a reaction product of an?,? - unsaturated monocarboxylic acid and / or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety Is a resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group such as a polybasic acid and / or an anhydride thereof in addition to the hydroxyl group generated by the reaction.

The resin obtained by reacting the polybasic acid and / or the anhydride with a compound having two or more substituents capable of reacting with the hydroxyl group before reacting the polybasic acid and / or the anhydride with the hydroxyl group, and then reacting the polybasic acid and / (b1) an epoxy (meth) acrylate resin.

The resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group which can further react is also included in the epoxy (meth) acrylate resin (b1).

As such, the epoxy (meth) acrylate resin has no chemical structure and substantially no epoxy group and is not limited to "(meth) acrylate", but an epoxy compound (epoxy resin) ) Acrylate &quot; is a representative example, so it is named according to the common usage.

The epoxy (meth) acrylate resin (b1-1) and / or the epoxy (meth) acrylate resin (b1-2) used as the (meth) (Hereinafter sometimes referred to as a &quot; carboxyl group-containing epoxy (meth) acrylate resin &quot;) is preferably used from the viewpoints of developability and reliability.

&Lt; Epoxy (meth) acrylate resin (b1-1) >

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting the polybasic acid and / or an anhydride thereof.

<Epoxy (meth) acrylate-series resin alkali-soluble resin (b1-2)>

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

Here, the epoxy resin is also referred to as a raw material compound before the resin is formed by thermal curing, and the epoxy resin can be appropriately selected from among known epoxy resins. As the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. As the phenolic compound, a compound having a phenolic hydroxyl group with a divalent or trivalent or more is preferable, and a monomer or a polymer may be used.

Examples of the raw material epoxy resin include cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolak type epoxy resin , Naphthalene novolak type epoxy resin, epoxy resin, adamanthyl group-containing epoxy resin, fluorene type epoxy resin and the like which are reaction products of dicyclopentadiene and phenol or cresol and epihalohydrin are preferably used , And thus having an aromatic ring in the main chain can be preferably used.

Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resins (for example, &quot; jER (registered trademark, the same hereinafter) 828 &quot;, &quot; jER1001 &quot;, &quot; jER1002 &quot; NER-1302 &quot; (epoxy equivalent 323, softening point 76 캜) obtained by reaction of an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example, (E.g., "jER807", "EP-4001", "EP-4002", and "EP-4004" manufactured by Mitsubishi Chemical Corporation), bisphenol F type resins NER-7406 &quot; (epoxy equivalent weight: 350, softening point: 66 占 폚) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether For &quot; YX-4000 &quot; manufactured by Mitsubishi Chemical Corporation EP-152 "manufactured by Mitsubishi Chemical Corporation," EP-154 "manufactured by Mitsubishi Chemical Corporation," DEN-EP-154 "manufactured by Dow Chemical Company), phenol novolak type epoxy resin EOCN (registered trademark, hereinafter the same) -102S "," EOCN-1020 "," EOCN-10 "manufactured by Nippon Kayaku Co., 104S "), triglycidylisocyanurate (for example," TEPIC (registered trademark) "manufactured by Nissan Chemical Industries, Ltd.), trisphenol methane type epoxy resin (for example," EPPN (Hereinafter, referred to as the same) -501, EPPN-502, and EPPN-503), alicyclic epoxy resins ("Celloxide (registered trademark)", "Celloxide EHPE" Epoxy resin obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol (for example, &quot; EXA-7200 &quot; manufactured by DIC Corporation, &quot; NC-730 0 "), and epoxy resins represented by the following general formulas (B1) to (B4). Specifically, "XD-1000" manufactured by Nippon Yakusha Co., Ltd., "NC-3000" manufactured by Nippon Yakusha Co., Ltd. as an epoxy resin represented by the following general formula (B2) As the epoxy resin represented by the formula (B4), "ESF-300" manufactured by Shinnitetsu Sumikin Chemical Co., Ltd. and the like can be mentioned.

[Chemical Formula 6]

In the general formula (B1), a is an average value of 0 to 10, and each R ¹¹¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, , A naphthyl group, or a biphenyl group. A plurality of R &lt; ^{111 &gt;} in each molecule may be the same or different.

(7)

In the general formula (B2), b is an average value and represents a number of 0 to 10, and each R ¹²¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, , A naphthyl group, or a biphenyl group. The plurality of R ¹²¹ present in one molecule may be the same or different.

[Chemical Formula 8]

In the general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, it includes at least one adamantane structure in the molecular structure. c represents 2 or 3;

[Chemical Formula 9]

In the general formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, An alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent, and * indicates a bond.

[Chemical formula 10]

In the general formula (B4), p and q each independently represent an integer of 0 to 4, R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹⁴³ And R ¹⁴⁴ each independently represent an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or more.

Among them, it is preferable to use an epoxy resin represented by any one of the general formulas (B1) to (B4).

Examples of the?,? - unsaturated monocarboxylic acid ester having an?,? -unsaturated monocarboxylic acid or a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl succinic acid, (Meth) acryloyloxypropyl succinic acid, 2 (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxy (Meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with? -Caprolactone,? -Propiolactone,? -Butyrolactone (anhydrous) phthalic acid, (anhydrous) phthalic acid, (meth) acrylate, and pentaerythritol tri (meth) acrylate, or a monomer having a lactone such as δ- Monomers having an acid (anhydride) added thereto such as maleic acid, and (meth) acrylic acid dimer.

Of these, in view of sensitivity, (meth) acrylic acid is particularly preferable.

As a method for adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin, a known technique may be used. For example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst . Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride Etc. may be used.

Further, each component of the epoxy resin, the?,? -Unsaturated monocarboxylic acid or the?,? - unsaturated monocarboxylic acid ester having a carboxyl group and the esterification catalyst may be used singly, More than one species may be used in combination.

The amount of the?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin, more preferably 0.7 To 1.1 equivalents. When the amount of the?,? - unsaturated monocarboxylic acid ester having an?,? -unsaturated monocarboxylic acid or a carboxyl group is set to the lower limit value or more, insufficient introduction of the unsaturated group can be suppressed and the subsequent addition of the polybasic acid and / It is easy to make the reaction with the organic solvent to be sufficient. On the other hand, by keeping the content below the above upper limit, the unreacted materials of the?,? - unsaturated monocarboxylic acid esters having an?,? - unsaturated monocarboxylic acid or a carboxyl group can be restrained and tend to be easily cured Is confirmed.

Examples of the polybasic acid and / or anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, Hydrofluoric acid, chlorophthalic acid, hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof, and the like.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrous tetrahydrophthalic acid, or biphenyltetracarboxylic acid dianhydride.

The addition reaction of a polybasic acid and / or an anhydride thereof can be carried out by a known method, and an addition reaction of an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and Under the same conditions, the target product can be obtained by continuous reaction. The addition amount of the polybasic acid and / or the anhydride component thereof is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g. &lt; / RTI &gt; When the amount is above the lower limit value, the alkali developability tends to be good, and when it is not more than the upper limit value, the curing performance tends to become good.

In addition, polyfunctional alcohols (polyhydric alcohols) such as trimethylolpropane, pentaerythritol and dipentaerythritol may be added during the addition reaction of the polybasic acid and / or anhydride thereof to introduce a multibranched structure.

The carboxyl group-containing epoxy (meth) acrylate resin is usually prepared by reacting a reaction product of an epoxy resin and an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group with a polybasic acid and / , Or after mixing a reaction product of an epoxy resin and an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group with a polybasic acid and / or an anhydride thereof and a polyfunctional alcohol , &Lt; / RTI &gt; In this case, the mixing order of the polybasic acid and / or the anhydride thereof and the polyfunctional alcohol is not particularly limited. By heating, a polybasic acid and / or a polybasic acid may be added to any hydroxyl groups present in a mixture of an epoxy resin and an α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxyl group and a polyfunctional alcohol The anhydride undergoes addition reaction.

Examples of the epoxy (meth) acrylate resin include those described in Korean Patent Publication No. 10-2013-0022955, and the like.

The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin as measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 1000 or more, preferably 1,500 or more, more preferably 2,000 or more Preferably not less than 3000, more preferably not less than 4000, particularly preferably not less than 5000, and usually not more than 10,000, preferably not more than 8,000, more preferably not more than 7,000. When the amount is above the lower limit value, there is a tendency that the solubility in the developer is prevented from becoming too high. When the amount is less than the upper limit value, the solubility in the developer tends to be good. For example, the combination of the upper limit and the lower limit is preferably from 1,000 to 10,000, more preferably from 1,500 to 8,000, even more preferably from 2,000 to 8,000, even more preferably from 3,000 to 8,000, and particularly preferably from 4,000 to 8,000 And most preferably 5,000 to 7,000.

The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, even more preferably 40 mgKOH / g or more, More preferably not more than 200 mg KOH / g, more preferably not more than 150 mg KOH / g, even more preferably not more than 120 mg KOH / g, even more preferably not more than 100 mg KOH / g Is particularly preferable. When the amount is above the lower limit value, adequate developing solubility tends to be obtained. When the amount is less than the upper limit value, the development tends to proceed excessively to prevent the film from dissolving. For example, the combination of the upper limit and the lower limit is preferably from 10 to 200 mgKOH / g, more preferably from 20 to 150 mgKOH / g, still more preferably from 40 to 100 mgKOH / g, MgKOH / g are particularly preferable.

Although the chemical structure of the epoxy (meth) acrylate resin is not particularly limited, from the viewpoint of developability and reliability, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b1-I) An epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b1-II) (hereinafter sometimes abbreviated as "(b1-I) epoxy (meth) (B1-II) epoxy (meth) acrylate-based resin ").

(11)

Formula (I-b1) of, R ¹¹ is a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, and * represents a bonding hand. The benzene ring in the formula (b1-I) may be further substituted by an arbitrary substituent.

[Chemical Formula 12]

In the formula (b1-II), each R ¹³ independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, And m and n each independently represent an integer of 0 to 2, and * represents a bonded linkage.

<(b1-I) Epoxy (meth) acrylate resin>

First, an epoxy (meth) acrylate resin having a partial structure represented by the general formula (b1-I) will be described in detail.

[Chemical Formula 13]

Formula (I-b1) of, R ¹¹ is a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, and * represents a bonding hand. The benzene ring in the formula (b1-I) may be further substituted by an arbitrary substituent.

(R ¹² )

In the above formula (b1-I), R ¹² represents a divalent hydrocarbon group which may have a substituent.

Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group having at least one divalent aliphatic group and at least one divalent aromatic ring group linked to each other.

Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Of these, a linear type is preferable from the viewpoint of developing solubility. On the other hand, from the viewpoint of reducing penetration of the developer into the exposed portion, it is preferable to use a ring. The number of carbon atoms thereof is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, a n-hexylene group, and an n-heptylene group . Among them, a methylene group is preferable in view of rigidity of the skeleton.

Examples of the divalent branched-chain aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec- Butyl group, tert-butyl group, and the like.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the amount is higher than the lower limit value, the film becomes a strong film, and the substrate adhesion tends to be good. When it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed and resolution is improved. Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, And groups obtained by removing two hydrogen atoms from a ring such as dicyclopentadiene. Among these, from the viewpoint of rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring and an adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of easiness of synthesis, it is preferable that it is indefinite.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms thereof is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.

The aromatic hydrocarbon ring in the bivalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include groups having two free valences such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole A thiophenol ring, a thiophenol ring, a thiophenol ring, a thiophenol ring, a thienophenol ring, a benzoisooxazole ring, a thiophenol ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzoimidazole ring, A benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

Of these, benzene rings or naphthalene rings having two free valences are preferable, and benzene rings having two free valences are more preferable in view of the patterning property.

Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Of these, from the viewpoint of solubility in development, unsubstituted is preferable.

The group in which at least one divalent aliphatic group and at least one divalent aromatic ring group are linked includes a group in which one or more of the above-mentioned divalent aliphatic groups is linked to one or more of the aforementioned divalent aromatic ring groups.

The number of the bivalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 3.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 3.

Specific examples of the group linking at least one bivalent aliphatic group and at least one bivalent aromatic ring group include the groups represented by the following formulas (b1-I-A) to (b1-I-F). Among them, the group represented by the following formula (b1-I-A) is preferable from the viewpoints of rigidity of the skeleton and hydrophobicity of the film.

[Chemical Formula 14]

As described above, the benzene ring in the formula (b1-I) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among them, from the viewpoint of the patterning characteristic, it is preferable that it is irregular.

The partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of simplicity of synthesis.

[Chemical Formula 15]

In the formula (b1-I-1), R ¹¹ and R ¹² have the same meanings as those of the formula (b1-I), R ^X represents a hydrogen atom or a polybasic acid residue, and * represents a bonding bond. The benzene ring in the formula (b1-I-1) may be further substituted by an arbitrary substituent.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, There may be mentioned one or two or more selected from acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.

Of these, from the viewpoint of the patterning property, it is preferable to use maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid, , Tetrahydrophthalic acid, biphenyltetracarboxylic acid, biphenyltetracarboxylic acid.

(b1-I) an epoxy (meth) partial structure represented by the formula (b1-I-1) contained in the acrylate-based resin 1 molecule, the least one member, and may be two or more kinds, for example, R ^X is A hydrogen atom, and R ^x may be a polybasic acid residue.

The number of partial structures represented by the formula (b1-I) contained in one molecule of the epoxy (meth) acrylate resin (b1-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more , More preferably 20 or less, and further preferably 15 or less. When the content is not less than the above lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and if it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed, have. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15.

 The weight average molecular weight (Mw) of the (b1-I) epoxy (meth) acrylate based resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1,000 or more, More preferably not less than 2000, still more preferably not less than 3,000, particularly preferably not less than 4,000, most preferably not less than 5,000, further preferably not more than 30,000, more preferably not more than 20,000, And still more preferably 8000 or less. When the ratio is above the lower limit value, the residual film ratio of the photosensitive coloring composition tends to be good. When the content is made lower than the upper limit value, the resolution tends to be good. For example, the combination of the upper limit and the lower limit is preferably from 1,000 to 30,000, more preferably from 1,500 to 20,000, still more preferably from 2,000 to 10,000, even more preferably from 3,000 to 10,000, and particularly preferably from 4,000 to 80,000 And most preferably 5,000 to 8,000.

The acid value of the epoxy resin (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, G, more preferably at least 50 mgKOH / g, particularly preferably at least 80 mgKOH / g, even more preferably at most 200 mgKOH / g, even more preferably at most 150 mgKOH / g, MgKOH / g or less, and particularly preferably 100 mgKOH / g or less. When the amount is above the lower limit value, development solubility is improved and the resolution tends to be good. When the amount is less than the upper limit value, the residual film ratio of the photosensitive coloring composition tends to become good. For example, the combination of the upper limit and the lower limit is preferably from 10 to 200 mgKOH / g, more preferably from 20 to 150 mgKOH / g, still more preferably from 40 to 100 mgKOH / g, MgKOH / g is more preferable, and 80-100 mgKOH / g is particularly preferable.

Specific examples of the (b1-I) epoxy (meth) acrylate resin are given below. Also, in the example, * indicates a combined hand.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

<(b1-II) Epoxy (meth) acrylate resin>

Next, the epoxy (meth) acrylate resin having the partial structure represented by the general formula (b1-II) will be described in detail.

[Chemical Formula 20]

In the formula (b1-II), each R ¹³ independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, And m and n each independently represent an integer of 0 to 2, and * represents a bonded linkage.

(R ¹⁴⁾

Wherein in the formula (b1-II), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the content is not less than the above lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and if it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed, have. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 3.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, Is particularly preferable. When the content is not less than the above lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and if it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed, have. For example, the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and even more preferably 8 to 20.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, and the like. . Of these, adamantane rings are preferable from the viewpoint of the residual film ratio and resolution of the photosensitive coloring composition.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, desirable. When the content is not less than the above lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and if it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed, have. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 3 to 4.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 10 or more, particularly preferably 12 or more, More preferably 20 or less, and particularly preferably 15 or less. When the amount is higher than the lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and when it is made lower than the upper limit value, the patterning property tends to become good. For example, the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15.

Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, An acenaphthene ring, a fluoranthene ring, and a fluorene ring. Among them, from the viewpoint of the patterning property, a fluorene ring is preferable.

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, at least one divalent aliphatic group and at least one divalent group And a group connecting an aromatic ring group.

Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Of these, a linear type is preferred from the viewpoint of developing solubility, and a cyclic type is preferable from the viewpoint of reducing penetration of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, a n-hexylene group, and an n-heptylene group . Among them, a methylene group is preferable in view of rigidity of the skeleton.

Examples of the divalent branched-chain aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec- Butyl group, tert-butyl group, and the like.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the amount is higher than the lower limit value, the film becomes a strong film, and the substrate adhesion tends to be good. When it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed and resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 3.

Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. And a group obtained by removing two hydrogen atoms from the ring of R &lt; 2 &gt; Among these, from the viewpoint of rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of easiness of synthesis, it is preferable that it is indefinite.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms thereof is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.

The aromatic hydrocarbon ring in the bivalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring having two free valences, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, , A carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzoisoxazole ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzoimidazole ring, a benzoimidazole ring, An imidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Of these, benzene rings or naphthalene rings having two free valences are preferable, and benzene rings having two free valences are more preferable in view of the patterning property.

Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Of these, from the viewpoint of solubility in development, unsubstituted is preferable.

The group in which at least one divalent aliphatic group and at least one divalent aromatic ring group are linked includes a group in which one or more of the above-mentioned divalent aliphatic groups is linked to one or more of the aforementioned divalent aromatic ring groups.

The number of the bivalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 3.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 3.

Specific examples of the group linking at least one bivalent aliphatic group and at least one bivalent aromatic ring group include the groups represented by the above formulas (b1-I-A) to (b1-I-F). Among them, the group represented by the above formula (b1-I-C) is preferable from the viewpoints of rigidity of the skeleton and hydrophobicity of the film.

The bonding state of the cyclic hydrocarbon group as a side chain with respect to these bivalent hydrocarbon groups is not particularly limited. For example, there may be mentioned an embodiment in which one hydrogen atom of an aliphatic group or aromatic ring group is substituted with a side chain thereof, A cyclic hydrocarbon group having a side chain including one of carbon atoms is constituted.

(R ¹⁵ , R ¹⁶ )

In the general formula (b1-II), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Of these, a linear type is preferred from the viewpoint of developing solubility, and a cyclic type is preferable from the viewpoint of reducing penetration of the developing solution into the exposed portion. The number of carbon atoms thereof is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When the content is not less than the above lower limit value, a strong film is easily obtained, surface roughness hardly occurs, and adhesiveness to the substrate tends to be good. When the content is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development can be suppressed, There is a tendency that the resolution is improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, a n-hexylene group, and an n-heptylene group . Among them, a methylene group is preferable in view of rigidity of the skeleton.

Examples of the divalent branched-chain aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec- Butyl group, tert-butyl group, and the like.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the amount is higher than the lower limit value, the film becomes a strong film, and the substrate adhesion tends to be good. When it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed and resolution is improved. For example, as the combination of the upper limit and the lower limit, 1 to 12 is preferable, and 2 to 10 is more preferable.

Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, And groups obtained by removing two hydrogen atoms from a ring such as dicyclopentadiene. Among these, from the viewpoint of rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring and an adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of easiness of synthesis, it is preferable that it is indefinite.

(m, n)

In the general formula (b1-II), m and n each independently represents an integer of 0 to 2. When the amount is above the lower limit value, the patterning titration tends to be good and the surface roughness tends to be hard to occur. On the other hand, when the amount is less than the upper limit value, the developing property tends to be good. From the viewpoint of developability, it is preferable that m and n are 0. On the other hand, from the viewpoints of patterning titration and surface roughness, m and n are preferably 1 or more.

The partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1) from the viewpoint of adhesiveness to a substrate.

[Chemical Formula 21]

In the formula (b1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in the formula (b1-II), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent, p is an integer of 1 or more, . The benzene ring in the formula (b1-II-1) may be further substituted by an arbitrary substituent.

(R ^? )

In the general formula (b1-II-1), R ^? Represents a monovalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the amount is higher than the lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and when it is made lower than the upper limit value, the patterning property tends to become good. For example, the combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 2 to 4, and still more preferably 2 to 3.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, Is particularly preferable. When the amount is higher than the lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and when it is made lower than the upper limit value, the patterning property tends to become good. For example, the combination of the upper limit and the lower limit is preferably from 4 to 40, more preferably from 6 to 30, still more preferably from 8 to 20, and particularly preferably from 8 to 15.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, and the like. . Of these, adamantane rings are preferred from the viewpoint of strong film properties.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and preferably 5 or less. When the amount is higher than the lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and when it is made lower than the upper limit value, the patterning property tends to become good. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 3 to 5.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. When the amount is higher than the lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and when it is made lower than the upper limit value, the patterning property tends to become good. For example, the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and a fluorene ring. Among them, a fluorene ring is preferable from the viewpoint of developing solubility.

Examples of the substituent which the cyclic hydrocarbon group may have include a carbon number such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- An alkyl group of 1 to 5; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of easiness of synthesis, unsubstituted is preferable.

p represents an integer of 1 or more, but is preferably 2 or more, and is preferably 3 or less. When the amount is higher than the lower limit value, the film curability and the residual film tends to be good, and when it is less than the upper limit value, the developability tends to be good. For example, the combination of the upper limit and the lower limit is preferably 1 to 3, more preferably 2 to 3.

Among these, from the viewpoint of a strong film hardening degree, R ^? Is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

As described above, the benzene ring in the formula (b1-II-1) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among them, from the viewpoint of the patterning characteristic, it is preferable that it is irregular.

Specific examples of the partial structure represented by the above formula (b1-II-1) are shown below.

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

The partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2) from the viewpoints of rigidity of the skeleton and film hydrophobicity.

(27)

In the formula (b1-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in the formula (b1-II), R ^β denotes a divalent cyclic hydrocarbon group which may have a substituent, and * denotes a bonding hand. The benzene ring in the formula (b1-II-2) may be further substituted by an arbitrary substituent.

(R ^? )

In the above formula (b1-II-2), R ^? Represents a divalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the content is not less than the above lower limit value, a strong film tends to be obtained, surface roughness tends not to be easily generated, and if it is made lower than the upper limit value, deterioration of the sensitivity and film reduction during development tends to be suppressed, have. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, and more preferably 2 to 5.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When the amount is not less than the above lower limit value, film tackiness at the time of development tends to be suppressed, and when it is not more than the upper limit value, deterioration of the sensitivity and reduction of film at the time of development tends to be suppressed and the resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, adamantane rings are preferable from the viewpoint of film reduction and resolution at the time of development.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and preferably 5 or less. By setting the value above the lower limit value, a strong film tends to be easily obtained, surface roughness tends not to occur easily, and if it is made lower than the upper limit value, deterioration of sensitivity and film reduction can be suppressed easily and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 3 to 5.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, further preferably 40 or less, more preferably 30 or less, More preferably 15 or less. By setting the value above the lower limit value, a strong film tends to be easily obtained, surface roughness tends not to occur easily, and if it is made lower than the upper limit value, deterioration of sensitivity and film reduction can be suppressed easily and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and a fluorene ring. Of these, fluorene rings are preferred from the viewpoint of developability.

Examples of the substituent which the cyclic hydrocarbon group may have include a carbon number such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- An alkyl group of 1 to 5; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of simplicity of synthesis, unsubstituted is preferable.

Among these, R &^lt; ^{beta &gt;} is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, from the viewpoint of suppression of film reduction and resolution.

On the other hand, from the viewpoint of the patterning property, R ^? Is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.

As described above, the benzene ring in the formula (b1-II-2) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Two benzene rings may be connected via a substituent. Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, -CH ₂ - and the like.

Among them, from the viewpoint of the patterning characteristic, it is preferable that it is irregular. In addition, from the viewpoint of preventing film reduction or the like from occurring, methyl group substitution is preferable.

Specific examples of the partial structure represented by the above formula (b1-II-2) are listed below. Also, in the example, * indicates a combined hand.

(28)

[Chemical Formula 29]

(30)

(31)

On the other hand, the partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoints of the coating film remaining ratio and the patterning property.

(32)

In the formula (b1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in the formula (b1-II), and R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. In addition, the added group is also removed by one OH, formula (b1-II-3) as shown, and may be shared with the R ^Z according to another molecule, that is, a plurality of R ^Z formula (b1-II- via the 3) may be connected.

Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, Acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and the like.

Of these, from the viewpoint of the patterning property, it is preferable to use maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid, , Tetrahydrophthalic acid, biphenyltetracarboxylic acid, biphenyltetracarboxylic acid.

(b1-II) The partial structure represented by the above formula (b1-II-3) contained in one molecule of the epoxy (meth) acrylate resin may be one or two or more, for example, R ^Z May be a hydrogen atom, and R ^Z may be a polybasic acid residue.

The number of the partial structure represented by the above formula (b1-II) contained in one molecule of the epoxy (meth) acrylate resin (b1-II) is not particularly limited, but is preferably 1 or more, And is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting the value above the lower limit value, a strong film tends to be easily obtained, surface roughness tends not to occur easily, and if it is made lower than the upper limit value, deterioration of sensitivity and film reduction can be suppressed easily and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and even more preferably 3 to 10.

The weight average molecular weight (Mw) of the (b1-II) epoxy (meth) acrylate based resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1,000 or more, More preferably 30,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less, still more preferably 7,000 or less, and particularly preferably 5,000 or less. When the amount is above the lower limit value, the patterning property tends to be good, and when it is not more than the upper limit value, a strong film tends to be obtained, and surface roughness tends not to occur easily. For example, the combination of the upper limit and the lower limit is preferably from 1,000 to 30,000, more preferably from 1,000 to 20,000, still more preferably from 2,000 to 10,000, even more preferably from 2,000 to 7,000, even more preferably from 2,000 to 5,000 .

The acid value of the epoxy resin (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, G, more preferably at least 60 mgKOH / g, particularly preferably at least 80 mgKOH / g, most preferably at least 100 mgKOH / g, even more preferably at least 200 mgKOH / g, MgKOH / g or less, and more preferably 120 mgKOH / g or less. When the amount is above the lower limit value, a strong film tends to be easily obtained, and when it is not more than the upper limit value, development solubility is improved and resolution is improved. For example, the combination of the upper limit and the lower limit is preferably from 10 to 200 mgKOH / g, more preferably from 20 to 150 mgKOH / g, still more preferably from 40 to 150 mgKOH / g, MgKOH / g is more preferable, and 80 to 120 mgKOH / g is particularly preferable.

The epoxy (meth) acrylate resin may be used singly or as a mixture of two or more resins.

A part of the above-mentioned epoxy (meth) acrylate resin may be substituted by another binder resin. That is, the epoxy (meth) acrylate resin may be used in combination with another binder resin. In this case, the proportion of the epoxy (meth) acrylate resin in the alkali-soluble resin (b) is preferably 50 mass% or more, more preferably 60 mass% or more, and more preferably 70 mass% or more , More preferably 80 mass% or more, and most preferably 100 mass% or less.

For example, the combination of the upper limit and the lower limit is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, still more preferably 70 to 100 mass%, and particularly preferably 80 to 100 mass% .

Other binder resins that can be used in combination with the epoxy (meth) acrylate-based resin are not limited and may be selected from resins commonly used in photosensitive coloring compositions. For example, binder resins described in JP-A-2007-271727, JP-A-2007-316620, JP-A-2007-334290 and the like can be given. Further, all of the other binder resins may be used alone or in combination of two or more.

As the alkali-soluble resin (b), from the viewpoint of compatibility with the pigment and the dispersant, (b2) an acrylic copolymer resin is preferably used, and those described in JP-A-2014-137466 can be preferably used.

Examples of the acrylic copolymer resin include an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter referred to as &quot; unsaturated monomer (b2-1) &quot;) and a copolymerizable ethylenically unsaturated monomer (hereinafter referred to as &quot; unsaturated monomer b2-2) &quot;). &lt; / RTI &gt;

Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, alpha -chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid, or anhydrides thereof; Mono [(meth) acryloyloxyalkyl] monovalent monocarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters; mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate; p-vinylbenzoic acid and the like.

These unsaturated monomers (b2-1) may be used alone or in combination of two or more.

Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Methylstyrene, p-vinylbenzylglycidylether and acenaphthylene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2- (Meth) acrylate, polyethylene glycol (polymerization degree 2 to 10), methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) , Polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide- (Meth) acrylate, 3,4- Acrylate such as (meth) acryloyloxymethyl (meth) acrylate, 3 - [(meth) acryloyloxymethyl] oxetane and 3 - [(meth) acryloyloxymethyl] ;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Vinyl ethers such as vinyl ether;

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These unsaturated monomers (b2-2) may be used singly or in combination of two or more.

In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) in the copolymer is preferably 5 to 50% by mass, 10 to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) in such a range, there is a tendency to obtain a photosensitive coloring composition excellent in alkali developability and storage stability.

Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, those described in JP-A-7-140654, JP-A-8-259876, Japanese Patent Application Laid-Open Nos. 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, And JP-A-2004-101728.

The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method. For example, JP-A-2003-222717, JP-A-2006-259680 The structure, Mw, and Mw / Mn can also be controlled by a method disclosed in International Publication No. 2007/029871.

< (c) Photopolymerization initiator >

(c) The photopolymerization initiator is a component having a function of directly absorbing light to generate a decomposition reaction or a hydrogen withdrawing reaction to generate a polymerization activity radical. If necessary, additives such as polymerization accelerators (chain transfer agents), sensitizing dyes and the like may be added and used.

Examples of the photopolymerization initiator include metallocene compounds containing a titanocene compound described in JP-A-59-152396 and JP-A-61-151197; Hexaarylbimidazole derivatives described in Japanese Patent Application Laid-Open No. 2000-56118; Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives described in JP-A-10-39503; alpha -aminoalkylphenone derivatives; Oxime ester compounds described in JP-A-2000-80068, JP-A-2006-36750, and the like.

Specific examples of the titanocene derivative include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2, 3, 4, 5, 6 (Pentafluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium Dicyclopentadienyltitanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,6-difluorophenyl) Pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro- - (pyrro-1-yl) -phenyl], and the like.

Examples of hexaaryl biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (2'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- Diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ Vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5 - [? - (2 '- (6 "-benzofuryl) 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, and the like.

Examples of halomethyl-s-triazine derived products include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) 4,6-bis (trichloromethyl) -s-triazine, and the like.

Examples of the? -Aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylamino Diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexane Diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone.

As the photopolymerization initiator, oxime ester compounds are effective, particularly in view of sensitivity and formability. When an alkali-soluble resin containing a phenolic hydroxyl group is used, oxime ester compounds having such excellent sensitivity are particularly useful Do. The oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure. Therefore, even a small amount of oxime ester compound has high sensitivity, is stable to thermal reaction, It is possible to obtain a photosensitive coloring composition.

As the oxime ester compound, for example, a compound represented by the following general formula (IV) can be mentioned.

(33)

In formula (IV), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent, and R ^21b represents an arbitrary substituent containing an aromatic ring or a hetero ring, R ^22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 15 or less in terms of solubility in a solvent and sensitivity. 10 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 2 to 15, and even more preferably 2 to 10.

Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4- (2-methoxy- -Acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, it is preferable that the group is indefinite.

^Examples of the aromatic ring group in R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in a photosensitive coloring composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the combination of the upper limit and the lower limit is preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among them, a phenyl group or a naphthyl group is preferable from the viewpoint of developability, and a phenyl group is more preferable.

Examples of the substituent which the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group and a group to which a substituent thereof is connected. One group is preferable, and the connected alkoxy group is more preferable.

Among them, from the viewpoint of developability, R ^21a is preferably an aromatic ring group which may have a substituent, more preferably an aromatic ring group which has a connected alkoxy group in a substituent.

Examples of R ^21b include a carbazolyl group which may be substituted, a thioxanthonyl group which may be substituted, or a diphenylsulfide group which may be substituted. Among them, a carbazolyl group which may be substituted is preferable from the viewpoint of sensitivity. On the other hand, from the viewpoint of electrical reliability, a diphenyl sulfide group which may be substituted is preferable.

The number of carbon atoms of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility and sensitivity to a solvent. More preferably 10 or less, still more preferably 5 or less. For example, the combination of the upper limit and the lower limit is preferably 2 to 20, more preferably 2 to 15, still more preferably 3 to 10, and particularly preferably 3 to 5.

Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.

Examples of the substituent which the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group, and from the viewpoint of ease of synthesis, it is preferable that the substituent is indeterminate.

The number of carbon atoms of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility and sensitivity to a solvent. More preferably 10 or less. Specific examples of the aryloxy group include a benzoyl group and a naphthoyl group. For example, the combination of the upper limit and the lower limit is preferably 7 to 20, more preferably 8 to 15, and even more preferably 8 to 10.

Examples of the substituent which the arylthio group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group, and from the viewpoint of ease of synthesis, an amorphous is preferable.

Of these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and more preferably an acetyl group.

One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

The photopolymerization initiator may be compounded with a sensitizing dye and a polymerization promoter depending on the wavelength of the image exposure light source, for the purpose of increasing the sensitivity of sensitivity, if necessary. Examples of the sensitizing dye include those described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335 Coumarin dyes having heterocyclic rings, 3-ketocoumarin compounds described in JP-A Nos. 3-239703 and 5-289335, pyromethene dyes described in JP-A No. 6-19240, In addition, JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A-52-112681 Japanese Patent Application Laid-Open No. 58-15503, Japanese Laid-Open Patent Publication No. 60-88005, Japanese Laid-Open Patent Application No. 59-56403, Japanese Laid-Open Patent Application No. 2-69, Japanese Laid-Open Patent Publication No. 57-168088 JP-A-5-107761, JP-A-5-210240, and JP-A- Described in No. Hei 4-288818 it can be mentioned the dye or the like having a dialkyl aminobenzene skeleton.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'- Benzophenone compounds such as phenone, 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; Benzooxazole, 2- (p-dimethylaminophenyl) benzooxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (P-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzothiazole, 2- Diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p- dimethylaminophenyl) quinoline, Phenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone is most preferable.

The sensitizing dye may be used singly or in combination of two or more species.

Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, mercapto compounds described later, and the like Is used. The polymerization accelerator may be used alone or in combination of two or more.

< (d) Ethylenically unsaturated compound >

The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (d) By containing an ethylenically unsaturated compound, the sensitivity is improved.

The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenic unsaturated group in the molecule. Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, and carboxylic acid having one ethylenic unsaturated bond and monoester of polyhydric or monohydric alcohol have.

In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule. The number of ethylenic unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less , And more preferably 7 or less. The above-mentioned lower limit value tends to give higher sensitivity, and when it is lower than the upper limit value, the solubility in a solvent tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 2 to 8, more preferably 4 to 7, and still more preferably 5 to 7.

Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; An ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; Aliphatic polyhydroxy compounds, and aromatic polyhydroxy compounds, and esters obtained by esterification reaction of an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, Examples of the aliphatic polyhydroxy compound such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate include acrylic acid Esters, methacrylic acid esters in which acrylates of these exemplified compounds are replaced by methacrylates, itaconic acid esters in place of itaconates in the same manner, crotonic acid esters in place of crotonates, or maleic esters in place of maleate To have.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include aromatic polyesters such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinodiacrylate, resorcine dimethacrylate and pyrogallol triacrylate; Acrylic acid esters and methacrylic acid esters of hydroxy compounds, and the like.

The esters obtained by the esterification reaction between the polybasic carboxylic acid and the unsaturated carboxylic acid and the polyhydric hydroxy compound are not necessarily a single substance. Representative examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol, acrylic acid, maleic acid Acid and condensation products of diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, and the like.

Examples of the polyfunctional ethylenic monomer used in the present invention include urethane (meth) acrylate obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate or polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) Acrylates; Epoxy acrylates such as polyaddition epoxy compounds and addition reactants of hydroxy (meth) acrylate or (meth) acrylic acid; Acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; And vinyl group-containing compounds such as divinyl phthalate.

Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Yakusha), U-2PPA, U- UA-510H, UF-8001G (manufactured by Kyowa Chemical Industry Co., Ltd.), UV-1700B (manufactured by Shin-Nakamura Chemical Industrial Co., Ltd.), UA-10PA, U-33H, UA-53H, UA- , UV-7600B, UV-7605B, UV-7630B and UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

Among them, from the viewpoint of the curability, it is preferable to use (meth) acrylic acid alkyl ester as the ethylenically unsaturated compound (d), and it is more preferable to use dipentaerythritol hexaacrylate.

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

<(e) Solvent>

The photosensitive coloring composition of the present invention contains (e) a solvent. (e) By containing a solvent, (a) the colorant can be dissolved or dispersed in a solvent, and the application is facilitated.

The photosensitive coloring composition of the present invention is usually prepared by a method comprising the steps of (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) Various materials are used in a state dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferable from the viewpoints of dispersibility and coatability.

Among organic solvents, those having a boiling point in the range of 100 to 300 占 폚 are preferably selected from the viewpoint of coatability, and those having a boiling point in the range of 120 to 280 占 폚 are more preferable. The boiling point referred to here means the boiling point at a pressure of 1013.25 hPa, and the boiling point is all the same.

Examples of such an organic solvent include the following.

Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Glycol monoalkyl ethers such as butoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether ;

Ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether But are not limited to, acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol mono Glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate and 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanediol acetate;

Alkyl acetates such as cyclohexanol acetate;

Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether;

Examples of the solvent include acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, Ketones such as ketone, methyl nonyl ketone, methoxymethyl pentanone;

But are not limited to, monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, Ryu;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane;

Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene and cumene;

Ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, methyl isobutyrate, ethyl isobutyrate, ethyl propionate, propyl propionate, isobutyl butyrate, methyl isobutyrate, Ethyl propionate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Chain or cyclic esters such as butyl methoxypropionate and? -Butyrolactone;

Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride and amyl chloride;

Ether ketones such as methoxymethylpentanone;

Nitriles such as acetonitrile, benzonitrile, and the like.

Examples of commercially available organic solvents include Mineral Spray, Barthol # 2, Acco # 18 Solvent, Afucosiner, SoCal Solvent No.1 and No.2, Solvesso # 150, Shell TS28 Solvent, , Ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) .

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

When a colored spacer is formed by a photolithography method, it is preferable to select an organic solvent having a boiling point of 100 to 200 캜. More preferably a boiling point of 120 to 170 占 폚.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent to be used in combination, glycol monoalkyl ethers are particularly preferable. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of the constituent components in the composition. The glycol monoalkyl ether has a high polarity. When the amount of the glycol monoalkyl ether to be added is too large, the pigment tends to aggregate and the storage stability such as the viscosity of the resulting photosensitive colored composition tends to be lowered. Therefore, Is preferably from 5% by mass to 30% by mass, and more preferably from 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 150 캜 or more (hereinafter sometimes referred to as a &quot; high boiling point solvent &quot;). When such a high-boiling solvent is used in combination, the photosensitive coloring composition is not dried well, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of a coloring agent or the like at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate and diethylene glycol monoethyl ether acetate are particularly preferable from the viewpoint of high effect.

When the high boiling point solvent is used in combination, the content ratio of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, still more preferably 5% by mass to 30% Particularly preferred. By setting the temperature at or above the lower limit value, for example, the coloring material or the like precipitates and solidifies at the tip of the slit nozzle to prevent occurrence of foreign matter defects. In addition, Problems such as defective tack in the reduced-pressure drying process and pin marks on pre-baking tend to be suppressed.

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

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

<(f) Dispersant>

In the photosensitive coloring composition of the present invention, (f) a dispersing agent is contained because (a) finely dispersing the colorant and stabilizing the dispersed state are important for securing the stability of the quality.

As the (f) dispersing agent, a polymer dispersing agent having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxyl group; Phosphate group; Sulfonic acid group; Or a base thereof; A primary, secondary or tertiary amino group; Quaternary ammonium salt group; A polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is preferable. Among them, a primary, secondary or tertiary amino group; Quaternary ammonium salt group; A polymer dispersant having a basic functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferable from the viewpoint that the pigment can be dispersed with a small amount of a dispersant when the pigment is dispersed.

Examples of the polymer dispersing agent include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallyl amine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, An ester-based dispersant, a polyether phosphoric acid-based dispersant, a polyester phosphoric acid-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified polyester-based dispersant.

Specific examples of such dispersants include, but are not limited to, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BICKEMISA), DIPARON (registered trademark, (Registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyowa Chemical Industry Co., Ltd.) and Ajisper (registered trademark by Ajinomoto Co., Ltd.).

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100000 or less, preferably 50000 or less. For example, as the combination of the upper limit and the lower limit, 700 to 100000 is preferable, and 1000 to 50000 is more preferable.

Among them, from the viewpoint of dispersibility of the pigment, (f) the dispersant preferably contains a urethane-based polymer dispersant having functional groups and / or an acrylic polymer dispersant, and particularly preferably contains an acrylic polymer dispersant.

In view of dispersibility and preservability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.

Examples of the urethane-based and acrylic-based polymer dispersing agents include DISPERBYK 160 to 166 and 182 series (all-urethane type), DISPERBYK 2000, 2001 and BYK-LPN21116 (all acrylic type).

For example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, a compound having an active hydrogen and a tertiary amino group And a dispersion resin having a weight average molecular weight of 1,000 to 200,000. By treating them with a quaternizing agent such as benzyl chloride, all or a part of the tertiary amino group can be quaternary ammonium salt group.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene- Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, isophorone diisocyanate, 4,4 ', 4,4'-tetramethylene diisocyanate and the like, aromatic diisocyanates such as toluidine diisocyanate, Alicyclic diisocyanates such as methylenebis (cyclohexylisocyanate) and omega'-diisocyanate dimethylcyclohexane, xylylene diisocyanate, and aromatic rings such as alpha, alpha, alpha ', alpha'-tetramethyl xylylene diisocyanate Alicyclic diisocyanate, lysine ester triisocyanate, 1,6,11- (Isocyanatophenyl) thiophosphate, and the like can be used. Examples of the isocyanate compound include decanediisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, Triisocyanates, trimer thereof, water adducts thereof, and polyol adducts thereof. The polyisocyanate is preferably a trimer of an organic diisocyanate, most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used singly or in combination of two or more.

As a method for producing the trimer of isocyanate, the above polyisocyanate is reacted with an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, And then the polymerization is terminated by addition of a catalyst poison. Thereafter, unreacted polyisocyanate is removed by solvent extraction or thin-film distillation to obtain a desired isocyanurate group-containing polyisocyanate .

Examples of the compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols and the like, and compounds in which the terminal hydroxyl groups of these compounds have 1 to 25 carbon atoms Alkoxylated with an alkyl group, and mixtures of two or more thereof.

Examples of the polyether glycol include polyether diol, polyether ester diol, and mixtures of two or more thereof. Examples of the polyether diol include those obtained by using an alkylene oxide alone or by copolymerization, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, And mixtures of two or more thereof.

Polyetherester diols include those obtained by reacting a mixture with an ether group-containing diol or other glycol with a dicarboxylic acid or anhydride thereof, or by reacting an alkylene oxide with a polyester glycol, for example, poly Oxytetramethylene) adipate, and the like. Polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms is most preferable as the polyether glycol.

Examples of the polyester glycol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3- 2-methyl-1,3-propanediol, 1,5-pentanediol, 1, 2-methyl- Methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5- Aliphatic glycols such as 5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, Aromatic glycols such as glycols and bishydroxyethoxybenzenes, , N-alkyldialkanolamines such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, Or a polylactone diol or polylactone monool obtained by using the diol or a monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone, and a mixture of two or more thereof . The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone having an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, Isoprene glycol and the like.

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

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.

Compounds having active hydrogen and tertiary amino groups in the same molecule used in the present invention will be described.

Examples of the active hydrogen atom, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group and a thiol group. Among them, an amino group, The atom is preferred.

The tertiary amino group is not particularly limited and includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl- 1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N , N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, , N-dibutyl-1,4-butanediamine, and the like.

Examples of the nitrogen-containing heterocyclic ring when the tertiary amino group is a nitrogen-containing heterocyclic ring structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, A nitrogen-containing hetero 5 membered ring such as imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring , A nitrogen-containing hetero-six-membered ring such as a quinoline ring, an acridine ring, and an isoquinoline ring. Preferred among these nitrogen-containing heterocyclic rings are imidazole rings or triazole rings.

Specific examples of the compound having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole and 1- (2-aminoethyl) imidazole. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino- 1, 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, -Triazole is preferred.

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

The preferable mixing ratio of the starting materials in the production of the urethane polymer dispersant is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule per 100 parts by mass of the polyisocyanate compound Preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule in an amount of 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

The production of the urethane-based polymeric dispersant is carried out according to a known method of producing a polyurethane resin. As the solvent in the preparation, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, Examples of the solvent include hydrocarbons such as benzene, toluene, xylene and hexane, alcohols such as diacetone alcohol, isopropanol, secondary butanol and tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether Aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and the like are used. These may be used singly or in combination of two or more.

In the above production, usually, a urethanization reaction catalyst is used. Examples of the catalyst include tin-based catalysts such as dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dioctoate and stannous octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; Tertiary amines such as ethylamine and triethylenediamine, and the like. These may be used singly or in combination of two or more.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g of the amine after the reaction. And more preferably in the range of 5 to 95 mgKOH / g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing the basic amino group with an acid. When the amount is above the lower limit value, the dispersing ability tends to be good. When the amount is less than the upper limit value, the decrease in developability tends to be suppressed.

Further, when the isocyanate group remains in the polymer dispersant in the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product increases.

The weight average molecular weight (Mw) of the urethane type polymeric dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When the amount is above the lower limit value, the dispersibility and the dispersion stability tend to be good. When the amount is less than the upper limit value, the decrease in solubility and dispersibility tends to be suppressed.

On the other hand, as the acrylic polymer dispersant, a random copolymer of an unsaturated group-containing monomer having a functional group (the functional group mentioned above is a functional group contained in the polymer dispersant as described above) and an unsaturated group-free monomer having no functional group, It is preferable to use a block copolymer. These copolymers can be prepared by known methods.

Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- Unsaturated monomers having a tertiary amino group and a quaternary ammonium salt group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and quaternary compounds thereof, such as unsaturated monomers having a carboxyl group such as hydrophthalic acid and dimethacrylic acid, Specific examples include: These may be used singly or in combination of two or more.

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (Meth) acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone , Styrene and its derivatives, N-substituted maleimides such as? -Methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) Rate macro maco Macromonomers such as nomar, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer and polycaprolactone macromonomer. These may be used singly or in combination of two or more.

Particularly preferably, the acrylic polymer dispersant is an AB or BAB block copolymer comprising an A block having a functional group and a B block having no functional group. In this case, in the A block, a portion derived from the monomer containing an unsaturated group containing the functional group Or may contain a partial structure derived from an unsaturated group-containing monomer containing no functional group, and these may be contained in the A block in any of random copolymerization and block copolymerization. The proportion of the partial structure containing no functional group in the A block is usually 80 mass% or less, preferably 50 mass% or less, more preferably 30 mass% or less.

The B block is composed of a partial structure derived from an unsaturated group-containing monomer not containing the above-mentioned functional group. However, one B block may contain a partial structure derived from two or more kinds of monomers. Or block copolymerization.

The AB or B-A-B block copolymer is prepared, for example, by a living polymerization method shown below.

Examples of the living polymerization method include anionic polymerization, cationic living polymerization, and radical living polymerization. Of these, the anionic living polymerization method is a polymerization activity type anion, and is represented by the following scheme, for example.

(34)

In the scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are each an integer of 1 or more.

The radical living polymerization method is a polymerization active radical, and is represented by the following scheme, for example.

(35)

Wherein Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are each an integer of 1 or more, R ^a is a hydrogen atom or a monovalent organic group, R ^b is ^a hydrogen atom or a monovalent organic group different from R ^a .

When this acrylic polymer dispersant is synthesized, it is disclosed in JP-A-9-62002, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. 36, 366 (1987), Higashimura Toshinobu, Mitsuo Sawamoto, Polymer, Journal of Polymer, 46, 189 (1989), 17, 977 (1985), 18, 1037 , M. Kuroki, T. Aida, J. Am. Chem. (1987), DY Sogoh, WR Hertler et al., Macromolecules, 20, 1473 (1987), etc. can do.

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer. The A block / B block ratio constituting the copolymer is 1/99 to 80/20, 60/40 (mass ratio), and if it is within this range, there is a tendency that a balance between dispersibility and storage stability can be secured.

The amount of the quaternary ammonium salt group in 1 g of the AB block copolymer and the BAB block copolymer which can be used in the present invention is preferably 0.1 to 10 moles, and if it is within this range, There is a tendency.

Such an amino group may be contained in the block copolymer in an amount of usually 1 to 100 mgKOH / g, and preferably 10 mgKOH / g or more from the viewpoint of dispersibility , More preferably not less than 30 mgKOH / g, even more preferably not less than 50 mgKOH / g, still more preferably not more than 90 mgKOH / g, even more preferably not more than 80 mgKOH / g, 75 mgKOH / g or less. For example, the combination of the upper limit and the lower limit is preferably 10 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g, and 50 to 75 mgKOH / g.

Here, the amine value of the dispersant such as the block copolymer is represented by the amount of the basic group per 1 g of the solid component excluding the solvent in the dispersant sample and the mass of the equivalent KOH, and is measured by the following method. The combination of the upper limit and the lower limit is preferably 10 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g, and still more preferably 50 to 75 mgKOH / g.

Precisely weigh 0.5 to 1.5 g of the dispersant sample in a 100 ml beaker and dissolve in 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized with 0.1 mol / l HClO ₄ acetic acid solution. Using the inflection point of the appropriate pH curve as the appropriate end point, the amine value is obtained by the following formula.

Amine value [mgKOH / g] = (561 x V) / (W x S)

(Where W is the amount of the dispersant sample taken out [g], V is the titration amount [ml] at the appropriate end point, and S is the solid content concentration [mass%] of the dispersant sample]

The amine value of the block copolymer is generally preferably low, usually 10 mgKOH / g or less, and the weight average molecular weight (Mw (g)) of the block copolymer is preferably 10 mgKOH / g or less, though it may vary depending on the presence or kind of an acid group ) Is preferably in the range of 1,000 to 100,000. Within the above range, good dispersibility tends to be secured.

When the acrylic polymer dispersant has a quaternary ammonium salt group as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, the repeating unit represented by the following formula (i) ) May be used.

(36)

In the formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³¹ to R ³³ R ³⁴ is a hydrogen atom or a methyl group, X is a divalent linking group, and Y ^- is a counter anion.

The number of carbon atoms of the alkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 1 to 6.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. Or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. It may be either linear or branched. It may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. The combination of the upper limit and the lower limit is preferably 6 to 16, more preferably 6 to 12.

Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. Of these, a phenyl group, a methylphenyl group, an ethylphenyl group, An ethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The number of carbon atoms of the aralkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. The combination of the upper limit and the lower limit is preferably 7 to 16, more preferably 7 to 12.

Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group and a phenylisopropyl group. A propyl group or a phenylbutyl group, more preferably a phenylmethyl group or a phenylethyl group.

Of these, R ³¹ to R ³³ are preferably independently an alkyl group or an aralkyl group, and more specifically, R ³¹ and R ³³ are each independently a methyl group or an ethyl group, and R ³² is A phenylmethylene group, or a phenylethylene group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethylene group.

When the acrylic polymer dispersant has a tertiary amine as a functional group, it is preferable to have a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as a "repeating unit (ii)") from the viewpoint of dispersibility .

(37)

In the formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, and R ³⁵ and R ³⁶ May be bonded to each other to form a cyclic structure, R ³⁷ is a hydrogen atom or a methyl group, and Z is a divalent linking group.

As the alkyl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ^{33 in the} above formula (i) can be preferably employed.

Similarly, the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii) is preferably an aryl group exemplified as R ³¹ to R ^{33 in the} above formula (i). As the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ^{33 in the} above formula (i) can be preferably employed.

Among them, R ³⁵ and R ³⁶ are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.

Examples of the substituent which the alkyl group, aralkyl group or aryl group in R ³¹ to R ³³ of the formula (i) and R ³⁵ and R ³⁶ of the formula (ii) may have include a halogen atom, an alkoxy group, a benzoyl group, And the like.

Examples of the divalent linking groups X and Z in the formulas (i) and (ii) include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ⁴³ group, ^(Wherein R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], and the like, R &lt; ⁴⁴ &gt; - group.

In the above formula (i), Y ^{- of the} counteranion may be Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited, but from the viewpoint of dispersibility, the sum of the content ratio of the repeating unit represented by the above formula (i) and the content ratio of the repeating unit represented by the above formula (ii) Is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less and preferably 5 mol% or more , More preferably at least 10 mol%, even more preferably at least 20 mol%, and particularly preferably at least 30 mol%. For example, the combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, particularly preferably 30 to 40 mol% .

The content of the repeating unit represented by the above formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, More preferably 10 mol% or more, further preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, particularly preferably 15 mol% or less. For example, the combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 20 mol%, and particularly preferably 10 to 15 mol% .

The content ratio of the repeating unit represented by the formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more from the viewpoint of dispersibility, , More preferably not less than 15 mol%, particularly preferably not less than 20 mol%, more preferably not more than 60 mol%, more preferably not more than 40 mol%, further preferably not more than 30 mol% Is particularly preferable. For example, the combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol% .

The polymeric dispersant is preferably a repeating unit represented by the following formula (iii) (hereinafter referred to as a "repeating unit (iii)") from the viewpoint of improving compatibility with a binder component such as a solvent and improving dispersion stability ).

(38)

In the formula (iii), R ⁴⁰ is an ethylene group or a propylene group, R ⁴¹ is an alkyl group which may have a substituent, R ⁴² is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.

The number of carbon atoms of the alkyl group which may have a substituent in R ⁴¹ in the formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 10 or less, and even more preferably 6 or less . For example, the combination of the upper limit and the lower limit is preferably 1 to 10, and more preferably 2 to 6.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. Or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. It may be either linear or branched. It may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

In the formula (iii), n is preferably 1 or more, more preferably 2 or more, further preferably 10 or less, and more preferably 5 or less, from the viewpoint of compatibility and dispersion with respect to the binder component such as a solvent desirable. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, and more preferably 2 to 5.

The content of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and 4 mol% or more , More preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. Within the above range, compatibility with the binder component such as a solvent tends to be compatible with dispersion stability. For example, the combination of the upper limit and the lower limit is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, still more preferably 4 to 10 mol%.

The polymer dispersant is preferably a repeating unit represented by the following formula (iv) (hereinafter referred to as a &quot; repeating unit (iv) &quot;) in terms of improving compatibility with a binder component such as a solvent of a dispersant and improving dispersion stability ).

[Chemical Formula 39]

In the formula (iv), R ³⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³⁹ is a hydrogen atom or a methyl group.

The number of carbon atoms of the alkyl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and is preferably 10 or less , And more preferably 8 or less. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 8, and even more preferably 4 to 8.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. Or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. It may be either linear or branched. It may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ of the formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, desirable. The combination of the upper limit and the lower limit is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 8.

Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. Of these, a phenyl group, a methylphenyl group, an ethylphenyl group, An ethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The number of carbon atoms of the aralkyl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, desirable. The combination of the upper limit and the lower limit is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 10.

Specific examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenylbutyl group More preferably a phenylmethyl group or a phenylethyl group.

Of these, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group, or a phenylmethyl group, from the viewpoint of solvent compatibility and dispersion stability.

Examples of the substituent that the alkyl group in R ³⁸ may have include a halogen atom, an alkoxy group, and the like. Examples of the substituent which the aryl group or the aralkyl group may have include a chain-like alkyl group, a halogen atom and an alkoxy group. The chain alkyl group represented by R ³⁸ includes both linear and branched chain types.

The content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 50 mol% or more , More preferably 80 mol% or less, and still more preferably 70 mol% or less. For example, the combination of the upper limit and the lower limit is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, still more preferably 50 to 70 mol%.

The polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii) and the repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylic acid salt monomers such as (meth) acrylic acid chloride; (Meth) acrylamide, N-methylol acrylamide, and other (meth) acrylamide monomers; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; And repeating units derived from monomers such as N-methacryloylmorpholine.

The polymer dispersant is preferably a block copolymer having an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii) Chain is preferable. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing a quaternary ammonium group as well as a tertiary amino group in the A block, the dispersing ability of the dispersing agent tends to remarkably improve remarkably. The B block preferably has a repeating unit (iii), and more preferably a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization or block copolymerization. The repeating unit (i) and the repeating unit (ii) may contain two or more kinds of repeating units in each of the A blocks. In this case, the repeating units may be either random copolymerization or block copolymerization Or may be contained in a form.

The repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block. Examples of such repeating units include repeating units derived from the above-mentioned (meth) . The content of the repeating units other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol% Most preferably.

The repeating units other than the repeating units (iii) and (iv) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylic acid salt monomers such as (meth) acrylic acid chloride; (Meth) acrylamide, N-methylol acrylamide, and other (meth) acrylamide monomers; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; And repeating units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol% Most preferably not contained.

From the viewpoint of improving the dispersion stability, (f) the dispersant is preferably used in combination with the pigment derivative described later.

&Lt; Other components of photosensitive coloring composition >

The photosensitive coloring composition of the present invention may contain, in addition to the above-described components, adhesion promoting agents such as silane coupling agents, surfactants (coating property improving agents), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, An ultraviolet absorber, and an antioxidant can be appropriately added.

(1) Adhesion improving agent

The photosensitive coloring composition of the present invention may contain an adhesion improving agent in order to improve adhesion with the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.

As the type of silane coupling agent, various types such as epoxy type, (meth) acryl type, amino type, etc. may be used singly or in combination of two or more kinds.

Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Epoxy silanes such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, 3-ureidopropyl Ureido silanes such as triethoxy silane, and isocyanate silanes such as 3-isocyanate propyl triethoxy silane. Particularly preferred are silane coupling agents of epoxysilanes.

The phosphate group-containing compound is preferably a (meth) acryloyl group-containing phosphate, and is preferably represented by the following general formula (g1), (g2) or (g3).

(40)

In the above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l 'are integers of 1 to 10, and m is 1, 2 or 3.

These phosphoric acid group-containing compounds may be used singly or in combination of two or more.

(2) Surfactants

The photosensitive coloring composition of the present invention may contain a surfactant in order to improve the coating property.

As the surfactant, various kinds of surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant in view of a low possibility of adversely affecting various properties, and in particular, a fluorine-based or silicone-based surfactant is effective in terms of application.

Such surfactants include, for example, TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325 and BYK- (Manufactured by Shin-Etsu Silicone), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning), DS- Manufactured by Nippon Unicar Co., Ltd.) and FC4430 (manufactured by 3M Co., Ltd.).

The surfactant may be used alone or in combination of two or more in any combination.

(3) Pigment derivatives

In the photosensitive coloring composition of the present invention, a pigment derivative may be contained as a dispersion auxiliary agent in order to improve dispersibility and storage stability.

Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, Pyrrole, dioxazine and the like. Of these, phthalocyanine and quinophthalone are preferred.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group and the like directly to the pigment skeleton or an alkyl group, an aryl group, , And preferably a sulfonic acid group. These substituents may be substituted by plural substituents on one pigment skeleton.

Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfonic acid derivative . These may be used singly or in combination of two or more.

(4)

The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and by the action of an acid generated upon exposure, a cross-linking agent such as a melamine compound is allowed to advance the cross-linking reaction. Of these photoacid generators, those having a high solubility in a solvent, particularly a solvent used in a photosensitive coloring composition, are preferred. For example, diphenyliodonium, ditolyl iodonium, phenyl (p- anisyl) iodine Iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl ( diaryl iodonium such as p-tolyl) iodonium and p-isopropylphenyl (p-tolyl) iodonium, or chloride, bromide, or boronate of triarylsulfonium such as triphenylsulfonium, hexafluorophosphate (Pentafluorophenyl) borate salts and the like, sulfonium organic boron complexes such as diphenylphenazylsulfonium (n-butyl) triphenylborate, or the like, 2-methyl-4,6-bist trichloromethyltriazine , And 2- (4-methoxyphenyl) -4,6-bistricloromethyltriazine, but the present invention is not limited thereto.

(5) Crosslinking agent

In the photosensitive coloring composition of the present invention, a crosslinking agent may be further added, and for example, a melamine or guanamine-based compound may be used. These crosslinking agents include, for example, melamine or guanamine-based compounds represented by the following general formula (6).

(41)

In the formula (6), R ⁶¹ represents an -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ represents -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ and one of R ⁶⁷ a represents a group -CH ₂ OR ^68, R ⁶¹ in this case, an aryl group having 6 to 12, R ^62, R ^63, R ⁶⁴ and one R ⁶⁵ represents a group -CH ₂ OR ^68, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or a -CH ₂ OR ⁶⁸ group, and R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and the phenyl group or the naphthyl group may have a substituent such as an alkyl group, an alkoxy group or a halogen atom. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

Examples of the melamine compound corresponding to the general formula (6), that is, the compound represented by the general formula (6-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethyl Melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, and the like.

(42)

When one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ in the formula (6-1) is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is -CH ₂ OR ^And the remaining of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, and R ⁶⁸ represents a hydrogen atom or an alkyl group.

In addition, a guanamine compound corresponding to the formula (6), that is, a compound wherein R ⁶¹ in the formula (6) is aryl includes tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo Guanamine, tetraethoxymethylbenzoguanamine, and the like.

A crosslinking agent having a methylol group or a methylol alkyl ether group may also be used. An example is given below.

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

These crosslinking agents may be used singly or in combination of two or more kinds. The amount when the crosslinking agent is used is preferably from 0.1 to 15% by mass, particularly preferably from 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

(6) Mercapto compound

As a polymerization promoter, a mercapto compound may also be added in order to improve adhesion to a substrate.

Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol Butadiene bis-thioglycolate, trimethylolpropane tris-thioglycolate, trimethylolpropane tris-thiopropionate, trimethylolpropane tristy- thioglycolate, , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tris thiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyl (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tri (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutylate), butanediol bis (3-mercaptoisobutyl Triethylolpropane tris (3-mercaptoisobutylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 1H, 3H, 5H) -trione, and the like, and the like. These may be used alone or in combination of two or more.

(7) Polymerization inhibitor

The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in view of shape control. By containing a polymerization inhibitor, it is considered that the taper angle (the angle formed by the support body and the cured product in cross section of the cured product) can be controlled because it inhibits radical polymerization in the layer under the coating film.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol and 2,6-di-tert-butyl-4-cresol (BHT). Among them, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control. From the viewpoint of safety to the human body, hydroquinone monomethyl ether and methylhydroquinone are preferable.

The polymerization inhibitor preferably contains one kind or two or more kinds thereof. (b) when the alkali-soluble resin is produced, the polymerization inhibitor may be contained in the resin and may be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor, the same or different polymerization inhibitors May be added during the production of the photosensitive coloring composition.

When the photosensitive coloring composition contains a polymerization inhibitor, the content thereof is not particularly limited, but it is usually 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass or more in the total solid content of the photosensitive coloring composition And is generally 0.3 mass% or less, preferably 0.2 mass% or less, and more preferably 0.1 mass% or less. There is a tendency that the shape can be controlled by setting the upper limit value to be higher than the lower limit value, and when it is made lower than the upper limit value, the necessary sensitivity tends to be maintained. For example, the combination of the upper limit and the lower limit is preferably from 0.0005 to 0.3 mass%, more preferably from 0.001 to 0.2 mass%, still more preferably from 0.01 to 0.1 mass%.

<Content Ratio of Each Component in Photosensitive Coloring Composition>

In the photosensitive coloring composition of the present invention, the content ratio of the coloring agent (a) is not particularly limited, but is preferably 10 mass% or more, more preferably 20 mass% or more, and more preferably 25 mass% or more in the total solid content in the photosensitive coloring composition More preferably 30% by mass or more, particularly preferably 32% by mass or more, most preferably 35% by mass or more, further preferably 60% by mass or less, more preferably 50% By mass, more preferably 45% by mass or less, further preferably 40% by mass or less, particularly preferably 38% by mass or less, most preferably 35% by mass or less. When the content of the colorant (a) is set to the lower limit value or more, sufficient light shielding property tends to be obtained. When the content is less than the above upper limit value, sufficient plate making characteristics are easily obtained and electrical reliability tends to be excellent. For example, the combination of the upper limit and the lower limit is preferably 10 to 60 mass%, more preferably 20 to 50 mass%, still more preferably 25 to 45 mass%, still more preferably 30 to 40 mass% By mass, more preferably from 32 to 38% by mass, and particularly preferably from 35 to 38% by mass.

(a1) The content of the organic black pigment is not particularly limited, but it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more in the total solid content of the photosensitive coloring composition, More preferably 30 mass% or less, further preferably 25 mass% or less, particularly preferably 20 mass% or less. When the value is equal to or more than the lower limit value, sufficient light shielding property tends to be obtained, and when it is less than the upper limit value, electrical reliability tends to be increased. For example, the combination of the upper limit and the lower limit is preferably 5 to 40 mass%, more preferably 5 to 30 mass%, still more preferably 10 to 25 mass%, and particularly preferably 15 to 20 mass% .

(a2) The content ratio of the CI Pigment Blue 60 is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more in the total solid content of the photosensitive coloring composition, More preferably at least 6% by mass, particularly preferably at least 8% by mass, most preferably at least 10% by mass. It is more preferably 15 mass% or less, more preferably 12 mass% or less, further preferably 10 mass% or less, even more preferably 9 mass% or less, particularly preferably 8 mass% or less. The transmittance of about 700 nm tends to be lowered by setting it at the lower limit value or more, and when it is less than the upper limit value, electrical reliability tends to be high and sufficient plate making characteristics tend to be obtained. For example, the combination of the upper limit and the lower limit is preferably 2 to 15 mass%, more preferably 3 to 15 mass%, still more preferably 4 to 12 mass%, and particularly preferably 6 to 12 mass% .

(a3) The content of the carbon black is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, more preferably 4% By mass or less, more preferably 10% by mass or less, further preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 7% by mass or less, and most preferably 5% desirable. If it is at least the lower limit value, sufficient light shielding property tends to be obtained, and if it is less than the upper limit value, the transmittance in the near infrared region tends to be increased. For example, the combination of the upper limit and the lower limit is preferably from 1 to 10 mass%, more preferably from 2 to 9 mass%, still more preferably from 3 to 8 mass%, even more preferably from 4 to 7 mass% By mass, and particularly preferably 4 to 5% by mass.

When the photosensitive coloring composition contains a purple pigment as the other coloring agent, the content thereof is not particularly limited, but is preferably at least 1% by mass, more preferably at least 2% by mass, and most preferably at least 3% by mass, based on the total solid content of the photosensitive coloring composition , More preferably not less than 4 mass%, even more preferably not less than 4 mass%, particularly preferably not less than 6 mass%, most preferably not less than 7 mass%, most preferably not more than 15 mass% , More preferably 10 mass% or less, and particularly preferably 8 mass% or less. When the value is equal to or more than the above lower limit value, sufficient light shielding property tends to be obtained, and when it is made lower than the upper limit value, electric reliability tends to be increased. For example, the combination of the upper limit and the lower limit is preferably from 1 to 15 mass%, more preferably from 2 to 12 mass%, still more preferably from 3 to 10 mass%, still more preferably from 4 to 8 mass% By mass, particularly preferably from 6 to 8% by mass, and most preferably from 7 to 8% by mass.

The content of the organic black pigment (a1) relative to the total coloring agent, that is, (a) the coloring agent contained in the photosensitive coloring composition is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, More preferably 50 mass% or more, still more preferably 60 mass% or more, further preferably 80 mass% or less, more preferably 75 mass% or less, and 70 mass% or less , And particularly preferably at most 65 mass%. When the value is equal to or more than the lower limit value, sufficient light shielding property tends to be obtained, and when it is less than the upper limit value, electrical reliability tends to be increased. For example, the combination of the upper limit and the lower limit is preferably from 20 to 80 mass%, more preferably from 30 to 80 mass%, still more preferably from 40 to 75 mass%, still more preferably from 50 to 70 mass% .

In addition, the content ratio of (a2) CI Pigment Blue 60 to the total colorant contained in the photosensitive coloring composition, that is, (a) colorant is not particularly limited, but is preferably 10% by mass or more, more preferably 12% , More preferably at least 15 mass%, even more preferably at least 18 mass%, particularly preferably at least 20 mass%, even more preferably at least 24 mass%, particularly preferably at least 28 mass% Is preferably 50 mass% or less, more preferably 40 mass% or less, even more preferably 35 mass% or less, particularly preferably 30 mass% or less. The transmittance of about 700 nm tends to be lowered by setting it at the lower limit value or more, and when it is less than the upper limit value, electrical reliability tends to be high and sufficient plate making characteristics tend to be obtained. For example, the combination of the upper limit and the lower limit is preferably from 10 to 50 mass%, more preferably from 10 to 40 mass%, still more preferably from 18 to 40 mass%, still more preferably from 24 to 35 mass% By mass, and particularly preferably from 28 to 35% by mass.

The content ratio of (a3) carbon black to (a) the coloring agent is not particularly limited, but is preferably 10% by mass or more, more preferably 12% by mass or more, and more preferably 15% by mass , More preferably not less than 18 mass%, even more preferably not less than 20 mass%, particularly preferably not less than 35 mass%, more preferably not more than 30 mass%, and most preferably not more than 25 mass% And even more preferably 20 mass% or less. If it is at least the lower limit value, sufficient light shielding property tends to be obtained, and if it is less than the upper limit value, the transmittance in the near infrared region tends to be increased. For example, the combination of the upper limit and the lower limit is preferably 10 to 35 mass%, more preferably 12 to 30 mass%, still more preferably 15 to 25 mass%, and particularly preferably 18 to 20 mass% .

On the other hand, it is preferable to appropriately adjust the content ratio of (a1) organic black pigment and (a3) carbon black in the black pigment in order to achieve both transmittance and electrical reliability in the near infrared region. Since carbon black has a high absorbance in the visible region, it is possible to effectively reduce the transmittance in the vicinity of the wavelength of 700 nm, to reduce the content of the coloring agent necessary for obtaining a predetermined light shielding property, and to have high electric reliability . On the other hand, since carbon black has absorption in the near infrared region, (a3) a predetermined amount of (a1) organic black pigment is added in addition to carbon black to ensure sufficient light shielding property after securing the transmittance in the vicinity of 900 nm .

(a3) The content of the organic black pigment (a1) relative to 100 parts by mass of carbon black is usually 150 parts by mass or more, preferably 180 parts by mass or more, more preferably 200 parts by mass or more, and 210 parts by mass or more, More preferably 250 parts by mass or more, particularly preferably 300 parts by mass or more, particularly preferably 350 parts by mass or more, even more preferably 400 parts by mass or more Particularly preferably not less than 450 parts by mass, and most preferably not less than 480 parts by mass. It is more preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, even more preferably 600 parts by mass or less, particularly preferably 500 parts by mass or less. The transmittance in the near infrared region tends to be higher by setting it to be equal to or higher than the lower limit value, and when it is made lower than the upper limit value, the electrical reliability tends to be increased. For example, the combination of the upper limit and the lower limit is preferably from 150 to 1000 parts by mass, more preferably from 180 to 800 parts by mass, still more preferably from 200 to 800 parts by mass, still more preferably from 210 to 600 parts by mass, More preferably from 600 to 600 parts by mass, particularly preferably from 250 to 600 parts by mass, particularly preferably from 300 to 600 parts by mass, still more preferably from 350 to 600 parts by mass, still more preferably from 400 to 600 parts by mass, Particularly preferably 500 parts by mass, and most preferably 480 to 500 parts by mass.

From the viewpoint of achieving both light shielding and transmittance in the vicinity of 900 nm, it is preferable to appropriately adjust the content ratio of (a3) the total organic pigment to carbon black.

(a3) The content ratio of the total organic pigment to 100 parts by mass of carbon black is usually 300 parts by mass or more, preferably 400 parts by mass or more, more preferably 500 parts by mass or more, further preferably 550 parts by mass or more, More preferably not less than 600 parts by mass, particularly preferably not less than 620 parts by mass, most preferably not less than 650 parts by mass, more preferably not more than 900 parts by mass, and most preferably not more than 800 parts by mass. The transmittance at a wavelength of 900 nm tends to be higher by setting it at the lower limit value or more, and when it is not more than the upper limit value, sufficient light shielding property can be obtained and light leakage around a wavelength of 700 nm tends to be suppressed. For example, the combination of the upper limit and the lower limit is preferably 300 to 900 parts by mass, more preferably 400 to 900 parts by mass, still more preferably 500 to 900 parts by mass, still more preferably 550 to 800 parts by mass, More preferably 800 to 800 parts by mass, particularly preferably 620 to 800 parts by mass, and most preferably 650 to 800 parts by mass.

From the viewpoint of suppressing light leakage in the vicinity of the wavelength of 700 nm, it is preferable to appropriately adjust the content ratio of (a3) C. I. pigment blue 60 to (a2) carbon black.

(a3) The content ratio of (a2) CI Pigment Blue 60 to 100 parts by mass of carbon black is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 150 parts by mass or more, and 180 More preferably not less than 200 parts by mass, particularly preferably not less than 200 parts by mass, particularly preferably not less than 200 parts by mass, more preferably not less than 210 parts by mass, particularly preferably not less than 220 parts by mass, most preferably not less than 240 parts by mass, Or less, more preferably 300 parts by mass or less. By setting the value above the lower limit value, light leakage around a wavelength of 700 nm tends to be suppressed, and when it is lower than the upper limit value, the transmittance around 900 nm tends to increase. For example, the combination of the upper limit and the lower limit is preferably 50 to 400 parts by mass, more preferably 100 to 400 parts by mass, further preferably 150 to 400 parts by mass, still more preferably 200 to 300 parts by mass, Particularly preferably 300 parts by mass, and most preferably 240 to 300 parts by mass.

When the photosensitive coloring composition contains a purple pigment as another coloring agent, it is preferable to appropriately adjust the content ratio of the purple pigment to (a1) the organic black pigment from the viewpoint of light shielding property.

(a1) The content of the violet pigment in 100 parts by mass of the organic black pigment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, and more preferably 55 parts by mass or more More preferably 60 parts by mass or more, particularly preferably 65 parts by mass or more, most preferably 70 parts by mass or more, most preferably 100 parts by mass or less, more preferably 90 parts by mass or less, More preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and particularly preferably 65 parts by mass or less. By setting the value to be equal to or more than the lower limit value, sufficient light shielding property can be ensured and reliability tends to be improved. Also, when the value is set to the upper limit value or less, light leakage around 700 nm tends to be suppressed. For example, the combination of the upper limit and the lower limit is preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass, still more preferably 40 to 100 parts by mass, still more preferably 55 to 100 parts by mass, More preferably 100 to 100 parts by mass, still more preferably 65 to 90 parts by mass, most preferably 70 to 90 parts by mass.

The content of the alkali-soluble resin (b) in the photosensitive coloring composition of the present invention is not particularly limited, but is generally 5% by mass or more, preferably 10% by mass or more, more preferably 20% , Preferably not less than 80 mass%, more preferably not more than 70 mass%, still more preferably not more than 60 mass%, and most preferably not more than 30 mass%, particularly preferably not less than 35 mass% More preferably 50 mass% or less, and particularly preferably 45 mass% or less. When the content of the alkali-soluble resin (b) is set to the lower limit value or more, the lowering of the solubility of the unexposed portion in the developer is suppressed, and the development defects can be suppressed. Further, by setting the amount to be the upper limit value or less, proper sensitivity can be maintained, dissolution of the developing solution in the exposed portion can be suppressed, and reduction in sharpness and adhesion of the pixel can be suppressed. For example, the combination of the upper limit and the lower limit is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, more preferably 35 to 60% , Even more preferably from 40 to 60 mass%, and particularly preferably from 40 to 50 mass%.

The content of the epoxy (meth) acrylate resin (b1) is not particularly limited, but is generally 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more in the total solid content of the photosensitive coloring composition of the present invention , More preferably not less than 20 mass%, particularly preferably not less than 25 mass%, and usually not more than 45 mass%, preferably not more than 40 mass%, and more preferably not more than 35 mass%. By setting the amount above the lower limit value, the solubility of the unexposed portion in the developing solution tends to be ensured. When the amount is less than the upper limit value, appropriate sensitivity can be maintained and dissolution of the developing solution in the exposed portion can be suppressed. There is a tendency that the reduction of sharpness and adhesion can be suppressed. For example, the combination of the upper limit and the lower limit is preferably 5 to 45 mass%, more preferably 10 to 40 mass%, still more preferably 15 to 40 mass%, and still more preferably 20 to 35 mass% By mass, and particularly preferably 25 to 35% by mass.

The content of the epoxy (meth) acrylate resin (b1) contained in the alkali-soluble resin (b) is not particularly limited, but is usually 20 mass% or more, preferably 30 mass% or more, more preferably 40 mass% Or more, and usually 90 mass% or less, preferably 85 mass% or less, and more preferably 80 mass% or less. By setting the amount above the lower limit value, the solubility of the unexposed portion in the developing solution tends to be ensured. When the amount is less than the upper limit value, appropriate sensitivity can be maintained and dissolution of the developing solution in the exposed portion can be suppressed. There is a tendency that the reduction of sharpness and adhesion can be suppressed. For example, the combination of the upper limit and the lower limit is preferably from 20 to 90 mass%, more preferably from 30 to 85 mass%, still more preferably from 40 to 80 mass%.

(c) the content of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1% by mass or more in the total solid content of the photosensitive coloring composition of the present invention , More preferably not less than 3 mass%, particularly preferably not less than 4 mass%, and usually not more than 15 mass%, preferably not more than 10 mass%, more preferably not more than 8 mass% More preferably, it is 7 mass% or less. (c) When the content of the photopolymerization initiator is set to the above-mentioned lower limit value or more, the sensitivity lowering can be suppressed. When the content is lower than the above upper limit value, deterioration of the solubility of the unexposed portion in the developer is suppressed, There is a tendency to be able to. For example, the combination of the upper limit and the lower limit is preferably from 0.1 to 15 mass%, more preferably from 0.5 to 10 mass%, still more preferably from 1 to 8 mass%, still more preferably from 2 to 8 mass% By mass, particularly preferably 3 to 8% by mass, and most preferably 4 to 7% by mass.

When the polymerization initiator (c) is used together with the photopolymerization initiator, the content of the polymerization promoter is not particularly limited, but is preferably 0.05% by mass or more, usually 10% by mass or less, Preferably 5% by mass or less, and the polymerization promoter is preferably used in a proportion of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass based on 100 parts by mass of the (c) photopolymerization initiator. When the content of the polymerization accelerator is set to the above-mentioned lower limit value or more, a decrease in sensitivity to exposure light tends to be suppressed. When the content is lower than the upper limit value, the degradation of the solubility of the unexposed portion in the developer is suppressed, There is a tendency to inhibit.

When the sensitizing dye (c) is used together with the photopolymerization initiator, the content is not particularly limited, but from the viewpoint of sensitivity, generally 20 mass% or less, preferably 15 mass% or less, of the total solid content in the photosensitive coloring composition , And more preferably 10 mass% or less.

The content of the ethylenically unsaturated compound (d) is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more in the total solid content of the photosensitive coloring composition of the present invention, Further, it is usually 30 mass% or less, preferably 20 mass% or less, and more preferably 15 mass% or less. When the amount is above the lower limit value, proper sensitivity can be maintained, dissolution of the developing solution in the exposed portion can be suppressed, and the sharpness and adhesion of the pixel can be suppressed from deteriorating. The permeability of the developer to the light portion is prevented from increasing, and a good image tends to be easily obtained. For example, the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 15% by mass.

The photosensitive coloring composition of the present invention can be obtained by using (e) a solvent, and the content ratio of the total solid content is usually 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% By mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. For example, the combination of the upper limit and the lower limit is preferably from 5 to 50 mass%, more preferably from 10 to 30 mass%, still more preferably from 15 to 25 mass%.

(f) The content of the dispersing agent is not particularly limited, but is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% , Preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less. When the content is above the lower limit value, sufficient dispersibility tends to be obtained. When the content is less than the upper limit value, the ratio of the other components is decreased, and sensitivity, plate formability and the like tend to be suppressed. For example, the combination of the upper limit and the lower limit is preferably 1 to 30 mass%, more preferably 3 to 20 mass%, still more preferably 5 to 15 mass%, and particularly preferably 5 to 10 mass% .

The content of the dispersing agent (f) in 100 parts by mass of the colorant (a) is more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, Particularly preferably 30 parts by mass or less. When the content is above the lower limit value, sufficient dispersibility tends to be obtained. When the content is less than the upper limit value, the ratio of the other components is decreased, and sensitivity, plate formability and the like tend to be suppressed. For example, the combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 30 parts by mass.

On the other hand, the content of the alkali-soluble resin (b) in 100 parts by mass of the ethylenically unsaturated compound (d) is preferably 80 parts by mass or more and 100 parts by mass or more, more preferably 150 parts by mass or more, More preferably not less than 250 parts by mass, particularly preferably not less than 700 parts by mass and not more than 500 parts by mass, more preferably not more than 400 parts by mass, and most preferably not more than 300 parts by mass. When the amount is above the lower limit value, there is a tendency that an appropriate dissolution phenomenon state in which there is no peeling or the like occurs. On the other hand, when it is made lower than the upper limit value, an appropriate dissolution time tends to be obtained with respect to the developer. The combination of the upper limit and the lower limit is, for example, preferably 80 to 700 parts by mass, more preferably 100 to 500 parts by mass, further preferably 150 to 400 parts by mass, particularly preferably 200 to 300 parts by mass, To 300 parts by mass are most preferable.

When the adhesion improver is used, the content is not particularly limited, but it is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 2% by mass in the total solid content of the photosensitive coloring composition. When the content ratio of the adhesion-improving agent is set to the above-mentioned lower limit value or more, the effect of improving adhesion can be sufficiently obtained. When the content is lower than the upper limit value, the sensitivity is lowered or the residue remains after development. .

When a surfactant is used, the content thereof is not particularly limited, but it is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content of the photosensitive coloring composition. , And most preferably 0.03 to 0.3 mass%. When the content ratio of the surfactant is set to the lower limit value or more, the smoothness and uniformity of the coated film tends to be exhibited. When the content is lower than the upper limit, smoothness and uniformity of the coated film are liable to occur, There is a tendency.

&Lt; Physical Properties of Photosensitive Coloring Composition >

The photosensitive coloring composition of the present invention can be preferably used for forming colored spacers, and preferably exhibits black color from the viewpoint of use as colored spacers. The optical density (OD) per 1 m of the film thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.3 or more, even more preferably 1.4 or more, particularly preferably 1.5 or more , And most preferably 1.8 or more, and is usually 4.0 or less, preferably 3.0 or less, and more preferably 2.5 or less. For example, the combination of the upper limit and the lower limit is preferably 1.0 to 4.0, more preferably 1.2 to 3.0, still more preferably 1.3 to 3.0, even more preferably 1.4 to 3.0, even more preferably 1.5 to 3.0 , And most preferably 1.8 to 2.5.

The photosensitive coloring composition of the present invention preferably has a transmittance at a wavelength of 700 nm of 2.5% or less, more preferably 2.0% or less, further preferably 1.5% or less, and usually 0.01% or more. By setting the value at or below the upper limit value, light leakage at a wavelength of 700 nm can be suppressed, and the displayed image tends to be suppressed from being red. The combination of the upper limit and the lower limit is preferably 0.01 to 2.5%, more preferably 0.01 to 2.0%, still more preferably 0.01 to 1.5%.

Meanwhile, the photosensitive coloring composition of the present invention preferably has a transmittance at a wavelength of 900 nm of 10% or more, more preferably 15% or more, more preferably 20% or more, and usually 100% or less. The combination of the upper limit and the lower limit is preferably 10 to 100%, more preferably 15 to 100%, still more preferably 20 to 100%.

Generally, since the color filter including the black matrix and the pixels is directly formed on the glass substrate, alignment of the photomask for forming the black matrix is not a problem. On the other hand, the coloring spacers may be formed on the array substrate (substrate on the TFT side), and in this case, it is necessary to form the coloring spacers in accordance with the position of the TFT pattern on the substrate. As a method of forming a colored spacer at a predetermined position, there is a method in which marks on the array substrate are read with light near a wavelength of 900 nm to align the photomask, but when the alignment is performed, It is important that the transmittance of the coating film at a wavelength of 900 nm is not less than a predetermined value. Therefore, when the transmittance of 900 nm or more is set to the lower limit value or more, the visibility of the mark is improved, and the coloring spacer tends to be easily formed at a predetermined position.

The transmittance of the photosensitive coloring composition at a wavelength of 700 nm or 900 nm can be measured by forming a cured film having a film thickness of 2.5 탆 using the photosensitive coloring composition and measuring the transmittance at a wavelength of 700 nm or 900 nm using a spectrophotometer do. The detailed measurement conditions and the like are not particularly limited, but can be measured by, for example, the method described in the following examples.

&Lt; Method for producing photosensitive coloring composition >

The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as &quot; resist &quot;) is produced by a conventional method.

Usually, (a) the colorant is preferably dispersed in advance by using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. (A) Since the colorant is made into fine particles by the dispersion treatment, the coating property of the resist is improved.

The dispersion treatment is preferably carried out in a system in which a part or all of (a) a colorant, (e) a solvent, (f) a dispersant and (b) an alkali-soluble resin are used in combination , And the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion"). Particularly, when (f) a polymeric dispersant is used as a dispersant, it is preferable that the obtained ink and resist are suppressed from increasing in time (excellent dispersion stability).

Thus, in the step of producing a resist, it is preferable to prepare a pigment dispersion containing at least a colorant, (e) a solvent, and (f) a dispersant.

As the (a) coloring agent, (e) organic solvent, and (f) dispersing agent which can be used in the pigment dispersion, those described as being usable in the photosensitive coloring composition can be preferably employed. In addition, as the content ratio of each coloring agent in the pigment dispersion (a), the content described as the content ratio in the photosensitive coloring composition can be preferably employed.

Further, when a dispersion containing the entire components to be blended in the photosensitive coloring composition is subjected to dispersion treatment, there is a possibility that the highly reactive component is denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymeric dispersant.

In the case of (a) dispersing the colorant with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are usually 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time differs depending on the composition of the liquid and the size of the dispersion treatment apparatus. It is the standard of dispersion that the gloss of the ink is controlled such that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the gloss of the resist is low, there is a possibility that the dispersion treatment is not sufficient and rough pigment (coloring material) particles remain in many cases, which may result in insufficient developability, adhesion, resolution and the like. If the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment tends to be broken and the dispersion stability tends to be rather deteriorated because many ultrafine particles are generated.

The dispersion particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 占 퐉 and is measured by a dynamic light scattering method or the like.

Next, the ink obtained by the dispersion treatment and the above-mentioned other components contained in the resist are mixed to obtain a homogeneous solution. In the process of producing a resist, fine dust may be mixed in the liquid. Therefore, the obtained resist is preferably subjected to filtration treatment with a filter or the like.

[Cured goods]

By curing the photosensitive coloring composition of the present invention, a cured product can be obtained. The cured product obtained by curing the photosensitive coloring composition can be preferably used as a coloring spacer.

[Coloring Spacer]

Next, the coloring spacer using the photosensitive coloring composition of the present invention will be described according to the production method thereof.

(1)

The support for forming the coloring spacer is not particularly limited as long as it has a suitable strength. As a material, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene and polyethylene, a thermoplastic resin such as polycarbonate, polymethyl methacrylate, polysulfone and the like A thermosetting resin sheet such as a sheet, an epoxy resin, an unsaturated polyester resin, and a poly (meth) acrylic resin, or various glasses. Of these, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than a transparent substrate, it may be formed on a TFT array.

The support may be subjected to a corona discharge treatment, an ozone treatment, a silane coupling agent, a thin film formation treatment of various resins such as a urethane resin, etc., if necessary, in order to improve surface physical properties such as adhesiveness.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When thin films of various resins are formed, the film thickness is usually in the range of 0.01 to 10 mu m, preferably 0.05 to 5 mu m.

(2) colored spacers

The photosensitive coloring composition of the present invention is used for the same purpose as the known photosensitive coloring composition for a color filter. Hereinafter, when used as a colored spacer (black photo spacer), a black color spacer using the photosensitive coloring composition of the present invention Will be described with reference to specific examples of the method for forming the film.

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

(3) Formation of colored spacers

[1] Method of supplying to substrate

The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. The supplying method can be carried out by a conventionally known method, for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, a spray coat method and the like. It may also be supplied in the form of a pattern by an ink-jet method or a printing method. Among them, the die coating method is preferable from the viewpoint of the comprehensive viewpoint that the amount of the coating liquid to be used is greatly reduced and the generation of foreign matter is not affected by the mist or the like adhering to the spin coating method.

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

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

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

[2] Drying method

The drying after supplying the photosensitive coloring composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. It is also possible to combine the vacuum drying method in which the drying is performed in the decompression chamber without raising the temperature.

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

[3] Exposure method

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

As a preferred embodiment of the present invention, in the case of simultaneously forming black photo spacers having different heights by a photolithography method, for example, a light shielding portion (light transmittance of 0%) and a plurality of openings having the highest average light transmittance An exposure mask having an opening portion (intermediate transmission opening portion) having a small average light transmittance with respect to the opening portion (full permeation opening portion) is used. By this method, a difference in the residual film ratio is caused by the difference in the average light transmittance between the intermediate transmission opening portion and the full transmission opening portion, that is, the difference in exposure amount.

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

The light source used for the above exposure is not particularly limited. Examples of the light source include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, , Excimer lasers, nitrogen lasers, helium cadmium lasers, blue violet semiconductor lasers, and near infrared semiconductor lasers. An optical filter may be used when irradiating light of a specific wavelength.

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

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

In the proximity exposure method, the distance between the object to be exposed and the mask pattern is usually 10 占 퐉 or more, preferably 50 占 퐉 or more, more preferably 75 占 퐉 or more, usually 500 占 퐉 or less, preferably 400 占 퐉 Or less, more preferably 300 m or less.

[4] Development method

After the exposure described above, an image pattern can be formed on the substrate by developing using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate Mono-di- or triethanolamine, mono- di- or trimethylamine, mono- di- or triethylamine, mono-di- or triethanolamine, mono-, di- or triethanolamine, Or organic alkaline compounds such as diisopropylamine, n-butylamine, mono- di- or triisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline and the like. These alkaline compounds may be a mixture of two or more kinds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters, An activator; Anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid salts, alkylsulfonic acid salts and sulfosuccinic acid ester salts; Amphoteric surfactants such as alkyl betaines and amino acids.

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

The developing conditions are not particularly limited and the developing temperature is usually in the range of 10 to 50 占 폚, preferably 15 to 45 占 폚, particularly preferably 20 to 40 占 폚, the developing method is the immersion developing method, , A brush developing method, an ultrasonic developing method, or the like.

[5] Additional exposure and heat curing treatment

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

The size, shape and the like of the colored spacer of the present invention are appropriately adjusted according to the specification of the color filter to which the color filter is applied. However, in the photosensitive coloring composition of the present invention, In this case, the height of the spacer is usually about 2 to 7 mu m, and the sub-spacer has a height generally lower than that of the spacer by about 0.2 to 1.5 mu m.

The optical density (OD) per 1 탆 of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, further preferably 1.8 or more, usually 4.0 or less and 3.0 Or less. Here, the optical density (OD) is a value measured by the method described later. For example, the combination of the upper limit and the lower limit is preferably 1.2 to 4.0, more preferably 1.5 to 3.0, and even more preferably 1.8 to 3.0.

[Color Filter]

The color filter can form red, green, and blue pixel coloring layers on a liquid crystal driving substrate (array substrate). Alternatively, the pixel coloring layer may be formed on a glass substrate as a transparent substrate.

[Image display device]

The image display apparatus of the present invention comprises the above-described coloring spacer of the present invention.

For example, an alignment film is formed on a liquid crystal driving substrate (array substrate) having a coloring spacer of the present invention, and a liquid crystal cell is formed by bonding to a counter electrode substrate. Liquid crystal is injected into the formed liquid crystal cell, An image display device such as a liquid crystal display device having the colored spacer of the present invention can be manufactured.

On the other hand, when the colored spacer of the present invention is provided on the counter substrate side, and the liquid crystal cell is formed by stacking with the liquid crystal drive substrate (array substrate), and the liquid crystal is injected into the formed liquid crystal cell, , An image display apparatus such as a liquid crystal display apparatus can be manufactured.

For example, as described in Japanese Patent Application Laid-Open No. 2014-215614, liquid crystal alignability can be improved by irradiating ultraviolet light after injecting liquid crystal into a liquid crystal cell using a specific alignment material.

Example

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.

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

<Alkali-soluble resin-I>

And 145 parts by mass of propylene glycol monomethyl ether acetate were stirred while substituting with nitrogen, and the temperature was raised to 120 占 폚. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2'-azobis -2-methylbutyronitrile was added dropwise over 3 hours, and further stirring was continued at 90 캜 for 2 hours. Subsequently, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 占 폚 for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 part by mass of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours. The alkali-soluble resin-I thus obtained had a weight-average molecular weight Mw of about 8400 and an acid value of 80 mgKOH / g, as measured by GPC.

<Alkali-soluble resin-II>

ZCR-1664H "(Mw = 6500, acid value = 60 mgKOH / g) manufactured by Nippon Kayaku Co.,

<Pigment-I>

Irgaphor (registered trademark) Black S 0100 CF "(having the chemical structure represented by the following formula (I-1)), manufactured by BASF. This corresponds to the colorant (a1).

(43)

<Pigment-II>

C. I. Pigment Blue 60. This corresponds to the colorant (a2).

<Pigment-III>

Carbon black. &Quot; RAVEN1060U &quot; (formerly &quot; R1060 &quot; This corresponds to the colorant (a3).

<Pigment-IV>

C. I. Pigment Blue 15: 6.

<Pigment-V>

C. I. Pigment Violet 29.

<Pigment-VI>

"Paliogen (registered trademark) Black L0086", manufactured by BASF Corporation. Perylene black. An organic black pigment other than the colorant (a1).

<Dispersant-I>

Quot; BYK-LPN21116 &quot; (an A block having a quaternary ammonium group and a tertiary amino group in the side chain, and an AB block copolymer comprising a B block having no quaternary ammonium group and tertiary amino group) MgKOH / g. Acid value is 1 mgKOH / g or less.)

The repeating units represented by the following formulas (1a) and (2a) are contained in the A block of the dispersant-I, and the repeating unit represented by the following formula (3a) is contained in the B block. The content of the repeating units represented by the following formulas (1a), (2a) and (3a) in the total repeating units of the dispersant-I was 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

(44)

<Dispersant-II>

&Quot; DISPERBYK-167 &quot; (urethane-based polymer dispersing agent)

<Pigment Derivative>

&Quot; Solsperse 12000 &quot; manufactured by Lubrizol Corporation

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxy-1-butanol

&Lt; Photopolymerization initiator-I >

An oxime ester initiator having the chemical structure described below.

[Chemical Formula 45]

&Lt; Photopolymerizable monomer >

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

<Additives>

Quot; KAYAMER PM-21 &quot; (methacryloyl group-containing phosphate) manufactured by Nippon Kayaku Co.,

<Surfactant>

&Quot; Megafac F-559 &quot; manufactured by DIC Corporation

<Preparation of pigment dispersions 1, 2, 4, 5 and 6>

The pigments, dispersant, dispersion assisting agent, alkali-soluble resin, and solvent described in Table 1 were mixed in a mass ratio as shown in Table 1. This mixed solution was subjected to dispersion treatment at 25 to 45 캜 for 3 hours by means of a paint shaker. As for the beads, zirconia beads of 0.5 mm phi were used and a mass of 2.5 times the dispersion was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersions 1, 2, 4, 5 and 6. Further, since the viscosity of the pigment-VI was dispersed under the same conditions as those of the pigment dispersion 2, the content of the dispersing agent in the pigment dispersion 6 was required to be set high.

<Preparation of Pigment Dispersion 3>

The pigment dispersions 1, 2, 4, and 5 were prepared in the same manner as in Example 1 except that the pigment, dispersant, dispersion assisting agent, alkali-soluble resin, and solvent described in Table 1 were mixed in the mass ratios shown in Table 1 and the dispersing treatment time was changed to 6 hours. And 6 in the same manner as in Example 1 to prepare a pigment dispersion 3.

[Examples 1 to 12 and Comparative Examples 1 to 5]

The above-prepared pigment dispersions 1 to 6 were used, and PGMEA was added thereto so that the ratio of the solid content to the total content of the solid content was 19 mass%, and the mixture was stirred, To prepare a photosensitive coloring composition, and evaluation was conducted in the following manner.

&Lt; Optical density per unit film thickness (unit OD value), measurement of transmittance >

The optical density per unit film thickness was measured in the following order.

First, each of the photosensitive color compositions thus prepared was applied to a glass substrate with a spin coater so that the film thickness after post-baking was 2.5 占 퐉, dried under reduced pressure for 1 minute, and then dried at 90 占 폚 for 90 seconds with a hot plate. Thereafter, the entire surface was exposed using a high-pressure mercury lamp at an exposure condition of 400 mJ / cm 2 and an illuminance of 45 mW / cm 2, and heated at 230 ° C for 20 minutes (post-baking) to obtain a resist coated substrate. The optical density (OD value) of the obtained substrate was measured by a transmission densitometer Gretech Macbeth D200-II and the film thickness was measured by a non-contact surface / layer sectional shape measuring system VertScan (R) 2.0 manufactured by Ryoka Corporation, (Unit OD value) per unit film thickness (1 占 퐉) was calculated from the film thickness (OD value) and the film thickness. Further, the OD value is a numerical value indicative of the shielding ability, and the larger the numerical value is, the higher order light is exhibited.

Using the same substrate, the transmittance at wavelengths of 700 nm and 900 nm was measured with a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation). At this time, a glass substrate to which the photosensitive coloring composition was not applied was regarded as a reference.

The transmittance at a wavelength of 700 nm is an index of light leakage, and a smaller value is preferable. If it is 2.5% or less, there is a preferable tendency.

The transmittance at a wavelength of 900 nm is an index of the readability of the mark for mask alignment, and a larger value is preferable. If it is 10% or more, there is a preferable tendency.

The measurement results of the unit OD value and the transmittance are shown in Tables 2 to 5.

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

The voltage holding ratio (VHR) and the ion density were evaluated by the method described below.

(Production of liquid crystal cell)

An electrode substrate A having an ITO film formed on the entire surface thereof (an entire surface of a glass ITO glass sheet for evaluation, manufactured by EHC Corporation) and an ITO film having a length of 1 cm and a lead electrode with a width of 2 mm connected to the central portion of the glass substrate, An electrode substrate B (20) (glass for evaluation SZ-B111MIN (B) manufactured by EHC Corporation) on which the film 2 was formed was prepared. Fig. 1 is a schematic view of the upper surface of the electrode substrate B (20).

Each of the photosensitive coloring compositions was coated on the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked on a hot plate at 90 DEG C for 90 seconds to obtain a coated film having a dry film thickness of 2.5 mu m. Thereafter, the outer edge portion was masked with a thickness of 2 mm, and image exposure was performed using a high-pressure mercury lamp at an exposure condition of 400 mJ / cm 2 and an illuminance of 45 mW / cm 2, respectively. Subsequently, a shower phenomenon of 0.15 MPa of water pressure at 25 캜 was performed using an aqueous 0.1% by mass aqueous solution of potassium hydroxide at 25 캜, and the development was stopped with pure water and rinsed with a water spray. The shower developing time was adjusted between 10 and 120 seconds, and was set to about 1.6 times of the time (break time) during which the photosensitive coloring composition layer of unexposed light was dissolved and removed.

The electrode substrate A thus formed was subjected to post-baking at 230 DEG C for 20 minutes to obtain an electrode substrate (resist substrate) on which the colored cured film 3 was formed. Thereafter, the polyimide solution was coated on the resist substrate, pre-baked on a hot plate at 70 DEG C for 2 minutes, and post-baked at 220 DEG C for 24 minutes. The thus-obtained resist substrate was cut into a substrate having a width of 2.5 cm and a length of 2.5 cm to complete an electrode substrate for evaluation A (8).

On the other hand, a polyimide solution was applied on the electrode substrate B (20), prebaked on a hot plate at 70 DEG C for 2 minutes, and post baked at 220 DEG C for 24 minutes to complete the evaluation electrode substrate B (9) .

Thereafter, an epoxy resin sealant 5 containing silica beads having a diameter of 5 탆 was applied on the outer circumference of the evaluation electrode substrate B (9) using a dispenser, and then the evaluation electrode substrate B (9) (Sealing side) of the evaluation electrode substrate A (8) with the coated surface of the evaluation electrode substrate A (8) being squeezed to manufacture empty cells. The prepared cell was heated in a hot air circulation furnace at 180 DEG C for 2 hours.

A liquid crystal 7 (MLC-6608, manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the periphery thereof was sealed with a UV curable sealant 6. The liquid crystal cell was subjected to annealing (heating at 105 ° C for 2.5 hours in a hot air circulation furnace) followed by ultraviolet irradiation at 18 J / cm 2 and an illuminance of 40 mW / cm 2 using a high-pressure mercury lamp to complete the measurement liquid crystal cell 30 . In the completed cell, the colored cured film is 1.7 cm long and the electrode portion is 1 cm long. 2 is a schematic view of a side surface of the liquid crystal cell for measurement 30 completed in FIG.

(Evaluation of voltage holding ratio (VHR)) [

A voltage was applied to the liquid crystal cell for measurement at a voltage of 5 V, 2.0 Hz, and a frame time of 1667 msec, and voltage retention ratio was measured with a &quot; liquid crystal physical property evaluation device -6254 type &quot; manufactured by Toyotechnika Co., . The voltage holding ratio is preferably as high as possible. The results are shown in Tables 2 to 5.

The voltage holding ratio was measured under the same conditions except that the frequency was changed to 0.6 Hz. The results are shown in Tables 2, 4 and 5.

(Evaluation of ion density)

The ion density can be measured, for example, by the method described in International Display Workshop (IDW) '06 Notice LCT7-1. Since the voltage is gradually applied to the ion density measurement, it is possible to measure the difference between the ion peak and the liquid crystal alignment peak, and to measure the difference in reliability in which the difference does not occur at the voltage holding ratio. In a liquid crystal display device, impurity ions sometimes cause display defects such as afterimage and flicker, and ion density measurement is effective for the evaluation.

In the measurement, the current when a triangular wave with a frequency of 0.1 Hz and a voltage of 5 V was applied to the liquid crystal cell for measurement was measured with time using a &quot; liquid crystal physical property evaluation apparatus -6254 type &quot; manufactured by Toyotechnika Co., . The area of the impurity ion peak portion 13 in the waveform was measured to determine the ion density. FIG. 3 shows schematic diagrams of the applied voltage value 11, the measured current value 12 and the impurity ion peak portion 13 when the time of one cycle is taken as the horizontal axis. The measurement results are shown in Tables 2, 4 and 5.

The photosensitive coloring compositions of Examples 1 to 4 and Comparative Examples 1 to 4 in Table 2 all had equivalent unit OD values of the coated substrate, that is, equivalent light shielding characteristics. Among them, the photosensitive coloring compositions of Examples 1 to 4 were used It was confirmed that the coated substrate had a sufficiently low transmittance at a wavelength of 700 nm and was excellent in shielding visible light in a long wavelength region and had a sufficiently high transmittance at a wavelength of 900 nm so that the readability of marks for mask alignment was good. It was also confirmed that since the voltage holding ratio at 2.0 Hz after irradiation with ultraviolet rays was high, the liquid crystal driving was not inhibited even when a panel manufacturing method of irradiating ultraviolet rays after the production of a liquid crystal cell was employed.

On the other hand, it was confirmed that the coated substrate using the photosensitive coloring composition of Comparative Example 1 had a low transmittance at a wavelength of 900 nm and insufficient readability of marks for mask alignment.

In addition, it was confirmed that the coated substrate using the photosensitive coloring compositions of Comparative Examples 2 and 3 had a high transmittance at a wavelength of 700 nm, insufficient shielding of visible light in the long wavelength region, and light leakage. It was also confirmed that the coated substrate using the photosensitive coloring composition of Comparative Example 2 had a low voltage holding ratio at 2.0 Hz after irradiation with ultraviolet light, thereby inhibiting liquid crystal driving.

On the other hand, the coated substrate using the photosensitive coloring composition of Comparative Example 4 had no problem with the transmittance of 900 nm wavelength and the transmittance of 700 nm wavelength, but the liquid crystal driving was inhibited because the voltage holding ratio at 2.0 Hz after irradiation with ultraviolet rays was low .

In the case of using a black pigment for securing the light-shielding property of the photosensitive coloring composition, among the black pigments, the carbon black has a high absorbance in the entire wavelength range of visible light, so that the transmittance at a wavelength of 700 nm can be sufficiently low, (A3) the content of (a1) organic black pigment is low relative to 100 parts by mass of carbon black as in Comparative Example 1. In other words, the content of the organic black pigment in the black pigment (a3) When the proportion of carbon black is high, the transmittance at a wavelength of 900 nm is lowered.

On the other hand, when (a3) carbon black is not present as in Comparative Example 2, (a1) the transmittance of the obtained coated substrate at a wavelength of 700 nm is also increased due to the fact that the transmittance of the organic black pigment at a wavelength of 700 nm is high Throw away. In addition, since the carbon black having a high absorbance is absent, the content of the pigment necessary for obtaining a predetermined OD value increases, and the voltage retention rate at 2.0 Hz after irradiation with ultraviolet rays deteriorates, and the electrical reliability lowers.

Further, even when (a2) CI Pigment Blue 60 was not present as in Comparative Example 3, (a1) the transmittance of the organic black pigment at a wavelength of 700 nm was high, The transmittance is also increased. On the other hand, it is considered that (a3) the transmittance at a wavelength of 700 nm can be lowered by increasing the content ratio of (a3) carbon black. However, as in Comparative Example 1, the transmittance at 900 nm is also expected to be lowered. Therefore, when C. I. Pigment Blue 60 (a2) is not present, it is considered that it is difficult to achieve both a transmittance of 700 nm and a transmittance of 900 nm.

Although it is effective to add a blue pigment to improve light leakage at a wavelength of 700 nm as described above, when a suitable pigment species is not selected as in Comparative Example 4, the voltage holding ratio at 2.0 Hz after irradiation with ultraviolet rays is low, Reliability is lowered.

For these Comparative Examples, as in Examples 1 to 4, by using a specific organic black pigment, a blue pigment, and carbon black in combination, and by appropriately adjusting the ratio of the specific organic black pigment and carbon black, the transmittance at a wavelength of 900 nm was sufficiently high , It is possible to sufficiently read marks of the mask alignment and sufficiently reduce the transmittance of 700 nm and to prevent light leakage. In particular, when CI Pigment Blue 60 is selected as the blue pigment, the voltage retention ratio at 2.0 Hz after irradiation with ultraviolet rays is high, and the electrical reliability can be increased. In particular, from the comparison between Example 2 and Example 1, and from the comparison between Example 1 and Examples 3 and 4, it was found that by increasing the content ratio of the total organic pigment to 100 parts by mass of carbon black, the transmittance at 900 nm Can be made higher.

On the other hand, all of the photosensitive coloring compositions of Examples 5 to 8 in Table 3 had equivalent unit OD values, that is, equivalent light shielding properties, excellent transmittance and electrical reliability at a wavelength of 900 nm, It was confirmed that the coated substrates using the photosensitive coloring compositions of Examples 7 and 8, particularly Example 8, had a very low transmittance at a wavelength of 700 nm and were particularly excellent in blocking the visible light in the long wavelength region. In this respect, it has become clear that the transmittance at 700 nm can be further reduced by increasing the content ratio of (a2) C. I. Pigment Blue 60 to 100 parts by mass of carbon black.

The photosensitive coloring compositions of Examples 9 to 12 in Table 4 were prepared so that the total pigment content was the same and the content ratio of the purple pigment to (a1) 100 parts by mass of the organic black pigment was changed. Among them, To 12, in particular, the photosensitive coloring composition of Examples 11 and 12 had a high unit OD value. From this point of view, it has become clear that (a1) the unit OD value can be increased by increasing the content ratio of the purple pigment to 100 parts by mass of the organic black pigment.

The photosensitive coloring compositions of Example 1 and Comparative Example 5 in Table 5 were of the same composition except that the kinds of the organic black pigment were different. The photosensitive coloring composition of Example 1 had a voltage holding ratio at 2.0 Hz after irradiation with ultraviolet light It was confirmed that the electrical reliability was good. In this respect, it has become clear that the use of the organic black pigment (a1) as the organic black pigment makes it possible to improve the electrical reliability.

Industrial availability

According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a coloring spacer having a low light leakage around 700 nm, an excellent transmittance at a wavelength of 900 nm and an excellent electrical reliability after irradiation with ultraviolet rays, It is possible to provide an image display apparatus having the same coloring spacers. Therefore, the present invention is very industrially applicable in the fields of photosensitive coloring compositions, cured products, colored spacers and image display devices.

1 Glass
2 ITO film
3 colored hardening film
4 polyimide film
5 Epoxy resin sealant
6 UV curing type sealant
7 LCD
8 Evaluation electrode substrate A
9 Evaluation electrode substrate B
11 Applied voltage value
12 Measured current value
13 Impurity ion peak portion
20 electrode substrate B
30 Liquid crystal cell for measurement

Claims (12)

A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f)
Wherein the (a) colorant comprises (a1) at least one compound selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound and a salt of a geometric isomer of the compound (A2) CI Pigment Blue 60, and (a3) carbon black,
Wherein the content of the organic black pigment (a1) in the (a3) 100 parts by mass of the carbon black is 150 parts by mass or more.
[Chemical Formula 1]

(In the formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
^{R 2, R 3, R 4} , R 5, R 7, R 8, R 9 and R ¹⁰ is a halogen atom, R ^11, COOH, COOR ^11, COO hydrogen atoms, each independently ^-, CONH _2, CONHR ^{11, CONR 11 R 12, CN, OH} , OR 11, COCR 11, OOCNH 2, OOCNHR 11, OOCNR 11 R 12, NO 2, NH 2, NHR 11, NR 11 R 12, NHCOR 12, NR 11 COR 12, N = ^{_{CH 2, N = CHR 11,}} N = CR 11 R 12, SH, SR 11, SOR 11, SO 2 R 11, SO 3 R 11, SO 3 H, SO 3 -, SO 2 NH 2, SO 2 NHR 11 or SO ₂ NR ¹¹ R ¹² and;
At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Or they may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR &lt; ¹¹ &gt; bridges;
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms ) The method according to claim 1,
The content of (a1) the organic black pigment in the (a3) 100 parts by mass of the carbon black is 200 parts by mass or more. 3. The method according to claim 1 or 2,
(A3) The content of the organic black pigment (a1) relative to 100 parts by mass of the carbon black is 210 parts by mass or more. 4. The method according to any one of claims 1 to 3,
(A3) the content ratio of (a2) CI Pigment Blue 60 to 100 parts by mass of carbon black is 200 parts by mass or more. 5. The method according to any one of claims 1 to 4,
Wherein the total content of the total organic pigment in (a3) 100 parts by mass of carbon black is 550 parts by mass or more. 6. The method according to any one of claims 1 to 5,
The content of the colorant (a) in the total solid content is 10% by mass or more. 7. The method according to any one of claims 1 to 6,
Wherein the content of the colorant (a) in the total solid content is 45 mass% or less. 8. The method according to any one of claims 1 to 7,
Wherein the alkali-soluble resin (b) comprises (b1) an epoxy (meth) acrylate resin. 9. The method according to any one of claims 1 to 8,
Wherein the optical density per 1 mu m of the thickness of the cured coating film is 1.0 or more. A cured product obtained by curing the photosensitive colored composition according to any one of claims 1 to 9. A colored spacer formed from the cured product according to claim 10. An image display device comprising the coloring spacer according to claim 11.

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