JP2023143785A - Photosensitive coloring resin composition, colored spacer, method for producing film substrate with colored spacer and dimming device - Google Patents

Abstract

To provide a photosensitive coloring resin composition which can process a thick-film colored spacer required for retaining a dimming body in a dimming layer and also can be cured sufficiently by a post-curing process using light even when the heat resistance of the base material is low.SOLUTION: There is provided a photosensitive coloring resin composition which comprises (A) an alkali-soluble resin, (B) zirconium compound particles, (C) a photosensitive agent and (D) a radically polymerizable compound, wherein the zirconium compound particles have a crystallite size of 10 nm or more and 60 nm or less as determined from a half-value width of the peak derived from a (111) plane of zirconium nitride in the X-ray diffraction spectrum when a CuμKα ray is used as the X-ray source; the photosensitive coloring resin composition comprises (D-1) a compound having a fluorene skeleton and (D-2) a trifunctional or more multifunctional acrylate compound as (D) the radically polymerizable compound and the content of (D-1) the compound having the fluorene skeleton is 5 to 35 pts.mass based on the amount of 100 pts.mass of (D-2) the trifunctional or more multifunctional acrylate compound.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive colored resin composition, a colored spacer, a method for producing a film substrate with a colored spacer, and a light control device.

There are various types of light control sheets that switch between a light-shielding state (or a cloudy state) and a transparent state, and they are used for various purposes. For example, by fixing the light control sheet to a transparent substrate such as glass, it can be used for window glass, partitions, vehicle components, etc., and is used as equipment to separate private space from public space.
According to the techniques described in Patent Documents 1 and 2, when a light control sheet equipped with a liquid crystal layer containing a dichroic dye is used as a light control layer, it is possible to exhibit a color according to the dichroic dye. , the design of the light control sheet can be improved. However, in order to meet the demands for increasingly sophisticated display design freedom, there is a need for spacers that can be formed with high precision using photosensitive colored resin compositions as colored spacers that play the role of holding the liquid crystal layer. Colored spacer materials, which require high film thickness, light shielding properties to prevent light leakage, and can be formed below the heat-resistant temperature of the base film, are produced by scattering colored spacer particles on a base material using a low-precision method. This could only be achieved through a method.
As a colored spacer using a photosensitive colored resin composition, according to the technology described in Patent Document 3, a thicker colored spacer is formed to prevent malfunction of TFT of a liquid crystal display and to change the panel structure. There was a demand for this, and it was discovered that it could be formed by using a specific colorant and a specific alkali-soluble resin together.

Japanese Patent Application Publication No. 2017-187775 JP 2021-193065 Publication Japanese Patent Application Publication No. 2020-126117

However, the colored spacer described in Patent Document 3 is insufficient in thickness required to maintain the liquid crystal layer of the light control sheet, and is difficult to cure when the base material has low heat resistance.

[1] Contains (A) an alkali-soluble resin, (B) zirconium compound particles, (C) a photosensitizer, and (D) a radically polymerizable compound, and uses the CuKα rays of the (B) zirconium compound particles as an X-ray source. The crystallite size determined from the half-value width of the peak derived from the (111) plane of zirconium nitride in the X-ray diffraction spectrum when a compound having a fluorene skeleton; and (D-2) a polyfunctional acrylate compound having three or more functionalities, wherein the content of the compound having the (D-1) fluorene skeleton is (D-2) a polyfunctional acrylate compound having three or more functionalities. A photosensitive colored resin composition in an amount of 5 to 35 parts by weight based on 100 parts by weight of the functional acrylate compound.

[2] The photosensitive colored resin composition according to [1], which includes (A-1) a cardo-based resin having two or more repeating units represented by the following structural formula (1) as the (A) alkali-soluble resin. .

[3] (D-1) The compound having a fluorene skeleton includes (D-1A) a compound having a fluorene skeleton, a condensed polycyclic aromatic ring other than fluorene, and one or more hydroxyl groups [1] or [2] The photosensitive colored resin composition described in .

[4] The photosensitive colored resin composition according to any one of [1] to [3], which contains (C-1) an oxime ester photopolymerization initiator as the (C) photosensitizer.

[5] (E) The photosensitive colored resin composition according to any one of [1] to [4], which contains a polyfunctional thiol compound.

[6] The photosensitive coloring according to any one of [1] to [5], which contains 1 to 20% by mass of (B) zirconium compound particles when the solid content of the photosensitive colored resin composition is 100% by mass. Resin composition.

[7] A colored spacer comprising a cured product of the photosensitive colored resin composition according to any one of [1] to [6], wherein the colored spacer has a film thickness of 5 to 20 μm and an aspect ratio of 1. A colored spacer that is between .0 and 3.0.

[8] A colored spacer is formed by applying the photosensitive colored resin composition according to any one of [1] to [6] onto a film substrate, drying, exposing, developing and curing the composition. A method for manufacturing a film substrate with colored spacers.

[9] A light control device comprising a light control layer comprising a colored spacer of the photosensitive colored resin composition according to any one of [1] to [6].

According to the present invention, it is possible to process a thick colored spacer required for retaining the light control body in the light control layer, and furthermore, when the base material has low heat resistance, it can be sufficiently cured by a post-curing process using light. can.

In this specification, unless otherwise specified, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.

The photosensitive colored resin composition of the present invention contains (A) an alkali-soluble resin, (B) zirconium compound particles, (C) a photosensitizer, and (D) a radically polymerizable compound.
(A) The alkali-soluble resin can impart developer solubility to the photosensitive colored resin composition. (B) Zirconium compound particles have excellent light transmittance in the ultraviolet region and low light transmittance in the visible region, so they have excellent light blocking properties. (B) By containing the zirconium compound particles, light in the ultraviolet region can be sufficiently transmitted to the bottom of the film in photolithography, making it easy to photocure and increase sensitivity. In addition, in the post-curing process using light, light in the ultraviolet region is sufficiently transmitted to the bottom of the film, making it easy to photocure and improve curability. By containing (C) a photosensitizer and (D) a radically polymerizable compound, photocurability can be imparted to the photosensitive colored resin composition.

In the present invention, (A) alkali-soluble resin has a hydroxyl group and/or carboxyl group as an alkali-soluble group, has an acid value of 10 mgKOH/g or more, and has a weight average molecular weight (Mw) of 500 to 150,000. Refers to a resin that is Here, the weight average molecular weight (Mw) refers to a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.
(A) Examples of the alkali-soluble resin include cardo resins, acrylic resins, novolak resins, polyimide resins, polyimide precursors, polybenzoxazole resins, polybenzoxazole precursors, and polyamides that meet the conditions for the alkali-soluble resins described above. Examples include resins and siloxane resins. Among these, from the viewpoint of pattern processability and coating film reliability, (A) alkali-soluble resin preferably contains one or more resins selected from the group consisting of cardo resins, acrylic resins, and polyimide resins. , (A-1) more preferably contains a cardo-based resin.

When the alkali-soluble resin (A) contains the cardo-based resin (A-1), a photosensitive colored resin composition with higher ultraviolet sensitivity can be obtained. By using such a photosensitive colored resin composition, even a thick coating film can be easily photolithographically processed.
(A-1) Cardo-based resin, for example, is a reaction product of an epoxy compound having a partial structure represented by structural formula (1) and a radically polymerizable group-containing monobasic acid compound, and further an acid dianhydride. It can be obtained by reaction.

(A-1) Examples of cardo-based resins include "WR-301 (trade name)" (manufactured by ADEKA Corporation), "V-259ME (trade name)" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), " “Ogsall” (registered trademark) CR-TR1 (product name)”, “Ogsall CR-TR2 (product name)”, “Ogsall CR-TR3 (product name)”, “Ogsall CR-TR4 (product name)”, “ Examples include "Ogsol CR-TR5 (trade name)" and "Ogusol CR-TR6 (trade name)" (manufactured by Osaka Gas Chemical Co., Ltd.). (A) The alkali-soluble resin may contain two or more of these.
Among them, the alkali-soluble resin (A) preferably includes (A-1) a cardo-based resin having two or more repeating units represented by the structural formula (1).
Examples of the cardo-based resin (A-1) having two or more repeating units represented by structural formula (1) include "WR-301" and "V-259ME".

The content of the alkali-soluble resin (A) is preferably 10 to 80% by mass, more preferably 30 to 50% by mass, based on 100% by mass of the solid content of the photosensitive colored resin composition.
Here, the solid content refers to the mass of components other than the solvent relative to the mass of all components when preparing the composition. (A) When the content of the alkali-soluble resin is 10% by mass or more, the adhesion of the colored spacer to the base material can be increased. On the other hand, when the content of the alkali-soluble resin (A) is 80% by mass or less, the hardness of the colored spacer can be improved.
(A-1) The content of cardo-based resin is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on 100% by mass of the total amount of (A) alkali-soluble resin. (A-1) When the content of cardo-based resin is 50% by mass or more, the sensitivity of the colored film can be improved.

The photosensitive colored resin composition of the present invention contains (B) zirconium compound particles. The zirconium compound particles contain zirconium nitride (ZrN). By using zirconium nitride as a coloring material, it is possible to achieve both high levels of light-shielding properties and insulation properties in the visible region. Generally, zirconium nitride is produced by using zirconium oxide (ZrO ₂ ), lower zirconium oxide expressed as Zr _n O _2n-1 (1≦n≦20), ZrO _x N _y (0< It contains zirconium oxynitride and the like represented by x<2.0, 0.1<y<2.0).

In the X-ray diffraction spectrum of zirconium compound particles containing zirconium nitride, zirconium oxide, and/or zirconium oxynitride when CuKα rays are used as the X-ray source, in the case of ZrN, the peak originating from the (111) plane is at the diffraction angle. It is observed near 2θ=33.5-34.0°. In the case of ZrO ₂ , a peak originating from the (011) plane is observed near the diffraction angle 2θ=30.3°, and a peak originating from the (−111) plane is observed near the diffraction angle 2θ=28.2°. In the case of Zr ₇ O ₈ N ₄ , a peak originating from the (211) plane is observed near 2θ=33.4°. Then, the crystallite size can be calculated from the half-widths of these X-ray diffraction peaks using the Scherrer equation shown in equation (2) below. In the present invention, the crystallite size of zirconium nitride is calculated.

K in the above formula (2) is a constant 0.9, and λ is 0.15406 [nm]. β is expressed by the following formula (3). θ is as described above.

In the above formula (3), β _e is the half-width of the diffraction peak, and β _O is the correction value of the half-width (0.12 [°]). However, β, βe and β _O are calculated in radians.

The X-ray diffraction spectrum is measured by wide-angle X-ray diffraction using CuKα rays as the X-ray source. As the X-ray diffraction device, RU-200R manufactured by Rigaku Co., Ltd. can be used. The measurement conditions are: output is 50 kV/200 mA, slit system is 1°-1°-0.15 mm-0.45 mm, measurement step (2θ) is 0.02°, and scan speed is 2°/min.

In order to make the effects of the present invention remarkable, it is preferable that the zirconium compound particles containing zirconium nitride do not contain zirconium oxide and zirconium oxynitride, which are by-products, to the extent that they are not observed as X-ray diffraction peaks. Preferably, it is reduced.
In the present invention, the zirconium compound particles are preferably composite fine particles consisting of zirconium nitride and metal particles. By compounding metal particles with zirconium nitride, it becomes possible to suppress oxidation of zirconium nitride, and it becomes possible to improve visible light shielding properties and improve stability as particles.

The term "metal" used in the metal particles used in the present invention has the usual meaning in the field of chemistry. (page 444). The Iwanami Science and Chemistry Dictionary (5th edition) provides the following definition of "metal":
"A substance that has a metallic luster, conducts electricity and heat well, and is highly malleable and ductile in its solid state. All except mercury are solid at room temperature. It can usually be subjected to various mechanical processes. Even when liquefied, Optical and electrical properties are often maintained. Most single metal crystals have a face-centered cubic, hexagonal close-packed, or body-centered cubic structure, and usually form an aggregate of microcrystals. ．Atoms in a crystal are connected by metallic bonds, and some of the electrons exist as free electrons.The properties of metals originate from metallic bonds.Metals with a small number of free electrons, such as elemental antimony and bismuth, are called metalloids. ．Not only a single substance but also a phase containing two or more metal elements or a metal element and a certain non-metal element (boron, carbon, etc.) also exhibits metallic properties.The electrical conductivity of metals varies with temperature. It decreases as the temperature rises, but it increases for non-metals, so from this we can clearly distinguish between the two.
The metal is not particularly limited, and preferable examples include titanium, aluminum, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, and niobium. , tantalum, calcium, titanium, bismuth, antimony, lead, or an alloy thereof. More preferred metals include titanium and aluminum.

The content of metal particles in the zirconium compound particles is preferably from 2% by mass to 20% by mass, more preferably from 3% by mass to 10% by mass, based on the total amount of the zirconium compound particles. By setting the content of metal particles to 2% by mass or more, light shielding properties can be further improved. On the other hand, by setting the content of metal particles to 20% by mass or less, the ultraviolet transmittance can be further improved.

Here, the content of zirconium atoms and the content of metal atoms can be analyzed by ICP emission spectrometry. The content of nitrogen atoms can be analyzed by an inert gas melting-thermal conductivity method. The content of oxygen atoms can be analyzed by inert gas melting-infrared absorption method.

In the present invention, the zirconium nitride contained in the zirconium compound particles has a crystallite size calculated from the half-value width of the X-ray diffraction peak derived from the (111) plane in the X-ray diffraction spectrum when CuKα rays are used as the X-ray source. It is important that the thickness is 10 nm or more and 60 nm or less. By setting the crystallite size of zirconium nitride within the above range, the transmitted light of the colored film exhibits a blue-violet color with a peak wavelength of 400 nm or less, and light transmittance in the ultraviolet region can be improved.
Since it has better transmittance in the ultraviolet region than conventional light-shielding materials, when used as a photosensitive colored resin composition, photocuring proceeds sufficiently even in thick films, and sensitivity can be improved.
If the crystallite size of zirconium nitride is less than 10 nm, the particle surface is likely to be oxidized, resulting in a decrease in light shielding properties. The crystallite size of zirconium nitride is more preferably 20 nm or more. On the other hand, when the crystallite size of zirconium nitride exceeds 60 nm, the transmission peak when formed into a colored film shifts to longer wavelengths, resulting in a decrease in light transmittance in the ultraviolet region and a decrease in light blocking performance in the visible region. The crystallite size of zirconium nitride is preferably 50 nm or less, more preferably 40 nm or less. Examples of means for adjusting the crystallite size within the above range include a method of adjusting crystal growth conditions during particle synthesis by gas phase reaction. For example, in the thermal plasma method, the crystallite size can be easily adjusted within the above range by adjusting the cooling time and cooling rate after vaporizing the particles.

The specific surface area of the zirconium compound particles is preferably 5 m ² /g or more and 100 m ^{2 /} g or less. By setting the specific surface area of the zirconium compound particles to 5 m ² /g or more, the particles can be easily dispersed finely, and the dispersion stability in the photosensitive colored resin composition and the flatness and adhesion of the colored spacer can be improved. I can do it. The specific surface area of the zirconium compound particles is more preferably larger than 20 m ² /g. Moreover, when the above-mentioned metal particles are not included, it is more preferable that the specific surface area is larger than 29.7 m ² /g. On the other hand, by controlling the specific surface area of the zirconium compound particles to 100 m ^{2 /} g or less, re-aggregation of the particles can be suppressed, and the dispersion stability in the photosensitive colored resin composition and the light-shielding property of the colored spacer can be further improved. I can do it. The specific surface area of the zirconium compound particles is more preferably 60 m ² /g or less. Here, the specific surface area of the zirconium compound particles can be determined by a BET multipoint method using a nitrogen gas adsorption method using a gas adsorption type specific surface area measuring device. Examples of means for adjusting the specific surface area within the above range include a method of adjusting crystal growth conditions during particle synthesis by gas phase reaction. For example, in the thermal plasma method, the specific surface area can be easily adjusted within the above range by adjusting the cooling time and cooling rate after vaporizing the particles.

As a method for producing zirconium compound particles containing zirconium nitride, a gas phase reaction method such as an electric furnace method or a thermal plasma method is generally used. Among these, the thermal plasma method is preferred because it is less contaminated with impurities, the particle size is easily uniform, and productivity is high. Examples of methods for generating thermal plasma include direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, and hybrid plasma. Among these, high-frequency plasma is preferred because it causes less contamination of impurities from the electrodes. Specifically, zirconium nitride is synthesized by vaporizing and turning zirconium into fine particles in a nitrogen atmosphere using a thermal plasma method (for example, Surface Science Vol. 5 (1984), No. 4), and zirconium chloride and ammonia are synthesized using an electric furnace method. A method of synthesizing zirconium nitride by a gas phase reaction (for example, Surface Science Vol. 8 (1987), No. 5), in which a mixture of zirconium dioxide, magnesium oxide, and metallic magnesium is fired at high temperature in a nitrogen atmosphere to produce lower zirconium oxide. - A method for obtaining a zirconium nitride composite (for example, Japanese Patent Application Laid-Open No. 2009-91205).

(B) The content of the zirconium compound particles is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, and 3 to 10% by mass, based on 100% by mass of the total solid content of the photosensitive colored resin composition. Mass % is more preferred. (B) When the content of the zirconium compound particles is 0.1 part by mass or more, light shielding properties can be improved. On the other hand, when the content of the zirconium compound particles (B) is 40 parts by mass or less, even a thick film can be photocured to the bottom.

The photosensitive colored resin composition of the present invention contains a photopolymerization initiator as (C) a photosensitizer. A photopolymerization initiator is a compound that generates radicals by bond cleavage and/or reaction upon exposure to light. By containing a photopolymerization initiator, the radically polymerizable compound (D) can be photocured by exposure. Examples of the photopolymerization initiator include carbazole photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, α-aminoalkylphenone photopolymerization initiators, and the like. Two or more types of these may be contained. Among these, in the exposure process described later, carbazole-based photopolymerization initiation is used as the (C) photosensitizer because it has high sensitivity to a mixed line consisting of i-line (365 nm), h-line (405 nm), and g-line (436 nm). It is preferable to contain an oxime ester photopolymerization initiator or (C-1) an oxime ester photopolymerization initiator. In particular, it is preferable to contain (C-1) an oxime ester photopolymerization initiator as the (C) photosensitizer.
(C-1) Examples of the oxime ester photopolymerization initiator include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4 -(phenylthio)-2-(o-benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) ) oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), and the like. Two or more types of these may be contained.

The content of the photosensitive agent (C) is preferably 1 to 60 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the radically polymerizable compound (D), from the viewpoint of improving sensitivity to exposure. (C) When the content of the photosensitizer is 1 part by mass or more, resistance to development peeling can be improved. On the other hand, when the content of the photosensitive agent (C) is 60 parts by mass or less, the deep curability against exposure can be improved.

The photosensitive colored resin composition of the present invention contains (D) a radically polymerizable compound. (D) The radically polymerizable compound contains (D-1) a compound having a fluorene skeleton and (D-2) a trifunctional or higher polyfunctional acrylate compound. (D) As the radically polymerizable compound, a compound having two or more radically polymerizable groups is preferable. (D) As the radically polymerizable group possessed by the radically polymerizable compound, a (meth)acryloyl group is preferable from the viewpoint of improving the sensitivity during exposure and improving the hardness of the colored spacer. The (meth)acryloyl group here refers to a methacrylic group or an acrylic group.
(D) The radically polymerizable compound includes (D-1) a compound having a fluorene skeleton. (D-1) Examples of compounds having a fluorene skeleton include 9,9-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3 -acryloxy-2-hydroxypropoxy)phenyl]fluorene and the component (D-1A) described later.
(D) The radically polymerizable compound more preferably contains (D-1A) a compound having a fluorene skeleton, a condensed polycyclic aromatic ring other than fluorene, and one or more hydroxyl groups. (D-1A) The fused polycyclic aromatic rings other than fluorene in the compound having a fluorene skeleton, a fused polycyclic aromatic ring other than fluorene, and one or more hydroxyl groups include pentalene, indene, naphthalene, heptalene, biphenylene, Examples include anthracene, phenanthrene, pentacene, pyrene, and tetracene. Among these, pentalene, indene, naphthalene, and hepthalene are preferred, and naphthalene is particularly preferred. (D) The radically polymerizable compound preferably includes a compound represented by formula (4). (D-1A) By containing a compound having a fluorene skeleton, a condensed polycyclic aromatic ring other than fluorene, and one or more hydroxyl groups, it achieves both solubility in the bottom developer and development adhesion, resulting in a fine pattern. can be processed. Moreover, the hardness of the colored spacer can be improved.

In formula (4), R ¹ and R ² each independently represent an alkylene group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, It represents a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group. R ⁷ to R ¹² are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms. group, a fluorocycloalkyl group having 4 to 10 carbon atoms, or a fluoroaryl group having 6 to 15 carbon atoms. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or COR ¹⁵ , at least one of which represents a hydrogen atom, and R ¹⁵ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, a carbon It represents an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms. p and q each independently represent an integer of 0 to 3, and r and s each independently represent a natural number of 1 to 3. t and u each independently represent an integer of 0 to 4, and v to y each independently represent an integer of 0 to 3. As the component (D-1A), for example, 9,9-bis[5-(3-(meth)acryloxy-2-hydroxypropoxy)naphthyl]fluorene, 9,9-bis[5-{3-methyl-( 3-(meth)acryloxy-2-hydroxypropoxy)}naphthyl]fluorene, 9,9-bis[5-{(3-(meth)acryloxy-2-hydroxypropoxy)ethoxy}-1-naphthyl]fluorene, 9, 9-bis[5-{(3-(meth)acryloxy-2-hydroxypropoxy)propoxy}-1-naphthyl]fluorene, 9,9-bis[5-(3-(meth)acryloxy-2-hydroxypropoxy) Anthryl] fluorene, etc.

Further, as (D) the radically polymerizable compound, (D-2) a trifunctional or higher functional acrylate compound is contained. (D-2) Trifunctional or higher polyfunctional acrylate compounds include, for example, trimethylolpropane tri(meth)acrylate, triacryl formal, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra( meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ε-caprolactone modified dipentaerythritol hexa(meth)acrylate, δ-valerolactone modified dipentaerythritol hexa(meth)acrylate, γ -Butyrolactone-modified dipentaerythritol hexa(meth)acrylate, β-propiolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

Examples of (D) radically polymerizable compounds other than (D-1) compounds having a fluorene skeleton and (D-2) trifunctional or higher polyfunctional acrylate compounds include poly(meth)acrylate carbamate, adipic acid 1,6 -Hexanediol (meth)acrylate, phthalic anhydride propylene oxide (meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-hydroxy-3-( meth)acryloyloxypropyl methacrylate, 2-hydroxy-3-(meth)acryloyloxypropyl acrylate, bis(meth)acrylic acid 1,6-hexanediylbis(oxy)bis(2-hydroxy-3,1-propane) diyl), bisphenol A diglycidyl ether di(meth)acrylate, and the like.

(D) The content of the radically polymerizable compound is preferably 5 to 80% by mass, and 15 to 60% by mass based on 100% by mass of the total content of (A) the alkali-soluble resin and (D) the radically polymerizable compound. is more preferable. (D) When the content of the radically polymerizable compound is 5% by mass or more, the hardness of the colored spacer can be improved. On the other hand, when the content of the radically polymerizable compound (D) is 80% by mass or less, thickening of the pattern line width relative to the designed value can be improved. Further, by setting the content of the radically polymerizable compound (D) in the range of 5 to 80% by mass, the reliability of the film after photocuring can be improved.
Further, the content of (D-1) a compound having a fluorene skeleton is preferably 5 to 35 parts by mass, and 10 to 30 parts by mass, based on 100 parts by mass of (D-2) trifunctional or higher polyfunctional acrylate compound. part is more preferable. (D-1) When the content of the compound containing a fluorene skeleton is 5 parts by mass or more and 35 parts by mass or less, it is excellent in both imparting hydrophobicity to the bottom part and achieving high crosslinking density, so that development when processing into a thick film is possible. Peeling resistance can be improved. (D-1) When the content of the compound containing a fluorene skeleton is 35 parts by mass or less, the crosslinking density becomes high and the hardness of the colored spacer can be improved.

In the present invention, it is preferable to contain (E) a polyfunctional thiol compound. (E) By containing a polyfunctional thiol compound, the sensitivity of the photosensitive colored resin composition can be improved. (E) A polyfunctional thiol compound is a compound having two or more thiol groups (mercapto groups) in the molecule. As the polyfunctional thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and a molecular weight of 150 to 1,000 is even more preferable. (E) The number of functional groups in the polyfunctional thiol compound is preferably 2 to 10 functional, more preferably 2 to 8 functional, and even more preferably 2 to 4 functional. The larger the number of functional groups, the better the membrane strength, while the smaller the number of functional groups, the better the storage stability. In the case of the above range, both of these can be achieved. (E) The thiol group in the polyfunctional thiol compound may be a primary thiol group, a secondary thiol group, or a tertiary thiol group, but the sensitivity and chemical resistance From this point of view, it is preferably a primary or secondary thiol group, and more preferably a secondary thiol group. Moreover, from the viewpoint of storage stability, a secondary or tertiary thiol group is preferable, and a secondary thiol group is more preferable. Examples of polyfunctional thiol compounds include pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5 tris(3-mercaptobutyryloxyethyl)-1, 3,5 triazine-2,4,6(1H,3H,5H) trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) propionate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and dipentaerythritol hexa Among these, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3 , 5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)trione and the like are more preferred. (E) Commercially available polyfunctional thiol compounds include, for example, Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1, TPMB, TEMB (manufactured by Showa Denko K.K.), Examples include TMMP, TEMPIC, PEMP, EGMP-4, and DPMP (manufactured by Sakai Chemical Industry Co., Ltd.). These polyfunctional thiol compounds (E) may be contained alone or in combination of two or more. The content of the polyfunctional thiol compound (E) is 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the radically polymerizable compound (D).

In the present invention, coloring pigments other than (B) zirconium compound particles can be contained. By containing a colored pigment, it becomes possible to adjust the reflected color tone of the colored spacer. Examples of coloring pigments include organic pigments and inorganic pigments that are commonly used in the field of electronic information materials. Examples of organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; aminoanthraquinone, diaminodianthraquinone, and anthraquinone. Anthraquinone pigments such as pyrimidine, flavanthrone, anthrone, indanthrone, pyrantrone, and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments ; quinophthalone pigments; threne pigments; metal complex pigments and the like. Inorganic pigments include, for example, titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron, and molybdenum. Red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, navy blue, cobalt blue, cerulean Examples include blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet. Examples of black colored pigments include black organic pigments, color-mixing organic pigments, and black inorganic pigments. Examples of the black organic pigment include carbon black, perylene black, aniline black, and benzofuranone pigments. Examples of mixed-color organic pigments include those obtained by mixing two or more types of pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan to create pseudo-black color. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; oxides, composite oxides, sulfides, and nitrides of the above metals. , oxynitrides, etc. Examples of white colored pigments include titanium dioxide, barium carbonate, calcium carbonate, barium sulfate, alumina white, and silicon dioxide.

In the present invention, dispersibility and coating properties can be adjusted by containing an organic solvent. Examples of the organic solvent include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.

Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl Ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-butyl ether, tripropylene glycol monomethyl Examples include ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran.

Examples of acetates include butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (hereinafter referred to as "PGMEA"), dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl -1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and the like.

Examples of esters include lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, and 3-methoxypropionate. Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate , ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc. .

Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene.
Examples of aromatic hydrocarbons include toluene and xylene. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.
Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, etc. It will be done. Two or more types of these may be contained.

The content of the organic solvent in the photosensitive colored resin composition of the present invention is preferably 40 to 95% by weight, more preferably 50 to 90% by weight, based on 100% by weight of the total amount of the photosensitive colored resin composition. When the content of the organic solvent is 40% by mass or more, the uniformity of the thickness of the coating film can be improved in the coating process. On the other hand, when the content of the organic solvent is 95% by mass or less, pigment precipitation can be suppressed.

The photosensitive colored resin composition of the present invention may contain a polymer dispersant. The term "polymer dispersant" refers to an agent that has both a pigment-affinity group that has a chemical bonding or adsorption effect on the pigment surface and a polymer chain or group that has solvent affinity. In wet media dispersion processing, polymeric dispersants improve the wettability of pigments to dispersion media, promote disaggregation of pigments, stabilize particle size and viscosity through steric hindrance and/or electrostatic repulsion effects, Furthermore, it has the effect of suppressing the occurrence of color separation during storage or application of the photosensitive colored resin composition.

Examples of the polymer dispersant include polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, polyallylamine polymer dispersants, carbodiimide polymer dispersants, and the like. Polymer dispersants include dispersants with an amine value of 1 mgKOH/g or more and an acid value of less than 1 mgKOH/g, dispersants with an acid value of 1 mgKOH/g or more and an amine value of less than 1 mgKOH/g, and amine values. dispersants have an acid value of 1 mgKOH/g or more and an acid value of 1 mgKOH/g or more, and dispersants have an amine value of less than 1 mgKOH/g and an acid value of less than 1 mgKOH/g. Two or more types of these may be contained. Among these, dispersants having an amine value of 1 mgKOH/g or more are preferred.

Examples of the polymer dispersant having an amine value of 1 mgKOH/g or more and an acid value of less than 1 mgKOH/g include "DISPERBYK" (registered trademark) 102, 160, 161, 162, 2163, 164, 2164, 166, 167, 168, 2000, 2050, 2150, 2155, 9075, 9077, "BYK" (registered trademark) - LP N6919, "DISPERBYK" (registered trademark) - LP N21116, "DISPERBYK" (registered trademark) - LP N21234 (and above) , all manufactured by Bick Chemie), "EFKA" (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4800 (all of the above) (manufactured by BASF), “Ajisper” (registered trademark) PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.), “SOLSPERSE” (registered trademark) 13240, 13940, 20000, 71000, 76500 (all manufactured by Lubrizol, Inc.) (manufactured by).

Examples of polymeric dispersants having an amine value of 1 mgKOH/g or more and an acid value of 1 mgKOH/g or more include "DISPERBYK" (registered trademark) 142, 145, 2001, 2010, 2020, 2025, 9076, Anti- Terra (registered trademark) -205 (all manufactured by Bik-Chemie), "SOLSPERSE" (registered trademark) 24000 (manufactured by Lubrizol Co., Ltd.), "Ajisper" (registered trademark) PB821, PB880, PB881 (all manufactured by Bikkemie), All manufactured by Ajinomoto Fine Techno Co., Inc.), “SOLSPERSE” (registered trademark) 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 326000, 33000, 34750, 35100, 35200, 37500, 39000 , 56,000 ( (manufactured by Lubrizol Co., Ltd.).

When the photosensitive colored resin composition of the present invention contains a polymer dispersant, the content of the polymer dispersant is preferably 10 to 100 parts by mass based on 100 parts by mass of (B) zirconium compound particles, More preferably 20 to 60 parts by mass. When the content of the polymer dispersant is 10 parts by mass or more, dispersion stability can be improved. On the other hand, when the content of the polymer dispersant is 100 parts by mass or less, the heat resistance and adhesion of the colored spacer can be improved.

The photosensitive colored resin composition of the present invention can contain a thermal crosslinking agent. A thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group in its molecule. The thermal crosslinking agent crosslinks the alkali-soluble resin (A) or other additive components, and can improve the heat resistance, chemical resistance, and hardness of the film after thermosetting.

Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include, for example, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (product name, Honshu (manufactured by Kagaku Kogyo Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (product name, NIKALAC MX-750LM) (manufactured by Sanwa Chemical).

Preferred examples of compounds having at least two epoxy groups include Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L (manufactured by Nagase ChemteX Co., Ltd.), GAN, GOT ( (manufactured by Nippon Kayaku Co., Ltd.), Epicort 828, Epicort 1002, Epicort 1750, Epicort 1007, YX8100-BH30, E1256, E4250, E4275 (manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon EXA-9583, HP4032 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), VG3101 (manufactured by Mitsui Chemicals, Inc.), Tepic S, Tepic G, Tepic P (manufactured by Nissan Chemical Industries, Ltd.), NC6000 (manufactured by Nippon Kayaku Co., Ltd.) (manufactured by Nippon Kayaku Co., Ltd.), Epotote YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, and NC3000 (manufactured by Nippon Kayaku Co., Ltd.).

Preferred examples of compounds having at least two oxetanyl groups include etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (manufactured by Ube Industries, Ltd.), and oxetanated phenol novolak. Two or more types of thermal crosslinking agents may be used in combination. The content of the thermal crosslinking agent is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). If the content of the thermal crosslinking agent is 0.1 to 30 parts by mass or less, the chemical resistance and hardness of the film after firing or curing can be improved, and the storage stability of the photosensitive colored resin composition can also be improved. Excellent.

The photosensitive colored resin composition of the present invention can contain a blocked isocyanate. Blocked isocyanate is a compound having two or more isocyanate groups blocked by a blocking agent. Since the blocking agent dissociates upon heating and the isocyanate group is regenerated, the blocked isocyanate has a long pot life, and the photosensitive colored resin composition containing it has excellent viscosity stability. In the photosensitive colored resin composition of the present invention, blocked isocyanate can be used as a curing agent. Blocked isocyanate is heated at a relatively low temperature to dissociate (deprotect) the blocking agent and regenerate the isocyanate group. The photosensitive colored resin composition is cured by the regenerated isocyanate group thermally reacting with the hydroxyl group and/or carboxyl group in the alkali-soluble resin (A). The type of isocyanate is not particularly limited, but includes aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, dimers or trimers obtained by modification of diisocyanates, and compounds containing terminal isocyanate groups. These may be used alone or in combination. Examples of the aromatic diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and dianisidine diisocyanate. Examples of aliphatic diisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter referred to as HMDI), and 2,2,4-trimethyl-1,6-hexamethylene. Examples include diisocyanates. Examples of the alicyclic diisocyanate include lysine diisocyanate, isophorone diisocyanate (hereinafter referred to as IPDI), 1,3-bis(isocyanatomethyl)-cyclohexane, and 4,4'-dicyclohexylmethane diisocyanate. Further examples include dimers and trimers obtained by modifying these diisocyanates. Examples of the modification method include biuret formation and isocyanurate formation. Or a terminal isocyanate group-containing compound obtained by reacting the aforementioned diisocyanate compound or polyisocyanate compound with an active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyol, polyether polyol, polyamide, etc. can be mentioned. Examples of the blocking agent include known blocking agents such as phenol, methyl ethyl ketoxime, and sodium bisulfite. Such blocking agents that can be dissociated at lower temperatures include active methylene compounds and pyrazole compounds. Examples of the active methylene compound include Meldrum's acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate. Examples of pyrazole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethyl Examples include pyrazole, 3-methyl-5-phenylpyrazole, and the like. Among them, diethyl malonate, 3,5-dimethylpyrazole and the like are preferred.

Blocked isocyanates are commercially available. For example, Coronate (registered trademark) AP Stable M, Coronate (registered trademark) 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate (registered trademark) 17B- 60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (Asahi Kasei Chemicals Co., Ltd. ), Desmodule BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur (registered trademark) BL31 75 (the above, Sumika Bayer (manufactured by Urethane Co., Ltd.) etc. can be preferably used. The content of the blocked isocyanate is preferably 1 to 300 parts by mass based on 100 parts by mass of the alkali-soluble resin (A).

The photosensitive colored resin composition used in the present invention may contain an adhesion improver. Examples of adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group containing Examples include compounds obtained by reacting silicon compounds. Two or more types of these may be contained. By containing these adhesion improvers, when developing a photosensitive colored resin film, it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO ₂ or silicon nitride. Furthermore, resistance to oxygen plasma used for cleaning and UV ozone treatment can be increased. The content of the adhesion improver is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the alkali-soluble resin (A).

The photosensitive colored resin composition used in the present invention may contain a surfactant, if necessary, for the purpose of improving wettability with the substrate and improving the uniformity of the thickness of the photosensitive colored resin film. It's okay. Commercially available compounds can be used as the surfactant. Specifically, silicone surfactants include the SH series, SD series, and ST series of Dow Corning Toray Silicone Co., Ltd., the BYK series of BYK Chemie Japan Co., Ltd. Examples include Shin-Etsu Silicone's KP series, NOF's Disform series, and Toshiba Silicone's TSF series.As for fluorine-based surfactants, Dainippon Ink Industries'"Megafac (registered trademark)" series, Examples include Sumitomo 3M's Florado series, Asahi Glass'"Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series, Shin-Akita Kasei Co., Ltd.'s EF series, and Omnova Solutions' Polyfox series. Examples of surfactants made of acrylic and/or methacrylic polymers include, but are not limited to, the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd. and the "Disparon (registered trademark)" series manufactured by Kusumoto Kasei Co., Ltd.
The content of the surfactant is preferably 0.001 to 1 part by mass based on 100 parts by mass of the alkali-soluble resin (A).

As a method for producing the photosensitive coloring composition of the present invention, for example, a resin solution containing (A) an alkali-soluble resin, (B) zirconium compound particles, and optionally a dispersant and an organic solvent is prepared using a dispersing machine. A preferred method is to prepare a dispersion liquid with a high concentration of zirconium compound particles by dispersing the zirconium compound particles, and then add other components such as (A) an alkali-soluble resin and (C) a photosensitizer, and stir the mixture. Filtration may be performed if necessary.

Examples of the dispersing machine include a ball mill, bead mill, sand grinder, three-roll mill, and high-speed impact mill. Among these, bead mills are preferred for improving dispersion efficiency and fine dispersion. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a dyno mill. Examples of beads used in the bead mill include titania beads, zirconia beads, and zircon beads. The bead diameter of the bead mill is preferably 0.03 to 1.0 mm. (B) When the primary particle size of the zirconium compound particles and the particle size of the secondary particles formed by agglomeration of the primary particles are small, it is preferable to use minute beads with a diameter of 0.03 to 0.10 mm. . In this case, a bead mill equipped with a centrifugal separator capable of separating minute beads and a dispersion liquid is preferred. On the other hand, when dispersing (B) zirconium compound particles containing coarse particles on the order of submicrons, it is preferable to use beads with a diameter of 0.10 mm or more in order to obtain sufficient crushing force.

Next, a method for producing a film substrate with colored spacers will be described, which is characterized in that colored spacers are formed by coating, drying, exposing, developing and curing the photosensitive colored resin composition of the present invention on a film substrate. do.
The method for manufacturing a film substrate with colored spacers includes a step of applying a photosensitive colored resin composition onto a film substrate to form a colored film before curing, a step of drying the colored film, a step of exposing the colored film to light, and a step of exposing the colored film to light. The method includes a step of developing the colored film, and a step of curing the colored film to form a colored spacer.

First, the process of applying a photosensitive colored resin composition to form a colored film will be described. In this step, the photosensitive colored resin composition of the present invention is applied onto a film substrate by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc. to obtain a colored film. Among these, the slit coating method is preferably used. The coating speed in the slit coating method is generally in the range of 10 mm/sec to 400 mm/sec. The thickness of the colored film varies depending on the solid content concentration, viscosity, etc. of the photosensitive colored resin composition, but the film thickness after drying is usually 3 to 40 μm, preferably 5 to 20 μm, and more preferably 9 to 20 μm. It is applied like this. Examples of film substrates include films such as plastic films and those on which electrodes are partially formed using conductive substances such as ITO, Cu, and Ag. Prior to coating, the film substrate to which the photosensitive colored resin composition is coated may be subjected to pretreatment such as UV treatment or plasma treatment.

Next, the process of drying the colored film will be described. In this step, after applying the photosensitive colored resin composition, the colored film is dried. Drying in this step refers to vacuum drying or heat drying. Both reduced pressure drying and heat drying may be carried out, or only one of them may be carried out. Let's talk about heat drying. This process is also called prebaking. For drying, use a hot plate, oven, infrared rays, etc. The heating temperature varies depending on the type and purpose of the photosensitive colored resin film, and is preferably carried out at a temperature of 50° C. to 120° C. for 1 minute to several hours.

Next, the process of exposing the colored film to light will be described. In this step, in order to form a pattern from the obtained colored film, the colored film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, but in the present invention, the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, and UV-LED Preferably, a light source is used.

Next, the process of developing the exposed colored film will be described. In this step, after exposure, a desired pattern is formed by removing unexposed areas using a developer. Examples of the developer include tetramethylammonium hydroxide (hereinafter referred to as TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, Aqueous solutions of alkaline compounds such as dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination. good. As the developing method, methods such as spray, paddle, immersion, and ultrasonic waves are possible. Next, the pattern formed by development is preferably rinsed with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may be added to distilled water for rinsing.

Next, the process of curing and forming colored spacers will be described. Curing is performed by irradiating with UV light. For example, it can be performed using a conveyor-type UV irradiation device or a low-pressure mercury lamp. The illuminance is preferably about 10 to 500 mW/cm ² , and the exposure amount is preferably 500 to 10,000 mJ/cm ² . The higher the illuminance, the less the influence of oxygen inhibition on the surface, and therefore the curability can be improved. The higher the exposure amount, the more the bottom part can be photocured, so the curability can be improved. In curing, heat treatment (post-bake) may be performed as necessary, simultaneously with UV light irradiation, or before or after UV light irradiation. The heat treatment may be performed in air, under a nitrogen atmosphere, or in a vacuum state. The heating temperature is preferably 60 to 120°C, and the heating time is preferably 0.25 to 5 hours. The heating temperature may be changed continuously or in steps.

The OD value of the colored spacer is determined by measuring the intensity of the incident light on the colored spacer and the intensity of the transmitted light transmitted through the colored spacer using an optical densitometer (361TVisual; manufactured by X-Rite), and using the following formula (5). It can be calculated by
OD value = log ₁₀ (I ₀ /I) ... Formula (5)
_I0 : Incident light intensity I: Transmitted light intensity.

The colored spacer obtained by curing the photosensitive colored resin composition of the present invention can be suitably used for producing wiring patterns of electronic components, light-shielding images such as black matrices, colored partition walls, and colored spacers. The colored spacer has the role of determining the thickness of the liquid crystal layer and making the thickness uniform. Coloring can prevent deterioration in design due to light leakage. Furthermore, the photosensitive colored resin composition of the present invention can be suitably used in display devices using liquid crystals. In particular, it is suitably used in a light control layer having a light control body between colored spacers.

The light control device includes a light control layer made of a colored spacer of a photosensitive colored resin composition. An example of a method for manufacturing a light control device including a light control layer will be described.
First, a colored spacer is formed on a transparent conductive film on which an electrode layer is formed as a base material by the above-described method of curing the photosensitive colored resin composition of the present invention to form a colored spacer. As the transparent conductive film, a transparent resin film formed by forming a transparent conductive film made of a transparent conductive material such as ITO, IZO, or a conductive polymer (organic conductive film) is preferable. A liquid crystal layer is sandwiched between the transparent electrodes facing each other. A suitable thickness of the transparent electrode is 80 nm or more and 150 nm or less.

Next, the application of the sealant will be described. A sealing agent is applied in a frame shape to the periphery of the transparent conductive layer of the transparent conductive film by screen printing. As the sealant, a material containing a mixture of polyfunctional acrylate and an ultraviolet absorber can be used.

Next, a method for forming the light control layer will be described. By applying the light control material to the inside of the sealant frame, the light control material can be filled between the colored spacers. The light control body is not particularly limited, and conventionally known light control bodies such as a light control body using a liquid crystal material and a light control body using an electrochromic compound can be used. In particular, when using a light control body using a liquid crystal material or a light control body with relatively high fluidity such as an SPD (Suspended Particle Device), the colored spacer made of the photosensitive colored resin composition of the present invention This is particularly effective because the thickness of the light control body can be stabilized. Thereafter, separately prepared transparent conductive films were stacked on each other so that the light control layer of the transparent conductive film having a light control body formed thereon was sandwiched between transparent electrode layers to obtain a laminate. The obtained laminate was irradiated with ultraviolet rays to cure the sealant, thereby forming a sealing layer. The laminate on which the sealing layer was formed was pressed and laminated at a temperature of 40 to 90°C to obtain a light control sheet having a light control layer.

Next, a method for forming the light control device will be described. When the light control layer wound into a roll is continuously unwound from the roll and supplied, an adhesive liquid is applied to the surface of the light control layer, and a release film is laminated while the light control layer is wound up. A roll-shaped adhesive-backed light control sheet is obtained. The obtained light control sheet with adhesive was bonded to a glass substrate using a method such as autoclaving to obtain a light control device.

The colored spacer formed by curing the photosensitive colored resin composition of the present invention can form a high-definition and rectangular spacer shape even in a thick film, so it can be used as a colored spacer for a light control device having a light control layer. Suitably used. By using the light control layer having the colored spacer of the present invention, it is possible to design a display device with higher precision than when using colored spacer particles, and the design of the display device can be improved.

Further, by using the photosensitive colored resin composition of the present invention, colored spacers with a high aspect ratio can be formed. The aspect ratio is expressed as H/W, where W is the width of the colored spacer and H is the height of the colored spacer. The width of the colored spacer was determined by checking the cross-sectional shape using a SEM ("S-4800 (trade name)" manufactured by Hitachi High-Technologies Corporation), and the width was defined as the narrowest part. Further, the height of the colored spacer was similarly measured from the cross-sectional shape using SEM. The higher the aspect ratio of the colored spacer, the more difficult it is to form because the insufficiently hardened bottom portion dissolves during development, causing problems such as the colored spacer peeling off from the substrate or falling down. Furthermore, in the case of a pattern shape that is isolated from the surroundings, such as a colored spacer, the developer is applied to the pattern portion from all directions around the circumference, making the above problem more likely to occur and making formation more difficult. The aspect ratio is preferably 0.6 to 5.0. The lower limit is more preferably 1.0 or more, even more preferably 1.5 or more, and even more preferably 1.8 or more. The upper limit is more preferably 3.0 or less, even more preferably 2.9 or less, even more preferably 2.4 or less, and even more preferably 2.1 or less.

The colored spacer is a colored spacer containing a cured product of a photosensitive colored resin composition, and preferably has a film thickness of 5 to 20 μm and an aspect ratio of 1.0 to 3.0. The higher the aspect ratio is, the higher the film thickness of the light control body can be, the larger the difference in the amount of light when the light is turned on and off, and the more highly functional the light control layer can be created. Furthermore, the higher the aspect ratio, the more precisely the colored spacers can be arranged and the aperture ratio can be improved, and the design of the light control device can be improved.

The present invention will be described in detail below with reference to Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto.

<Evaluation method>
[Crystal size of zirconium compound particles]
As samples for measuring the crystallite size of particles in colored spacers, the colored spacers obtained in each of the Examples and Comparative Examples were cut out from a substrate and packed into an aluminum standard sample holder. For these measurement samples, X-ray diffraction spectra were measured by wide-angle X-ray diffraction using an X-ray diffractometer DS ADVANCE (trade name) manufactured by Bruker AXS Co., Ltd. and using CuKα rays as the X-ray source. As for the measurement conditions, the output is 40kV/40mA, and the slit system is Div. Slit: 0.3°, measurement step (2θ) was 0.0171°, and measurement time was 0.5 seconds/step. The diffraction angle and half-width of the peak derived from the ZrN (111) plane observed around the diffraction angle 2θ = 33.8° were measured, and the particles were determined using the Scherrer equation expressed by the above formula (2). The size of the constituent crystallites was determined.

[Metal particle content]
After melting and decomposing the zirconium compound particles with an alkali, the melt was dissolved in hydrochloric acid, and a fixed volume was prepared with ultrapure water to prepare a test solution. Quantitative analysis of elements in the test solution was performed using ICP-AES (manufactured by SII Nanotechnology Co., Ltd., model SPS5100).

[Light blocking property]
The OD value of the colored spacer obtained in each Example and Comparative Example was measured using an optical densitometer 361TVisual manufactured by X-Rite. Light blocking properties were evaluated according to the following criteria.
◎: OD value is 2 or more ○: OD value is 1 or more and less than 2 ×: OD value is less than 1.

[Development adhesion]
The colored spacers of each opening pattern obtained in each example and comparative example (the diameter was changed in 1 μm increments in the range of 5 to 10 μm, and in 5 μm increments in the range of 10 to 50 μm) were examined using an optical microscope (manufactured by Olympus Sales Co., Ltd.). Using "BH3-MJL (product name)"), 100 locations per size were observed at a magnification of 50 times, and the development adhesion was evaluated based on the following criteria from the smallest aperture pattern with 90 or more remaining patterns. was evaluated.
◎: Minimum pattern is less than 10 μm ○: Minimum pattern is 10 μm or more and less than 20 μm ×: Minimum pattern is 20 μm or more.

[aspect ratio]
Regarding the colored spacer with the minimum opening pattern obtained in the evaluation of development adhesion, the width of the colored spacer was W, the height was H, and the aspect ratio expressed as H/W was measured. The width of the colored spacer was determined by checking the cross-sectional shape using a SEM ("S-4800 (trade name)" manufactured by Hitachi High-Technologies Corporation), and the width was defined as the narrowest part. Further, the height of the colored spacer was similarly measured from the cross-sectional shape using SEM.

[Rubbing test]
A substrate coated with a polyimide alignment film was attached to the colored spacer so that the polyimide surface was in contact with the colored spacer. While pressing a PTFE rod with Toraysee (ME Wiper) on its surface with a load of 100 g, it was rubbed at a speed of 90 mm/sec over a distance of 50 mm with 50,000 reciprocating strokes. The colored spacer after the test was observed with an optical microscope every 5000 times, and the rubbing test resistance was evaluated according to the following criteria.

◎: Deformation and peeling occurred when the number of strokes was 40,001 or more and 50,000 or less. Or, no deformation or peeling after 50,000 strokes ○: Deformation or peeling after 20,001 or more strokes and 40,000 or less strokes ×: Deformation or peeling after 20,000 strokes or less.

[Elastic recovery rate]
The elastic recovery rate of the truncated conical pattern colored spacer with the opening pattern of 20 μm obtained in each Example and Comparative Example was measured by the following method. Pressure was applied to the obtained colored spacer at 25° C. using a Fischerscope H100 (manufactured by Helmμut Fischer GmbH & Co) and a flat indenter with a diameter of 50 μm at a loading rate of 2.5 mN/sec until a load of 40 mN was reached. After holding for 5 seconds, the pressure was unloaded at an unloading rate of 2.5 mN/sec, and after reaching 0 mN, the pressure was held for 5 seconds. A hysteresis curve between the load and the amount of deformation was created. From the obtained hysteresis curve, the total amount of deformation Ha (μm) and the amount of plastic deformation Hb (μm) were determined, and the elastic recovery rate of the colored spacer was calculated from the following formula, and evaluated according to the following criteria.
Elastic recovery rate (%) = ((Ha-Hb)/Ha) x 100
◎: Elastic recovery rate is 90% or more. ○: Elastic recovery rate is 50% or more and less than 90%. ×: Elastic recovery rate is less than 50%.

(Synthesis Example 1 Synthesis of alkali-soluble resin (P-1))
A methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio 30/40/30) was synthesized by the method described in Example 1 of Japanese Patent No. 3120476. By adding 40 parts by mass of glycidyl methacrylate to 100 parts by mass of the obtained copolymer, reprecipitating with purified water, filtering and drying, an acrylic type with a mass average molecular weight of 15,000 and an acid value of 110 mgKOH/g was obtained. An alkali-soluble resin (P-1) was obtained. The acid value of the alkali-soluble resin is the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin (unit: mgKOH/g), and the mass average molecular weight is determined by gel permeation chromatography (mgKOH/g). GPC) "HLC-8220GPC" (Testing device manufactured by Tosoh Corporation) was used to measure in terms of polystyrene using tetrahydrofuran as the carrier.

(Synthesis Example 2: Synthesis of radically polymerizable compound (FA-1))
A radically polymerizable compound (FA-1) having a fluorene skeleton was synthesized by the method of Example 1 of Japanese Patent No. 5782281.

(Production Example 1 Production of colorant dispersion (DB-1))
140 g of zirconium compound particles (Zr-1) (manufactured by Nisshin Engineering Co., Ltd.), which are composite fine particles consisting of zirconium nitride and aluminum particles, produced by a thermal plasma method, 35% by mass PGMEA of alkali-soluble resin (P-1) 143 g of solution, 10 g of "DISPERBYK" (registered trademark) "LPN-21116" (manufactured by BYK Chemie) having a tertiary amino group and quaternary ammonium salt as a polymer dispersant, and 507 g of PGMEA were placed in a tank, and stirred for 20 minutes with a homomixer. A preliminary dispersion liquid was obtained. The obtained preliminary dispersion liquid was supplied to an Ultra Apex Mill, a dispersion machine manufactured by Hiroshima Metal & Machinery Co., Ltd., equipped with a centrifugal separator filled with 75% by volume of 0.10 mmφ zirconia beads, and was heated at a rotation speed of 9 m/s for 3 hours. Dispersion was performed to obtain a colorant dispersion (DB-1) with a solid content concentration of 25% by mass and a colorant/resin (mass ratio) of 70/30.

(Production Example 2 Production of colorant dispersion (DB-2))
Production Example 1 except that commercially available zirconium nitride particles (Zr-2) (manufactured by Japan Shinkinzoku Co., Ltd.) were used instead of zirconium compound particles (Zr-1) produced by a thermal plasma method as zirconium compound particles. A coloring material dispersion (DB-2) was obtained in the same manner.

(Production Example 3 Production of colorant dispersion (DB-3))
A coloring material dispersion (DB-3) was prepared in the same manner as in Production Example 1, except that carbon black whose surface was modified with a sulfonic acid group (TPK1227 manufactured by Cabot) was used instead of the zirconium compound particles (Zr-1). I got it.

(Production Example 4 Production of colorant dispersion (DB-4))
A coloring material dispersion ( DB-4) was obtained.

(Example 1)
To 5.1 g of colorant dispersion (DB-1), 56.9 g of a 35% by mass PGMEA solution of (P-1) was added as an alkali-soluble resin, and as a radically polymerizable compound, a compound having a fluorene skeleton was added. 5.2g of ``EA-0250P'', 6.1g of ``PE-3A'' as a trifunctional or higher polyfunctional acrylate compound, 0.1g of ``IC379'' as a photosensitizer, 0.1g of silicone surfactant ``BYK'' ( 333 (registered trademark) and 26.6 g of PGMEA were added to obtain a photosensitive colored resin composition (PB-1) with a total solid concentration of 30% by mass and pigment/resin (mass ratio) = 3/97. Ta.
Next, the obtained photosensitive colored resin composition (PB-1) was applied onto a non-alkali glass substrate (AN100) using a spinner (MS-A150) manufactured by Mikasa Co., Ltd. to obtain a film thickness after post-curing. The colored film was dried by heating on a hot plate at 100° C. for 3 minutes. For this colored film, a mask aligner (PEM-6M) manufactured by Union Optical Co., Ltd. was used to apply a negative mask manufactured by HOYA Co., Ltd. (Design colored spacer diameter: change the diameter in 1 μm increments in the range of 5 to 10 μm, 10 to 10 μm). Exposure to ultraviolet rays (g, h, i-line) at 300 mJ/cm ² (i-line equivalent) through a range of 50 μm (changed in 5 μm increments) and develop with an alkaline developer of 0.045 mass% potassium hydroxide aqueous solution. By doing so, a patterned substrate was obtained. The resulting patterned substrate was irradiated with ultraviolet light (g, h, i-line) at 7500 mJ/cm ² (i-line equivalent) using a conveyor-type UV irradiation device "UVC-1212" (manufactured by Ushio Inc.). ) was exposed to light to obtain a colored spacer (BK-1). Tables 1 and 2 show the results of evaluation of this colored spacer using the method described above.

(Example 2)
To 5.1 g of colorant dispersion (DB-1), 44.2 g of cardo-based alkali-soluble resin "WR-301" (manufactured by ADEKA Co., Ltd.) was added as an alkali-soluble resin, and fluorene skeleton was added as a radically polymerizable compound. 2.6g of "EA-0250P" (manufactured by Osaka Gas Chemical Co., Ltd.) as a compound having 7.5 g of "PE-3A" (manufactured by Kyoeisha Chemical Co., Ltd.) as a trifunctional or higher polyfunctional acrylate compound. 4g, as a photosensitizer, 0.1g of acetophenone initiator "IC379" (manufactured by BASF Japan Co., Ltd.), 0.03g of silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), PGMEA A photosensitive colored resin composition (PB-2) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-2) of the photosensitive colored resin composition (PB-2) was evaluated in the same manner as in Example 1.

(Example 3)
To 5.1 g of coloring material dispersion (DB-1), 25.0 g of "WR-301" was added as an alkali-soluble resin, and 5 g of "EA-0250P" was added as a radical polymerizable compound as a compound having a fluorene skeleton. .2g, 14.7g of "PE-3A" as a trifunctional or higher polyfunctional acrylate compound, 0.1g of "IC379" as a photosensitizer, 0.0g of silicone surfactant "BYK" (registered trademark) 333. .03 g and 49.8 g of PGMEA were added to obtain a photosensitive colored resin composition (PB-3) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97. The colored spacer (BK-3) of the photosensitive colored resin composition (PB-3) was evaluated in the same manner as in Example 1.

(Example 4)
Synthesis example: 5.1 g of colorant dispersion (DB-1), 25.0 g of cardo-based alkali-soluble resin "WR-301" as an alkali-soluble resin, and a compound having a fluorene skeleton as a radically polymerizable compound. 2.6g of compound 2 (FA-1), 14.7g of "PE-3A" as a trifunctional or higher functional acrylate compound, 0.1g of "IC379" as a photosensitizer, silicone surfactant A photosensitive colored resin composition (PB- 4) was obtained. The colored spacer (BK-4) of the photosensitive colored resin composition (PB-4) was evaluated in the same manner as in Example 1.

(Example 5)
A total solid concentration of 30 mass was obtained in the same manner as in Example 4, except that the oxime ester initiator "NCI-831" (manufactured by ADEKA Co., Ltd.) was used as the photosensitizer instead of the acetophenone initiator "IC379". %, pigment/resin (mass ratio) = 3/97, a photosensitive colored resin composition (PB-5) was obtained. The colored spacer (BK-5) of the photosensitive colored resin composition (PB-5) was evaluated in the same manner as in Example 1.

(Example 6)
To 5.1 g of colorant dispersion (DB-1), 24.9 g of cardo-based alkali-soluble resin "WR-301" was added as an alkali-soluble resin, and (FA 2.6g of -1), 14.7g of "PE-3A" as a trifunctional or higher polyfunctional acrylate compound, 0.1g of oxime ester-based initiator "NCI-831" as a photosensitizer, (E ) As a polyfunctional thiol compound, 0.06 g of "MT-PE1" (Showa Denko KK), 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 52.5 g of PGMEA were added, A photosensitive colored resin composition (PB-6) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-6) of the photosensitive colored resin composition (PB-6) was evaluated in the same manner as in Example 1.

(Example 7)
To 5.1 g of colorant dispersion (DB-1), 44.2 g of cardo-based alkali-soluble resin "WR-301" (manufactured by ADEKA Co., Ltd.) was added as an alkali-soluble resin, and fluorene skeleton was added as a radically polymerizable compound. As a compound having 0.9 g of "EA-0250P" (manufactured by Osaka Gas Chemical Co., Ltd.), and as a polyfunctional acrylate compound having 3 or more functions, "PE-3A" (manufactured by Kyoeisha Chemical Co., Ltd.) 8. 2 g, as photosensitizers, 0.1 g of acetophenone initiator "IC379" (manufactured by BASF Japan Ltd.), 0.03 g of silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK Chemie Co., Ltd.), PGMEA A photosensitive colored resin composition (PB-7) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-7) of the photosensitive colored resin composition (PB-7) was evaluated in the same manner as in Example 1.

(Example 8)
To 5.1 g of colorant dispersion (DB-1), 44.2 g of cardo-based alkali-soluble resin "WR-301" (manufactured by ADEKA Co., Ltd.) was added as an alkali-soluble resin, and fluorene skeleton was added as a radically polymerizable compound. 1.7g of "EA-0250P" (manufactured by Osaka Gas Chemicals Co., Ltd.) as a compound having 1.7g, and 7g of "PE-3A" (manufactured by Kyoeisha Chemical Co., Ltd.) as a trifunctional or higher polyfunctional acrylate compound. 8 g, as a photosensitizer, 0.1 g of acetophenone initiator "IC379" (manufactured by BASF Japan Ltd.), 0.03 g of silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK Chemie Co., Ltd.), PGMEA A photosensitive colored resin composition (PB-8) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-8) of the photosensitive colored resin composition (PB-8) was evaluated in the same manner as in Example 1.

(Example 9)
To 5.1 g of colorant dispersion (DB-1), 44.2 g of cardo-based alkali-soluble resin "WR-301" (manufactured by ADEKA Co., Ltd.) was added as an alkali-soluble resin, and fluorene skeleton was added as a radically polymerizable compound. 3.5 g of "EA-0250P" (manufactured by Osaka Gas Chemical Co., Ltd.) as a compound having 6. 9 g, as a photosensitizer, 0.1 g of acetophenone initiator "IC379" (manufactured by BASF Japan Ltd.), 0.03 g of silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK Chemie Co., Ltd.), PGMEA A photosensitive colored resin composition (PB-9) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-9) of the photosensitive colored resin composition (PB-9) was evaluated in the same manner as in Example 1.

(Example 10)
To 5.1 g of colorant dispersion (DB-1), 44.2 g of cardo-based alkali-soluble resin "WR-301" (manufactured by ADEKA Co., Ltd.) was added as an alkali-soluble resin, and fluorene skeleton was added as a radically polymerizable compound. 4.3g of "EA-0250P" (manufactured by Osaka Gas Chemical Co., Ltd.), and 6.3g of "PE-3A" (manufactured by Kyoeisha Chemical Co., Ltd.) as a trifunctional or higher polyfunctional acrylate compound. 5 g, as a photosensitizer, 0.1 g of acetophenone initiator "IC379" (manufactured by BASF Japan Ltd.), 0.03 g of silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), PGMEA A photosensitive colored resin composition (PB-10) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-10) of the photosensitive colored resin composition (PB-10) was evaluated in the same manner as in Example 1.

(Comparative example 1)
As an alkali-soluble resin, 46.4 g of cardo-based alkali-soluble resin "WR-301", as a radically polymerizable compound, 2.7 g of "EA-0250P" as a compound having a fluorene skeleton, and a trifunctional or higher polyfunctional acrylate. As a compound, 7.6 g of "PE-3A", as a photosensitizer, 0.1 g of "IC379", 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 43.1 g of PGMEA were added. A photosensitive colored resin composition (PB-11) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 0/100 was obtained. The colored spacer (BK-11) of the photosensitive colored resin composition (PB-11) was evaluated in the same manner as in Example 1.

(Comparative example 2)
The same method as in Example 1 was used except that (DB-3) was used instead of (DB-1) as the colored dispersion, with a total solid concentration of 30% by mass and pigment/resin (mass ratio) = 3/97. A photosensitive colored resin composition (PB-12) was obtained. The colored spacer (BK-12) of the photosensitive colored resin composition (PB-12) was evaluated in the same manner as in Example 1.

(Comparative example 3)
The same method as in Example 1 was used except that (DB-4) was used instead of (DB-1) as the colored dispersion, the total solid concentration was 30% by mass, and the pigment/resin (mass ratio) = 3/97. A photosensitive colored resin composition (PB-13) was obtained. The colored spacer (BK-13) of the photosensitive colored resin composition (PB-13) was evaluated in the same manner as in Example 1.

(Comparative example 4)
The same method as in Example 1 was used except that (DB-2) was used instead of (DB-1) as the colored dispersion, with a total solid concentration of 30% by mass and pigment/resin (mass ratio) = 3/97. A photosensitive colored resin composition (PB-14) was obtained. The colored spacer (BK-14) of the photosensitive colored resin composition (PB-14) was evaluated in the same manner as in Example 1.

(Comparative example 5)
5.1 g of colorant dispersion (DB-1), 44.2 g of cardo-based alkali-soluble resin "WR-301" as an alkali-soluble resin, and a trifunctional or higher polyfunctional acrylate compound as a radically polymerizable compound. , 8.7 g of "PE-3A", 0.1 g of "IC379" as a photosensitizer, 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 41.8 g of PGMEA were added. A photosensitive colored resin composition (PB-15) with a solid content concentration of 30% by mass and a pigment/resin (mass ratio) of 3/97 was obtained. The colored spacer (BK-15) of the photosensitive colored resin composition (PB-15) was evaluated in the same manner as in Example 1.

(Comparative example 6)
5.1g of colorant dispersion (DB-1), 44.2g of cardo-based alkali-soluble resin "WR-301" as an alkali-soluble resin, and "EA" as a compound having a fluorene skeleton as a radically polymerizable compound. -0250P" (manufactured by Osaka Gas Chemicals Co., Ltd.), 4.7 g of trifunctional or higher polyfunctional acrylate compound, 6.3 g of "PE-3A", 0.1 g of "IC379" as a photosensitizer, and silicone. A photosensitive colored resin composition containing 0.03 g of the surfactant "BYK" (registered trademark) 333 and 39.5 g of PGMEA, a total solid concentration of 30% by mass, and a pigment/resin (mass ratio) of 3/97. A product (PB-16) was obtained. The colored spacer (BK-16) of the photosensitive colored resin composition (PB-16) was evaluated in the same manner as in Example 1.

(Comparative example 7)
5.1g of colorant dispersion (DB-1), 44.2g of cardo-based alkali-soluble resin "WR-301" as an alkali-soluble resin, and "EA" as a compound having a fluorene skeleton as a radically polymerizable compound. -0250P'' (manufactured by Osaka Gas Chemicals Co., Ltd.), 5.2 g, trifunctional or higher polyfunctional acrylate compound, 6.1 g of PE-3A, photosensitizer, 0.1 g of IC379, silicone. A photosensitive colored resin composition containing 0.03 g of the surfactant "BYK" (registered trademark) 333 and 39.2 g of PGMEA, a total solid concentration of 30% by mass, and a pigment/resin (mass ratio) of 3/97. A product (PB-17) was obtained. The colored spacer (BK-17) of the photosensitive colored resin composition (PB-17) was evaluated in the same manner as in Example 1.

(Comparative example 8)
5.1g of colorant dispersion (DB-1), 44.2g of cardo-based alkali-soluble resin "WR-301" as an alkali-soluble resin, and "EA" as a compound having a fluorene skeleton as a radically polymerizable compound. -0250P" (manufactured by Osaka Gas Chemicals Co., Ltd.), 6.1 g of trifunctional or higher polyfunctional acrylate compound, 5.6 g of "PE-3A", 0.1 g of "IC379" as a photosensitizer, and silicone. A photosensitive colored resin composition containing 0.03 g of the surfactant "BYK" (registered trademark) 333 and 38.8 g of PGMEA, a total solid concentration of 30% by mass, and a pigment/resin (mass ratio) of 3/97. A product (PB-18) was obtained. The colored spacer (BK-18) of the photosensitive colored resin composition (PB-18) was evaluated in the same manner as in Example 1.

It can be seen that the photosensitive colored resin compositions of Examples have high light-shielding properties and are excellent in all of the results of development adhesion, rubbing test, and elastic recovery rate. On the other hand, when the photosensitive colored resin composition of the comparative example does not meet the requirements for the (B) zirconium compound particles according to claim 1, the sensitivity in the exposure step is poor, so the development adhesion is poor, and the hardness of the colored spacer is poor. It can be seen that the results of the elastic recovery rate are inferior because of the inferiority of the elastic recovery rate. In addition, when the photosensitive colored resin composition of the comparative example does not satisfy the content ratio of (D-1) and (D-2) according to claim 1, it is possible to achieve both hydrophobicity imparting to the bottom and high crosslink density. It can be seen that the development adhesion is poor because it is not possible.

(Example 11)
To 1.7 g of colorant dispersion (DB-1), 26.0 g of cardo-based alkali-soluble resin "WR-301" was added as an alkali-soluble resin, and (FA 2.7g of -1), 15.0g of "PE-3A" as a trifunctional or higher polyfunctional acrylate compound, 0.1g of oxime ester-based initiator "NCI-831" as a photosensitizer, (E ) As a polyfunctional thiol compound, 0.06 g of "MT-PE1" (Showa Denko KK), 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 54.5 g of PGMEA were added, A photosensitive colored resin composition (PB-19) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 1/99 was obtained. The colored spacer (BK-19) of the photosensitive colored resin composition (PB-19) was evaluated in the same manner as in Example 1 regarding the items of [light shielding property], [development adhesion], and [aspect ratio]. Ta.

(Example 12)
To 8.5 g of colorant dispersion (DB-1), 23.9 g of cardo-based alkali-soluble resin "WR-301" was added as an alkali-soluble resin, and (FA -1), 2.5 g of trifunctional or higher polyfunctional acrylate compound, 14.4 g of "PE-3A", 0.1 g of oxime ester initiator "NCI-831" as a photosensitizer, (E ) As a polyfunctional thiol compound, 0.06 g of "MT-PE1" (Showa Denko KK), 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 50.5 g of PGMEA were added, A photosensitive colored resin composition (PB-20) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 5/95 was obtained. The colored spacer (BK-20) of the photosensitive colored resin composition (PB-20) was evaluated in the same manner as in Example 11.

(Example 13)
To 17.1 g of colorant dispersion (DB-1), 21.3 g of cardo-based alkali-soluble resin "WR-301" was added as an alkali-soluble resin, and (FA 2.4g of -1), 13.6g of "PE-3A" as a trifunctional or higher polyfunctional acrylate compound, 0.1g of oxime ester-based initiator "NCI-831" as a photosensitizer, (E ) As a polyfunctional thiol compound, 0.05 g of "MT-PE1" (Showa Denko KK), 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 45.5 g of PGMEA were added, A photosensitive colored resin composition (PB-21) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 10/90 was obtained. The colored spacer (BK-21) of the photosensitive colored resin composition (PB-21) was evaluated in the same manner as in Example 11.

(Example 14)
To 25.6 g of colorant dispersion (DB-1), 18.7 g of cardo-based alkali-soluble resin "WR-301" was added as an alkali-soluble resin, and (FA 2.3g of -1), 12.8g of "PE-3A" as a trifunctional or higher polyfunctional acrylate compound, 0.1g of oxime ester-based initiator "NCI-831" as a photosensitizer, (E ) As a polyfunctional thiol compound, 0.05 g of "MT-PE1" (Showa Denko KK), 0.03 g of silicone surfactant "BYK" (registered trademark) 333, and 40.5 g of PGMEA were added, A photosensitive colored resin composition (PB-22) with a total solid concentration of 30% by mass and a pigment/resin (mass ratio) of 15/85 was obtained. The colored spacer (BK-22) of the photosensitive colored resin composition (PB-22) was evaluated in the same manner as in Example 11.

The photosensitive colored resin compositions of Examples 11, 6, 12, 13, and 14 had excellent light shielding properties, development adhesion, and aspect ratio. It can be seen that all the results are excellent. When the content of the zirconium compound particles is 1 to 20 parts by mass, the light blocking property is high, but the light transmittance in the ultraviolet region is also high. Pattern processing can be achieved.

(Example 15)
The photosensitive colored resin composition (PB-6) obtained in Example 6 was coated with a colored spacer (BK -23) was obtained. The colored spacer (BK-23) was evaluated in the same manner as in Example 11.

(Example 16)
A colored spacer (BK-24) was prepared and evaluated in the same manner as in Example 15, except that the coating was applied so that the film thickness after post-curing was 9.0 μm.

(Example 17)
A colored spacer (BK-25) was prepared and evaluated in the same manner as in Example 15, except that the coating was applied so that the film thickness after post-curing was 12.0 μm.

(Example 18)
A colored spacer (BK-26) was prepared and evaluated in the same manner as in Example 15, except that the coating was applied so that the film thickness after post-curing was 20.0 μm.

(Example 19)
A colored spacer (BK-27) was prepared and evaluated in the same manner as in Example 15, except that the coating was applied so that the film thickness after post-curing was 30.0 μm.

The colored spacers of Examples 15, 16, 17, 6, 18, and 19 had excellent light shielding properties, development adhesion, and aspect ratio, and the colored spacers of Examples 16, 17, 6, and 18 had particularly good results. It can be seen that both are excellent.

The photosensitive colored resin composition and colored spacer of the present invention can be suitably used for producing wiring patterns of electronic components, light-shielding images such as black matrices, colored partition walls, and colored spacers. Further, the photosensitive colored resin composition of the present invention is suitably used in a light control layer having a light control body between colored spacers.

Claims (9)

(A) an alkali-soluble resin, (B) zirconium compound particles, (C) a photosensitizer, and (D) a radical polymerizable compound, and when CuKα rays of the (B) zirconium compound particles are used as an X-ray source. The crystallite size determined from the half-width of the peak derived from the (111) plane of zirconium nitride in the X-ray diffraction spectrum is 10 nm or more and 60 nm or less, and (D) has a fluorene skeleton as the radically polymerizable compound (D-1). and (D-2) a trifunctional or more polyfunctional acrylate compound, the content of the compound having a fluorene skeleton (D-1) is (D-2) a trifunctional or more polyfunctional acrylate compound. A photosensitive colored resin composition in an amount of 5 to 35 parts by weight per 100 parts by weight. The photosensitive colored resin composition according to claim 1, comprising (A-1) a cardo-based resin having two or more repeating units represented by the following structural formula (1) as the alkali-soluble resin (A).

(D-1) Photosensitivity according to claim 1 or 2, comprising (D-1A) a compound having a fluorene skeleton, a condensed polycyclic aromatic ring other than fluorene, and one or more hydroxyl groups, as the compound having a fluorene skeleton. Colored resin composition. The photosensitive colored resin composition according to claim 1 or 2, which contains (C-1) an oxime ester photopolymerization initiator as the (C) photosensitizer. (E) The photosensitive colored resin composition according to claim 1 or 2, containing a polyfunctional thiol compound. The photosensitive colored resin composition according to claim 1 or 2, which contains 1 to 20% by mass of (B) zirconium compound particles based on 100% by mass of solid content of the photosensitive colored resin composition. A colored spacer comprising a cured product of the photosensitive colored resin composition according to claim 1 or 2, wherein the colored spacer has a film thickness of 5 to 20 μm and an aspect ratio of 1.0 to 3.0. colored spacers. A method for producing a film substrate with colored spacers, comprising forming colored spacers by applying the photosensitive colored resin composition according to claim 1 or 2 onto a film substrate, drying, exposing, developing and curing the composition. . A light control device comprising a light control layer comprising a colored spacer of the photosensitive colored resin composition according to claim 1 or 2.