CN104714367B - Coloring composition, coloring cured film and display element - Google Patents
Coloring composition, coloring cured film and display element Download PDFInfo
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- CN104714367B CN104714367B CN201410781873.0A CN201410781873A CN104714367B CN 104714367 B CN104714367 B CN 104714367B CN 201410781873 A CN201410781873 A CN 201410781873A CN 104714367 B CN104714367 B CN 104714367B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
The present invention provides a colored cured film having excellent adhesion and solvent resistance, a colored composition for forming the cured film, and a display element having the cured film, wherein the colored composition is characterized by comprising (A) a colorant, (B) a binder resin, (C) a radical polymerizable compound, (D) a photo radical generator, and (E) a compound having a structure in which a group represented by the following formula (E0) is directly bonded to an aromatic ring, ＊ - (CR 0)II 2)x－O－RI(E0) (in the formula (E0), RIIs a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RIIIs a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, x is 1 or 2, and "＊" represents a bond directly bonded to an aromatic ring.)
Description
Technical Field
The invention relates to a coloring composition, a colored cured film and a display element. More particularly, the present invention relates to a colored composition for forming a colored cured film suitable for a display device such as a transmission-type or reflection-type color liquid crystal display, an organic EL display device, and electronic paper, and a solid-state imaging device such as a CMOS image sensor, a colored cured film formed from the colored composition, and a display device having the colored cured film.
Background
To manufacture a color filter using the coloring composition, the following methods are known: a pigment-dispersed radiation-sensitive coloring composition is applied onto a substrate to form a coating film, and then the coating film is exposed to a desired pattern shape and developed to obtain pattern-like pixels of various colors (patent documents 1 and 2). As a method for producing a black matrix, a method for forming a black matrix in a pattern by performing the same operation using a carbon black-dispersed radiation-sensitive coloring composition is known (patent document 3). There is also known a method of forming pattern-like pixels of various colors by applying and curing a pigment dispersion type coloring composition by an ink jet method (patent document 4).
In the above-described series of operations, a method of irradiating light to a coating film through a photomask having a desired pattern is generally employed in order to expose the coating film in a pattern. At this time, a predetermined close gap (exposure gap) is provided between the coating film and the photomask. Here, it is preferable that the light irradiated directly passes through the opening of the photomask and is blocked at the closed portion. However, since light is diffracted at the edge portion of the photomask, light having a lower intensity than a predetermined exposure amount (light leakage) is irradiated to the coating film located in the vicinity of the opening portion in the closed portion.
In the coating film, whether the intermediate region where light is irradiated to leak is required to have the same properties as the opening region (exposed region) or the closed region (dark region) depends on the process configuration, the purpose of the product, and the like. That is, in the case of a negative-type colored composition, there is a case where a colored composition having high photosensitivity, in which the intermediate region is cured in the same manner as the exposed portion, is required, and on the other hand, there is a case where a colored composition having small mask variation (high reproducibility of the size of the mask for forming a pattern), in which the intermediate region is not cured (i.e., developed) in the same manner as the unexposed portion, is required. High photosensitivity and small mask variation are conflicting characteristics and are generally difficult to achieve.
With regard to the conventionally known coloring composition, it is known whether the light sensitivity is high or the mask misalignment is small, and it is difficult to separately produce a high sensitivity type coloring composition and a low mask misalignment type coloring composition while maintaining the same characteristics only by trial and error.
However, patent document 5 teaches that a colored cured film having an excellent pattern shape and high adhesion to a substrate can be formed with high accuracy by using a colored composition containing a specific phenol compound in the colored composition. This technique is indeed an excellent technique for improving adhesion and pattern shape, but the inventors of the present invention have found through studies that the solvent resistance of the resulting colored cured film is insufficient.
Accordingly, the art has recognized the necessity of being able to form a colored cured film excellent in both adhesiveness and solvent resistance.
Patent documents:
patent document 1: japanese laid-open patent publication No. 2-144502
Patent document 2: japanese laid-open patent publication No. 3-53201
Patent document 3: japanese laid-open patent publication No. 6-35188
Patent document 4: japanese patent laid-open No. 2000-310706
Patent document 5: japanese patent laid-open publication No. 2009-204895
Disclosure of Invention
The present invention has been made to overcome the above-described situation.
Accordingly, an object of the present invention is to provide a colored cured film excellent in both adhesiveness and solvent resistance, a coloring composition for forming the colored cured film, and a display element having the cured film.
The colored composition is preferably prepared by selecting any one of a high-photosensitivity type and a small-sized mask variation and optionally separating them.
According to the present invention, the above objects and advantages of the present invention are achieved by the following coloring composition:
the coloring composition contains:
(A) a colorant,
(B) A binder resin,
(C) A radically polymerizable compound,
(D) A photo-radical generator,
(E) A compound having a structure in which a group represented by the following formula (E0) is directly bonded to an aromatic ring,
＊－(CRII 2)x－O－RI(E0)
in the formula (E0), the following formula (E0),
RIis a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
RIIeach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
x is 1 or 2, and X is a hydrogen atom,
"＊" represents a bond directly to an aromatic ring ]
The above object and advantages 2 of the present invention are achieved by a colored cured film formed using the above colored composition.
The above object and advantage 3 of the present invention are achieved by a display element having the colored cured film described above.
According to the present invention, a colored cured film excellent in both adhesiveness and solvent resistance, a colored composition for forming the colored cured film, and a display element having the cured film are provided.
By selecting the compound (E), the colored composition can be produced in a manner that allows for separation between a high photosensitivity type and a small mask variation.
Detailed Description
< colorant (A) >
The colorant (a) contained in the coloring composition of the present invention may not be particularly limited in use. The coloring composition of the present invention can be used by appropriately selecting the color, material, and the like of the colorant (a).
As the colorant (a), 1 or more selected from pigments and dyes can be used.
When the coloring composition of the present invention is used to form each color pixel constituting a color filter, it is preferable to use 1 or more selected from organic pigments and organic dyes as the colorant (a) because a pixel having high brightness, contrast, and color purity can be easily obtained. On the other hand, in the case of forming a black matrix (matrix) or a black spacer (spacer) using the coloring composition, it is preferable to use an inorganic pigment as the (A) colorant.
As the pigment, organic pigments and inorganic pigments are available.
Preferred examples of the organic pigment include pigments named as c.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 224, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment blue 15:6, c.i. pigment blue 80, c.i. pigment yellow 83, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 180, c.i. pigment yellow 211, c.i. pigment orange 38, c.i. pigment violet 23, and other pigment indexes (c.i.);
lake pigments, and the like. Examples of the lake pigment include triarylmethane-based lake pigments obtained by subjecting a triarylmethane-based dye to lake formation with a homo-or heteropoly acid as disclosed in, for example, Japanese patent application laid-open publication No. 2011-186043;
xanthene lake pigments obtained by laking xanthene dyes with isopoly acids, heteropoly acids, etc., as disclosed in jp 2010-191304 a and the like; and so on.
Preferable examples of the inorganic pigment include carbon black and titanium black.
The pigment can be used after being purified by, for example, recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or the like, or a combination of these methods;
or the surface of the particle can be modified by resin for use;
it can also be used after the primary particles thereof are pulverized by a salt milling method as disclosed in, for example, Japanese patent application laid-open No. H08-179111.
The pigment may be used together with a dispersant, a dispersion aid, and the like as needed. As the dispersant, for example, a suitable dispersant such as a cationic dispersant, an anionic dispersant, a nonionic dispersant, etc. can be used, but a polymer dispersant or a pigment derivative is preferably used. Examples of the polymer dispersant include acrylic copolymers (acrylic dispersants), polyurethanes (polyurethane dispersants), polyester dispersants, polyethyleneimines, and polyallylamine dispersants.
The above-mentioned polymeric dispersants are commercially available. Specific examples thereof may be as follows:
examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, BYK-LPN 21116 and BYK-LPN 22102 (which are products of Bikk chemical (BYK) Co., Ltd.);
examples of the polyurethane dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (BYK chemical, Inc., mentioned above), Solsperse 76500 (product of Lubomoisten, Japan);
examples of the polyester-based dispersants include Ajisper-PB 821, Ajisper-PB 822, Ajisper-PB 880, and Ajisper-PB 881 (hereinafter, Ajinomoto Fine-Techno Co.);
examples of the above-mentioned polyethyleneimine-based dispersant include Solsperse-24000 (product of Robotun, Japan) and BYK-LPN 21324 (product of Bikk chemical (BYK)).
Examples of the pigment derivative include sulfonic acid derivatives of pigments. Specific examples thereof include copper phthalocyanine sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, sulfonic acid derivatives of quinophthalone, and the like.
The amount of the dispersant used is preferably 60 parts by mass or less, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass, based on 100 parts by mass of the pigment in the colorant (A).
As the dye, an organic dye is preferably used, and examples thereof include xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, and the like. More specifically, organic dyes disclosed in, for example, Japanese patent application laid-open Nos. 2010-32999, 2010-254964, 2011-138094, PCT 2010/123071, 2011-116803, 2011-117995, 2011-133844, 2011-174987 and the like are suitable. Specifically, for example, compounds represented by the following formulae (A-2-1) to (A-2-9) may be mentioned.
[ chemical formula 1 ]
[ chemical formula 2 ]
In the above chemical formula, the compounds represented by (A-2-1) and (A-2-3) to (A-2-5) are xanthene dyes;
the compounds respectively represented by (A-2-2) and (A-2-6) are triarylmethane dyes;
the compounds respectively represented by (A-2-7) and (A-2-8) are cyanine dyes;
the compound represented by (A-2-9) is an anthraquinone dye.
The pigment and dye as the colorant (a) in the coloring composition of the present invention may be used alone in 1 kind, or may be used by mixing any 2 or more kinds. In addition, a pigment and a dye may be mixed for use.
In this field, it is generally considered that a colored cured film formed using a coloring composition containing a dye lacks solvent resistance. However, the colored composition of the present invention can form a colored cured film having excellent solvent resistance even when it contains a dye as the colorant (a). In this case, the dye content in the colorant (a) can be adjusted to 10% by mass or more, further 20% by mass or more, and particularly 30% by mass or more, based on the total amount of the colorant (a), and a colored cured film having excellent solvent resistance can be obtained.
The content ratio of the colorant (a) in the coloring composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, further preferably 50% by mass or less, particularly preferably 45% by mass or less, and particularly preferably 40% by mass or less, based on the total of solid components (components excluding the solvent in the coloring composition, the same applies hereinafter) of the coloring composition. The content of the colorant (a) in the coloring composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass, and particularly preferably 15 to 45% by mass, based on the total solid content of the coloring composition. When the content ratio of the colorant (a) is within the above range, the formed colored cured film has high luminance, excellent color purity and excellent heat resistance when it is a pixel, and has excellent heat resistance and light-shielding property when it is a black matrix or a black spacer.
In addition, from the viewpoint of obtaining a coloring composition having more excellent sensitivity, the content ratio of the colorant (a) in the coloring composition of the present invention is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and particularly preferably 20 to 40% by mass, based on the total solid content of the coloring composition.
On the other hand, from the viewpoint of obtaining a colored composition with less mask variation, the content ratio of the colorant (a) in the colored composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and particularly preferably 15 to 45% by mass, based on the total solid content of the colored composition.
The coloring composition of the present invention can form a colored cured film having excellent solvent resistance and adhesion even when the content ratio of the coloring agent is high, and therefore, can be suitably used for forming green pixels and red pixels which generally tend to have a high content ratio of the coloring agent, and particularly, can be suitably used for forming green pixels.
< adhesive resin (B) >
The binder resin (B) in the coloring composition of the present invention is not particularly limited, but is preferably a resin having an acidic functional group. More preferably, a resin having a carboxyl group or a phenolic hydroxyl group, and particularly preferably a resin having a carboxyl group.
As the binder resin (B) in the present invention, particularly preferred are, for example:
(b1) ethylenically unsaturated monomer having 1 or more carboxyl groups and
(b2) other copolymerizable ethylenically unsaturated monomers
The copolymer of (4) (carboxyl group-containing polymer (1));
a polymer having a carboxyl group and a polymerizable unsaturated bond (carboxyl group-containing polymer (2)), and the like.
Examples of the unsaturated monomer (b1) as a raw material of the carboxyl group-containing polymer (1) include (meth) acrylic acid, maleic anhydride, succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester, ω -carboxy polycaprolactone mono (meth) acrylate, and p-vinylbenzoic acid.
These unsaturated monomers (b1) may be used alone or in combination of 2 or more.
Examples of the unsaturated monomer (b2) include N-substituted maleimide, aromatic vinyl compounds, (meth) acrylic acid esters, vinyl ethers, and macromonomers. Specific examples of these monomers include the following:
examples of the N-substituted maleimide include N-phenylmaleimide and N-cyclohexylmaleimide;
examples of the aromatic vinyl compounds include styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;
examples of the (meth) acrylate include (meth) acrylate, (meth) acrylic acid n-butyl ester, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclo [ 5.2.1.0 ] meth) acrylate2,6Decane-8-yl ester, tricyclo (meth) acrylate [ 5.2.1.0 ]2,6Decen-8-yl ester, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, 3-[ (meth) acryloyloxymethyl ] oxetane, 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane, etc.;
examples of the vinyl ether include cyclohexyl vinyl ether, isobornyl vinyl ether, and tricyclo [ 5.2.1.0 ]2 ,6Decane-8-yl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane, a compound represented by the following formula, etc.;
[ chemical formula 3 ]
Examples of the macromonomer include macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) may be used alone or in combination of 2 or more.
The copolymerization ratio of the unsaturated monomer (b1) in the carboxyl group-containing polymer (1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total of the unsaturated monomer (b1) and the unsaturated monomer (b 2). From the viewpoint of excellent storage stability and alkali developability, a coloring composition containing the carboxyl group-containing polymer (1) obtained by copolymerizing the unsaturated monomer (b1) at the copolymerization ratio described above is preferred.
Specific examples of the carboxyl group-containing polymer (1) are disclosed in, for example, Japanese patent application laid-open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 and 2004-101728.
As the carboxyl group-containing polymer (2), for example, polymers disclosed in Japanese patent laid-open Nos. 5-19467, 6-230212, 7-207211, 9-325494, 11-140144, 2008-181095 and the like can be used.
The binder resin (B) in the colored composition of the present invention preferably has a weight average molecular weight (Mw) of 1,000 to 100,000, more preferably 3,000 to 50,000, in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as an elution solvent. The use of the (B) binder resin having Mw as described above is preferable from the viewpoint of suppressing the occurrence of dried foreign matter at the time of coating as much as possible, forming a patterned cured film having a good shape with high resolution and a high residual film ratio, and further improving the heat resistance, electrical characteristics, solvent resistance, adhesiveness, and the like of the cured film obtained.
(B) The ratio (Mw/Mn) of Mw to the number average molecular weight Mn of the binder resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Here, Mn is a number average molecular weight in terms of polystyrene measured by GPC using tetrahydrofuran as an elution solvent.
The binder resin (B) as described above can be produced by a known method using an appropriate unsaturated monomer or a mixture thereof as a raw material. For example, a binder resin having a suitably controlled structure, Mw/Mn and the like can be produced by the methods disclosed in, for example, Japanese patent application laid-open Nos. 2003-222717, 2006-259680, and 2007/029871.
The binder resin (B) in the coloring composition of the present invention may be used alone or in combination of 2 or more kinds of the above-mentioned polymers.
The content of the binder resin (B) in the coloring composition of the present invention is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass, based on 100 parts by mass of the colorant (a). A colored composition containing the binder resin (B) within the above range is preferable from the viewpoint of excellent storage stability, good alkali developability of the coating film, and further improved solvent resistance, adhesion and chromaticity characteristics of the resulting cured film.
< free radical polymerizable Compound >
The radical polymerizable compound (C) in the colored composition of the present invention is a compound having 2 or more radical polymerizable groups in the molecule. Examples of the radical polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, an oxetane group, and an N-alkoxymethylamino group. The ethylenically unsaturated group is preferably a (meth) acryloyl group.
The radical polymerizable compound (C) in the present invention is preferably selected from compounds having 2 or more (meth) acryloyl groups in the molecule and compounds having 2 or more N-alkoxymethylamino groups in the molecule.
Examples of the compound having 2 or more (meth) acryloyl groups in the molecule include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, alkylene oxide-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate, and polyfunctional (meth) acrylates having a carboxyl group obtained by reacting a hydroxyl group-containing (meth) acrylate with an acid anhydride.
Examples of the aliphatic polyhydric compound include aliphatic polyhydric compounds having a valence of 2 such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, and aliphatic polyhydric compounds having a valence of 3 or more such as glycerol, trimethylolpropane, pentaerythritol and dipentaerythritol.
Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate;
examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
Examples of the acid anhydride include acid anhydrides of dibasic acids and acid dianhydrides of tetrabasic acids, and specific examples of the acid anhydrides include the following:
examples of the acid anhydride of the dibasic acid include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and the like;
examples of the acid dianhydride of the tetrabasic acid include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.
Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [ 0015 ] to [ 0018 ] of Japanese patent laid-open publication No. 11-44955. As the above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate, there may be mentioned, for example
Bisphenol A di (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide,
A tri (meth) acrylate isocyanurate modified with at least 1 kind selected from the group consisting of ethylene oxide and propylene oxide, a trimethylolpropane tri (meth) acrylate modified with at least 1 kind selected from the group consisting of ethylene oxide and propylene oxide,
Pentaerythritol tri (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide,
Pentaerythritol tetra (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide,
Dipentaerythritol penta (meth) acrylate modified with at least 1 selected from the group consisting of ethylene oxide and propylene oxide,
Dipentaerythritol hexa (meth) acrylate modified with at least 1 selected from ethylene oxide and propylene oxide, and the like.
The compound having 2 or more N-alkoxymethylamino groups in the molecule may be, for example, a compound having a melamine structure, a benzoguanamine structure, or a urea structure. Here, the melamine structure means a chemical structure having 1 or more triazine rings as a basic skeleton, and the benzoguanamine structure means a chemical structure having 1 or more phenyl-substituted triazine rings as a basic skeleton, and this concept includes melamine, benzoguanamine, and condensates thereof. Specific examples of the compound having 2 or more N-alkoxymethylamino groups in the molecule include N, N ', N ", N ″ -hexa (alkoxymethyl) melamine, N ' -tetrakis (alkoxymethyl) benzoguanamine, N ' -tetrakis (alkoxymethyl) glycoluril, and the like.
Among the compounds (C) of the radical polymerizable compound of the present invention, preferred compounds are polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydric compound having a valence of 3 or more with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, polyfunctional (meth) acrylates having a carboxyl group, N ', N ", N ″ -hexa (alkoxymethyl) melamine, and N, N' -tetrakis (alkoxymethyl) benzoguanamine. Trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate among polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydric compound having a valence of 3 or more with (meth) acrylic acid, and
among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythrityl triacrylate with succinic anhydride and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable in that the resulting colored cured product has high strength and excellent surface smoothness, and that scumming, film residue, and the like are less likely to occur on the substrate in unexposed portions and on the light-shielding layer.
In the coloring composition of the present invention, (C) the radical polymerizable compound may be used alone or in combination of 2 or more.
The content of the radical polymerizable compound (C) in the coloring composition of the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and particularly preferably 50 to 500 parts by mass, based on 100 parts by mass of the colorant (a).
A colored composition containing (C) the radical polymer compound in the above range is preferable because the developability of the coating film is excellent, the occurrence of defects such as scumming and film residue on the substrate in the unexposed area or on the light-shielding layer can be controlled as much as possible, and the curability of the coating film is excellent.
[ photo radical generating agent (D) ]
The photo radical generator (D) contained in the coloring composition of the present invention is a compound that generates a radical that can be an active species for initiating radical polymerization of the radical polymerizable compound (C) by irradiating light such as visible light, ultraviolet light, salt ultraviolet light, electron beam, or X.
Examples of the photo radical generator (D) include thioxanthone compounds, acetophenone compounds, bisimidazoles compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -diketone compounds, polyquinone compounds, diazo compounds, and imide sulfonate compounds.
In the coloring composition of the present invention, (D) the photo radical generator may be used alone or in combination of 2 or more.
The photo radical generator (D) in the present invention is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, bisimidazoles, triazine compounds, and O-acyloxime compounds, and particularly preferably contains an O-acyloxime compound.
(D) Specific examples of the photo radical generating agent are as follows.
Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone;
examples of the acetophenone compounds include 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one;
examples of the bisimidazoles include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -bisimidazole, 2 '-bis (2, 4-dichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -bisimidazole, 2 '-bis (2,4, 6-trichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -bisimidazole, and the like;
examples of the triazine compounds include 2,4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, triazine compounds having a halomethyl group such as 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine;
examples of the O-acyloxime compounds include 1, 2-octanedione, 1- [ 4- (phenylthio) phenyl ] -2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone, 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone, 1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (O-acetyloxime), and the like. Examples of commercially available O-acyloximes include NCI-831, NCI-930 (see above, the product of ADEKA), DFI-020, and DFI-091 (see above, the product of Daito Chemix).
When the bisimidazole compound is used as the (D) photo radical generator in the present invention, it is preferable to use a hydrogen donor together from the viewpoint of further improving the photosensitivity. Here, the "hydrogen donor" refers to a compound capable of donating a hydrogen atom to a radical generated from the bisimidazole compound by irradiation with light. Examples of such hydrogen donors include thiol hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, and amine hydrogen donors such as 4,4 '-bis (dimethylamino) benzophenone and 4, 4' -bis (diethylamino) benzophenone. These hydrogen donors may be used alone or in combination of 2 or more, and from the viewpoint of greatly improving the photosensitivity, it is preferable to use at least 1 of thiol hydrogen donors and at least 1 of amine hydrogen donors in combination.
On the other hand, in the case where a photo radical generator other than the bisimidazoles compound, preferably at least 1 selected from the group consisting of a thioxanthone compound, an acetophenone compound, a triazine compound and an O-acyloxime compound is used as the (D) photo radical generator in the present invention, a sensitizer may be used together with these photo radical generators. Examples of such a sensitizer include 4,4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminoprophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone, and at least 1 compound selected from these compounds can be used.
The content ratio of the photoradical generator (D) in the coloring composition of the present invention is preferably 0.01 to 120 parts by mass, and more preferably 1 to 100 parts by mass, based on 100 parts by mass of the radical polymerizable compound (C). Setting the content ratio of the photoradical generator (D) within the above range is preferable from the viewpoint that the curability of the colored composition can be improved.
When a bisimidazole compound is used as the (D) photo-radical generator and a hydrogen donor is used together with the bisimidazole compound, the hydrogen donor content is preferably 500 parts by mass or less, more preferably 50 to 300 parts by mass, per 100 parts by mass of the bisimidazole compound.
When a photo-radical generator other than the bisimidazoles is used as the (D) photo-radical generator and a sensitizer is used together with the photo-radical generator, the content of the sensitizer is preferably 300 parts by mass or less, and more preferably 50 to 150 parts by mass, per 100 parts by mass of the photo-radical generator other than the bisimidazoles.
< Compound (E) >
The compound (E) in the present invention has a structure in which a group represented by the formula (E0) is directly bonded to an aromatic ring.
R in the above-mentioned (E0)IExamples of the alkyl group of (2) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. RIPreferably an alkyl group, more preferably a methyl or ethyl group.
RIIMay each independently be a hydrogen atom and as RIThe alkyl group of (a) is preferably a hydrogen atom, as one of the groups listed above.
x is preferably 1.
The compound (E) in the present invention is preferably a compound having 2 or more groups represented by the above formula (E0) in the molecule, and more preferably a compound having 4 or more groups. Particularly preferably having 6 to 10 of the above groups. 2 or more groups represented by the above formula (E0) may be bonded to 1 aromatic ring.
The compound (E) in the present invention is preferably a compound having at least 1 group selected from a 1-valent group represented by the following formula (E0-1) and a 2-valent group represented by the following formula (E0-2).
[ chemical formula 4 ]
[ E0 in the formulae (E0-1) and (E0-2) is a group represented by the above formula (E0),
z independently represents a hydroxyl group or a 1-valent organic group,
"+" indicates a bond;
in the formula (E0-1), a1 is an integer of 1-5, b1 is an integer of 0-4, and a1+ b1 is 1-5; furthermore, it is possible to provide a liquid crystal display device,
(E0-2) wherein a2 is an integer of 1 to 4 and b2 is an integer of 0 to 3, and the relationship of a2+ b2 is 1 to 4. Angle (c)
Preferably, a1 in the formula (E0-1) and a2 in the formula (E0-2) each independently represent 1 or 2, more preferably 2.
A1 in the formula (E0-1) and Z in the formula (E0-2) are a hydroxyl group or a 1-valent organic group. Examples of the organic group include an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, a2, 3-glycidoxy group, and a2, 3-dihydroxypropoxy group. Z is preferably a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkoxy group having 2 to 6 carbon atoms or an acyloxy group having 2 to 4 carbon atoms, from the viewpoint of improving the stability of the obtained colored composition. As specific examples of these groups, as the alkoxy group, there are, for example, methoxy, ethoxy, propoxy, butoxy and the like;
examples of the alkoxyalkoxy group include 1-methoxyethoxy group, 2-methoxyethoxy group, 1-ethoxyethoxy group, 2-ethoxyethoxy group, and 1-butoxyethoxy group;
examples of the acyloxy group include an acetoxy group and the like.
Preferably, b1 in the formula (E0-1) and b2 in the formula (E0-2) each independently represent 0 or 1.
The compound (E) having such a group in the present invention is preferably at least 1 compound selected from the compounds represented by the following formulae (E-1) to (E-5).
[ chemical formula 5 ]
[ chemical formula 6 ]
[ E0 and Z in the formulae (E-1) to (E-5) are synonymous with E0 and Z in the formulae (E0-1) and (E0-2), respectively,
r independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, a phenyl group or a naphthyl group,
a independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -SO-, -SO2－、－CR2- (wherein R is the same as above) or a group represented by the following formula (T-1);
[ chemical formula 7 ]
(in the formula (T-1), Z is synonymous with Z in the formulae (E0-1) and (E0-2), n is an integer of 0 to 4, and "+" represents a bond.)
C1, c2, d1 and d2 in formula (E-1) each independently represent an integer of 0 to 5, and satisfy the conditions that c1+ d1 is 0 to 5 and c2+ d2 is 0 to 5, and at least 1 of c1 and c2 is not 0;
in the formula (E-2), E1 to E3 and f1 to f3 each independently represent an integer of 0 to 5, and at least 1 of E1 to E3 is not 0, provided that E1+ f1 is 0 to 5, E2+ f2 is 0 to 5, and E3+ f3 is 0 to 5;
g1 to g4 and h1 to h4 in formula (E-3) each independently represent an integer of 0 to 5, and satisfy the conditions that g1+ h1 is 0 to 5, g2+ h2 is 0 to 5, g3+ h3 is 0 to 5, and g4+ h4 is 0 to 5, and at least 1 of g1 to g4 is not 0;
in formula (E-4), i1 to i3 and j1 to j3 each independently represent an integer of 0 to 5, i4 and j4 each independently represent an integer of 0 to 4, and satisfy the conditions that i1+ j1 is 0 to 5, i2+ j2 is 0 to 5, i3+ j3 is 0 to 5, and i4+ j4 is 0 to 4, and at least 1 of i1 to i4 is not 0;
in formula (E-5), k1, k2, L1 and L2 each independently represent an integer of 0 to 5, and k3 and L3 each independently represent an integer of 0 to 4, and satisfy the conditions that k1+ L1 is 0 to 5, k2+ L2 is 0 to 5, and k3+ L3 is 0 to 4, and at least 1 of k1 to k3 is not 0;
m is an integer of 1 to 5. Angle (c)
R in the above formulae (E-2) to (E-5) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
A is preferably a single bond, methylene, propane-2, 2-diyl group or a group represented by the above formula (T-1).
C1, c2, E1 to E3, g1 to g4, i1 to i3, and k1 to k3 in the above formulae (E-1) to (E-5) are each preferably 1 or 2, more preferably 2;
i4 is preferably 0;
d1, d2, f1 to f3, h1 to h4, j1 to j3 and L1 to L3 are each preferably 0 or 1, and more preferably 1.
Specific examples of such compounds (E) include the following: examples of the compound (E-1) include compounds represented by the following formulae (E-1-1) to (E-1-3);
examples of the compound (E-2) include compounds represented by the following formulae (E-2-1) and (E-2-2);
examples of the compound (E-3) include compounds represented by the following formula (E-3-1);
examples of the compound (E-4) include compounds represented by the following formulae (E-4-1) to (E-4-8);
examples of the compound (E-5) include compounds represented by the following formula (E-5-1).
[ chemical formula 8 ]
[ chemical formula 9 ]
[ chemical formula 10 ]
[ chemical formula 11 ]
[ in the formula (E-5-1),
m, n, r and s each independently represent an integer of 0 to 5,
p and q each independently represent an integer of 0 to 4,
l is 0 or any natural number representing the number of repeating units,
however, m + n and r + s are respectively in the range of 0 to 5, p + q is in the range of 0 to 4, and at least 1 of m, r and p is not 0. Angle (c)
The amount of the compound (E) used in the coloring composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 1 to 45 parts by mass, and most preferably 3 to 40 parts by mass, based on 100 parts by mass of the binder resin (B).
As described above, the preferred (E) compound in the present invention has both the group represented by (E0) and the group Z. Here, when a compound in which the group Z is a hydroxyl group is used as the compound (E), a colored composition with less mask variation can be obtained. The amount of the compound (E) used in this case is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, and preferably 40 parts by mass or less, more preferably 35 parts by mass or less, particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the binder resin (B). The content of the compound (E) in the coloring composition of the present invention is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and particularly preferably 3 to 30 parts by mass, based on 100 parts by mass of the binder resin (B).
On the other hand, when a compound in which the group Z is a 1-valent organic group is used as the compound (E), a coloring composition having high photosensitivity can be obtained. The amount of the compound (E) used in this case is preferably 1 part by mass or more, more preferably 2 parts by mass or more, particularly preferably 3 parts by mass or more, and preferably 45 parts by mass or less, more preferably 43 parts by mass or less, further preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, relative to 100 parts by mass of the binder resin (B). The content of the compound (E) in the coloring composition of the present invention is preferably 1 to 45 parts by mass, more preferably 2 to 40 parts by mass, even more preferably 3 to 35 parts by mass, and further may be 20 to 45 parts by mass, even more preferably 25 to 43 parts by mass, and particularly 30 to 40 parts by mass, based on 100 parts by mass of the binder resin (B).
< other ingredients >
The coloring composition of the present invention contains the above-mentioned components (a) to (E) as essential components, but may optionally contain other components within a range not impairing the effects of the present invention. As such other components, for example, a filler such as glass or alumina;
high molecular weight compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate);
surfactants such as fluorine-based surfactants and silicone-based surfactants;
adhesion promoters such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane;
antioxidants such as 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, pentaerythritol tetrakis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 3, 9-bis [ 2- [ 3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy ] -1, 1-dimethylethyl ] -2, 4,8, 10-tetraoxaspiro [ 5.5 ] undecane and thiodiethylene bis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ];
ultraviolet absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole and alkoxybenzophenone;
anticoagulants such as sodium polyacrylate;
residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, and 4-amino-1, 2-butanediol;
developability improvers such as mono [ 2- (meth) acryloyloxyethyl ] succinate, mono [ 2- (meth) acryloyloxyethyl ] phthalate and ω -carboxy polycaprolactone mono (meth) acrylate, and the like.
< solvent >
The coloring composition of the present invention contains the above-mentioned components (a) to (E) as essential components, and optionally other components, and is preferably prepared as a liquid composition further containing a solvent.
Here, the solvent is preferably a substance which can disperse or dissolve the above components, does not react with these components, and has appropriate volatility, and can be appropriately selected from solvents having such characteristics.
The solvent contained in the coloring composition of the present invention includes the following: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl 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, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.;
alkyl lactate esters such as methyl lactate and ethyl lactate;
(cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol and cyclohexanol;
ketols such as diacetone alcohol;
(poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;
other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;
ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;
diacetates such as propylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;
alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;
other esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;
aromatic hydrocarbons such as toluene and xylene;
amides or lactams such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; and so on.
Among these solvents, from the viewpoint of solubility, coatability, etc., and dispersibility of the pigment when the solvent is contained, it is preferable to use (poly) alkylene glycol monoalkyl ethers, alkyl lactate esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones, diacetate esters, alkoxycarboxylic acid esters, and other esters, and it is particularly preferable to use propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.
In the coloring composition of the present invention, the solvent may be used alone or in combination of 2 or more.
The most preferred solvent for the coloring composition of the present invention is one containing at least one member selected from the group consisting of (poly) alkylene glycol monoalkyl ethers and (poly) alkylene glycol monoalkyl ether acetates, or
Mixtures of (poly) alkylene glycol monoalkyl ethers and (poly) alkylene glycol monoalkyl ether acetates.
The content of the solvent in the coloring composition of the present invention is not particularly limited, and the solvent is preferably contained in an amount such that the solid content concentration of the coloring composition (the ratio of the total mass of the components other than the solvent in the coloring composition to the total mass of the coloring composition) is 5 to 50% by mass, more preferably 10 to 40% by mass. A coloring composition containing the solvent in the above-mentioned amount is preferable from the viewpoint that the dispersibility of each component contained therein is excellent, and thus the composition is also excellent in stability and also excellent in coatability.
< method for preparing coloring composition >
The coloring composition of the present invention can be prepared by a suitable method. For example, the components (a) to (E) and any other component may be mixed together with a solvent to prepare the composition.
For example, when the colorant (a) in the coloring composition of the present invention contains a pigment, the colorant (a) is preferably mixed and dispersed in a solvent together with a part of the binder resin (B) as appropriate in the presence of a dispersant, for example, by crushing using a bead mill, a roll mill or the like, to form a pigment dispersion, and then the binder resin (B) and the components (C) to (E) and optionally other components are added to the pigment dispersion in the remaining amount, followed by mixing.
< method for Forming colored cured film >
The colored cured film can be formed using the above-described colored composition of the present invention. The concept of the colored cured film of the present invention includes pixels of respective colors, black matrices, black spacers, and the like used in display elements and solid-state imaging elements.
To form a colored cured film using the coloring composition of the present invention, it is preferable to use any of the following methods.
The first method comprises the following steps: applying the coloring composition of the present invention on a substrate to form a coating film, and then irradiating at least a part of the coating film with light, followed by development, preferably further heating (post-baking);
the second method comprises the following steps: the coloring composition of the present invention is applied onto a substrate in a pattern by an ink jet method to form a coating film, and the coating film is optionally irradiated with light, preferably followed by further heating (post-baking).
In any of the above methods, a color filter can be formed by sequentially forming colored cured films to be pixels of each color using a coloring composition of three colors of red, green, and blue, or three colors of cyan, magenta, and yellow. On the other hand, by forming a black colored cured film using a black colored composition, a black matrix or a black spacer can be formed.
Examples of the substrate include substrates made of glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamide-imide, polyimide, and the like. These substrates may be subjected to a suitable pretreatment such as a chemical (e.g., silane coupling agent) treatment, a plasma treatment, an ion plating treatment, a sputtering treatment, a treatment by a vapor phase reaction method, a treatment by a vacuum deposition method, or the like, as necessary.
When the colored composition of the present invention is used for forming pixels of a color filter, a black matrix is preferably formed on a substrate, and the pixel region is preferably divided. The black matrix may be a thin metal (e.g., chromium) film having a predetermined pattern, a colored cured film formed from a colored composition, or the like. The patterned metal thin film can be formed by, for example, photolithography of a metal thin film formed on a substrate by sputtering, vapor deposition, or the like. The pattern-like colored cured film formed from the colored composition can be formed by the same method as that of the present invention using a black colored composition. In the second method using the ink jet method, the black matrix functions as a barrier in addition to the light shielding function, and color mixture of the respective color compositions ejected by the ink jet method does not occur. Therefore, the black matrix in this case preferably has a film thickness of a certain thickness or more, and therefore, the black matrix in this case is preferably a black cured film formed using a black coloring composition.
The substrate used when the colored composition of the present invention is used to form a black matrix is preferably a substrate on which a black matrix for partitioning pixel regions has not been formed.
Further, the substrate used when the coloring composition of the present invention is used to form the black spacer is preferably a substrate on which both a black matrix and pixels for partitioning a pixel region are formed.
In the first method, examples of the method for applying the coloring composition to the substrate include a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), and a bar coating method. Among these methods, spin coating or slot die coating is preferably used.
After the coating is performed by the above-described method or inkjet method, a method of heating (prebaking) the coated coloring composition to remove the solvent is preferably used to form a coating film. The prebaking is preferably performed under a condition of 70 to 110 ℃ and preferably about 1 to 10 minutes, and the prebaking is preferably performed under a reduced pressure. The degree of pressure reduction is preferably set to a limiting pressure (absolute pressure) of 50 to 200 Pa.
The thickness of the coating film is preferably 0.6 to 12 μm, more preferably 1.2 to 10 μm, in terms of the thickness after removal of the solvent.
As a light source used when the formed coating film is irradiated with light, for example, a light sourceLight sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps and the like, argon ion lasers, YAG lasers, XeCl excimer lasers, nitrogen lasers, ultraviolet LEDs and the like. The light to be irradiated is preferably light having a bright line in the range of 190 to 450 nm. The light irradiation amount is preferably 10 to 10,000J/m2More preferably 50 to 5,000J/m2。
The above development is carried out using an alkali developing solution. The unexposed portions of the coating film are removed by development treatment to form a patterned coating film. As the alkali developer, for example, an aqueous solution of sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1, 8-diazabicyclo- [ 5.4.0 ] -7-undecene, 1, 5-diazabicyclo- [ 4.3.0 ] -5-nonene, etc. is preferably used. If necessary, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the aqueous solution in an appropriate range.
As the developing method, for example, a shower developing method, a spray developing method, a dip (coating solution) developing method, or the like can be used. The developing condition is preferably 5 to 300 seconds at normal temperature. The coating film after development is preferably washed with water.
The post-baking may be performed at a temperature of 180 to 280 ℃ for 10 to 60 minutes, for example.
The film thickness of the colored cured film formed as described above is in the following range depending on the application.
Pixel: preferably 0.5 to 5 μm, more preferably 1 to 3 μm
Black matrix: preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm
Black spacer: preferably 0.5 to 10 μm, more preferably 1 to 7 μm
The pixel pattern obtained by forming the pixels of each color as described above can be used as a color filter of a display element by forming a protective film on the pixel pattern, if necessary, and then sequentially forming a transparent conductive film and a spacer.
< display element >
The display element of the present invention has at least one colored cured film selected from the group consisting of the pixel, the color filter, the black matrix, and the black spacer formed as described above. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element may employ a known appropriate liquid crystal mode such as TN (twisted nematic) mode, STN (super twisted nematic) mode, IPS (in-plane switching) mode, VA (vertical alignment) mode, or OCB (optically compensated birefringence).
The color liquid crystal display element may be a transmissive type or a reflective type, and may have a liquid crystal cell of an appropriate structure. As the structure of the liquid crystal cell, for example, the following structures can be cited: a structure in which a driving substrate on which a Thin Film Transistor (TFT) is disposed and an opposing substrate on which a color filter is formed are used in a pair, and a liquid crystal layer is interposed between the pair of substrates;
a structure in which a substrate having both a Thin Film Transistor (TFT) and a color filter and a substrate having an ITO (indium oxide doped with tin) electrode are used in pairs with a liquid crystal layer interposed between the pair of substrates, and the like.
The color liquid crystal display device may further include a backlight unit in addition to the liquid crystal cell. As the light source in the backlight unit, for example, a cold cathode fluorescent tube, a white LED, or the like can be used.
The organic EL display element may have any suitable structure, for example, the structure disclosed in japanese patent laid-open No. 11-307242.
The electronic paper may have any suitable structure, and for example, the structure disclosed in japanese patent application laid-open No. 2007-41169 may be used.
The solid-state imaging element may have any suitable structure, for example, the structure disclosed in japanese patent No. 4480740.
[ example ]
The following describes embodiments of the present invention more specifically by way of examples. However, the present invention is not limited to the following examples. < Synthesis of adhesive resin >
Synthesis example B1
100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. The content of the beaker was heated to 80 ℃ and a mixed solution composed of 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate and 6 parts by mass of 2, 2' -azobis (2, 4-dimethylvaleronitrile) was added dropwise at the same temperature over 1 hour and polymerized for 2 hours while maintaining the temperature. Then, the temperature of the reaction solution was raised to 100 ℃ and the reaction solution was further polymerized for 1 hour while being maintained at the temperature, thereby obtaining a solution containing the binder resin (B-1) (solid content concentration: 33 mass%). The Mw of the resulting binder resin (B-1) was 12,200 and the Mn was 6,500. < preparation of pigment Dispersion >
Modulation example P1
A mixed solution composed of 9.1 parts by mass of c.i. pigment green 58 and 3.9 parts by mass of c.i. pigment yellow 138 as (a) a colorant, 12.5 parts by mass of BYK-LPN 21116 (product of pycng chemical company, solid content concentration 40 mass%) as a solution of a dispersant, 15.2 parts by mass of a solution containing the binder resin (B-1) obtained in the above synthesis example B1 as a part of (B) a binder resin, and 59.3 parts by mass of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion liquid (a-1-1).
Preparation examples P2 to P6
Pigment dispersions (A-1-2) to (A-1-6) were prepared in the same manner as preparation example P1, except that the pigments of the type and amount shown in Table 1 were used as the colorant (A) in preparation example P1.
TABLE 1
| Kinds and amounts (parts by mass) of pigments | Name of pigment Dispersion | |
| Modulation example P1 | G58/Y138＝9.1/3.9 | A-1-1 |
| Modulation example P2 | G58/G7/Y129＝3.9/5.2./3.9 | A-1-2 |
| Modulation example P3 | G7/Y185＝9.1/3.9 | A-1-3 |
| Modulation example P4 | R254/R177＝6.5/6.5 | A-1-4 |
| Modulation example P5 | R254＝13 | A-1-5 |
| Modulation example P6 | B15∶6=13 | A-1-6 |
The abbreviations of the pigments in Table 1 are as follows.
G58: c.i. pigment green 58
Y138: c.i. pigment yellow 138
G7: c.i. pigment green 7
Y129: c.i. pigment yellow 129
Y185: c.i. pigment yellow 185
R254: c.i. pigment red 254
R177: c.i. pigment red 177
B15: 6: C.I. pigment blue 15:6
< Synthesis of dye >
Synthesis example SD1
A compound represented by the above formula (A-2-1) (compound (A-2-1)) was synthesized according to Synthesis example 1 of Japanese patent application laid-open No. 2013-190776.
Synthesis example SD2
The compound represented by the above formula (A-2-2) (compound (A-2-2)) was synthesized according to the method described in the colorant synthesis example 3 of Japanese patent laid-open No. 2012-108469.
< preparation of dye solution >
Preparation example SD1
10 parts by mass of the compound (A-2-1) obtained in Synthesis example SD1 was dissolved in 90 parts by mass of propylene glycol monomethyl ether to prepare a dye solution (A-2-1).
Preparation example SD2
10 parts by mass of the compound (A-2-2) obtained in Synthesis example SD2 was dissolved in 90 parts by mass of propylene glycol monomethyl ether to prepare a dye solution (A-2-2).
Example 1
< preparation of coloring composition >
100 parts by mass of the pigment dispersion (A-1-1) obtained in preparation example P1, 15 parts by mass of the solution containing the binder resin (B-1) as the binder resin (B) obtained in Synthesis example B1, 13 parts by mass of KAYARAD DPHA (trade name, a product of Nippon Chemicals, Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as the radical polymerizable compound (C), 0.7 parts by mass of IRGACURE 369 (trade name, a product of BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) as the photoradical generator (D), 0.6 parts by mass of ADEKA arcLuz NCI-831 (trade name, an O-acyloxime compound, a product of ADEKA), 1.0 part by mass of the compound represented by the formula (E-4-1) as the compound (E), and Megafac F-554 (trade name, a fluorine-based surfactant, DIC corporation) was added to the mixture in an amount of 0.05 parts by mass, and 3-methoxybutyl acetate (MBA) and Propylene Glycol Monomethyl Ether Acetate (PGMEA) were further added to prepare a coloring composition (S-1) containing components carried in the pigment dispersion, the solvent composition being MBA: PGMEA: 15: 85 (parts by mass) and the solid content concentration being 17% by mass.
The colored composition was evaluated by the following procedure.
The evaluation results are shown in Table 5.
< evaluation of coloring composition >
(1) Evaluation of solvent resistance
After the above coloring composition (S-1) was applied onto a glass substrate by spin coating, it was prebaked on a hot plate at 90 ℃ for 100 seconds to form a coating film having a thickness of 2.5. mu.m. The substrate with the coating film was allowed to cool to room temperature, and then exposed to 400J/m through a photomask having a line space pattern with a slit width of 90 μm and a space width of 210 μm2The coating was irradiated with a high-pressure mercury lamp (exposure pitch 300 μm). Then, the substrate with a coating film after the light irradiation was sprayed with a potassium aqueous solution having a concentration of 0.04 mass% as a developing solution at a temperature of 23 ℃ for 60 seconds under conditions of a developing pressure of 110KPa and a flow rate of the developing solution of 1.2 liters/minute, and subjected to shower development. The developed substrate with a coating film was cleaned with ultrapure water, air-dried, and then baked in a clean oven at 230 ℃ for 30 minutes, thereby forming a pixel pattern composed of a line space pattern on the substrate.
The substrate on which the pixel pattern was formed by the above method was immersed in N-methylpyrrolidone at 25 ℃ for 30 minutes, and the shape and film thickness of the pixel pattern before and after immersion were observed by a scanning electron microscope and evaluated according to the following criteria.
Evaluation criteria
The pixel pattern is not defective, and the film thickness after immersion is 95% or more of the film thickness before immersion: solvent resistance "good"
When the pixel pattern is partially defective or the film thickness after immersion is 80% or more but less than 95% of the film thickness before immersion: solvent resistance "poor"
The case where the pixel pattern is partially defective and the film thickness after immersion is less than 80% of the film thickness before immersion: solvent resistance "not"
(2) Evaluation of sensitivity and mask bias
A pixel pattern composed of a line space pattern was formed on the substrate by the same operation as in the above "(1) solvent resistance evaluation".
The pixel pattern obtained above was observed with an optical microscope to check whether or not the pattern edge was defective, and evaluated according to the following criteria.
Evaluation criteria
No defect was found in the pattern: sensitivity "Excellent"
Pattern slight defect condition: sensitivity "good"
Pattern with multiple defects: sensitivity "poor"
Further, the line width of the pixel pattern obtained above was measured, and the value obtained by subtracting the slit width (90 μm) of the photomask from the measured line width was obtained, and the mask bias was evaluated from the value.
The mask deviation can be evaluated approximately according to the following criteria.
Evaluation criteria
Case where the subtracted value is negative: poor curing and significantly poor sensitivity.
The value after subtraction is 0 μm or more and less than 10 μm: small mask variation (Excellent mask variation)
The value after subtraction is 10 μm or more: large mask variation (poor mask variation)
Here, if the photosensitivity of the colored composition is sufficiently high, a pattern (colored cured film) having excellent curability and adhesion to a substrate can be formed, and thus no chipping or peeling is observed in the formed pattern.
On the other hand, if the mask misalignment is small, a pattern having a size reproducing the photomask size is formed.
Therefore, the coloring composition can be suitably used in addition to the selection of the process design to be used, the application of the liquid crystal display element, and the like, as long as the characteristics of either the light sensitivity or the mask misalignment are excellent.
Examples 2 to 4,8 to 10 and 12 to 15
A coloring composition was prepared in the same manner as in example 1 except that the kinds and amounts of the components (a) to (E) in example 1 were changed as shown in table 2, and various evaluations were performed.
The evaluation results are shown in Table 5.
Example 5
85 parts by mass of the dispersion (A-1-5) obtained in preparation example P5 (containing 11 parts by mass of the pigment and 4.2 parts by mass of the binder resin (B-1)) and 20 parts by mass of the dye solution (A-2-1) obtained in preparation example SD1 (containing 2 parts by mass of the dye), 31 parts by mass of the solution of the binder resin (B-1) obtained in preparation example B1 as the binder resin (B-1) (corresponding to 10.2 parts by mass in terms of the binder (B-1) resin), 19 parts by mass of KAYARAD DPHA (trade name, a product of Nippon Chemicals, Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as the radical polymerizable compound (C), 1.0 part by mass of 2-hexyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 831 (product of ADCaCuK) as the photo radical generator (D), o-acyloxime compound (product of ADEKA corporation) 0.9 parts by mass, 1.5 parts by mass of the compound represented by the formula (E-4-1) as the compound (E) and 0.05 parts by mass of Megafac F-554 (product name, DIC corporation) as the fluorine-based surfactant were mixed, and MBA, PGMEA and Propylene Glycol Monomethyl Ether (PGME) were added to prepare a coloring composition having a solvent composition of MBA/PGMEA/PGME of 15: 75: 10 (parts by mass) and a solid content of 17% by mass, which contained the components taken in the pigment dispersion.
Various evaluations were made using the coloring composition in the same manner as in example 1.
The evaluation results are shown in Table 5.
Example 6
A coloring composition was prepared in the same manner as in example 5 except that the kind and amount of the component (a) in example 5 were changed to those shown in table 2, and various evaluations were performed.
The evaluation results are shown in Table 5.
Example 7
130 parts by mass (containing 13 parts by mass of the dye) of the dye solution (A-2-2) obtained in preparation example SD2, 62 parts by mass (equivalent to 20.5 parts by mass in terms of the binder resin (B-1)) of the binder resin (B-1) obtained in preparation example B1, KAYARADDPHA (product name, product of Nippon Chemicals Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as the radical polymerizable compound (C), 27 parts by mass of IRGACURE 369 (product name, product of BASF Co., 2-hexyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) and 2.5 parts by mass of ADEKA arc Luz NCI-831 (product name, O-acyloxime compound, product of ADEKA Co., Ltd.) as the photo-radical generator (D), 2.2 parts by mass of the dye solution (A-2-2) of the dye solution (containing 13 parts by mass), and 2.5 parts by mass of the adhesive resin (B-1) obtained in preparation example B35, 2.0 parts by mass of a compound represented by the formula (E-4-1) below as the compound (E) and 0.05 part by mass of Megafac F-554 (trade name, product of DIC Co., Ltd.) as the fluorine-based surfactant were added to the pigment dispersion, and a coloring composition containing components carried in the pigment dispersion and having a solvent composition of MBA: PGMEA: PGME: 15: 40: 45 (parts by mass) and a solid content concentration of 17% by mass was prepared.
Various evaluations were made using the coloring composition in the same manner as in example 1.
The evaluation results are shown in Table 5.
Example 11
A coloring composition was prepared and evaluated in the same manner as in example 7, except that the kind and amount of the component (E) in example 7 were changed to those shown in table 2.
The evaluation results are shown in Table 5.
Examples 16, 17 and 20 to 24 and comparative examples 1 and 4
A coloring composition was prepared in the same manner as in example 1 except that the kinds and amounts of the components (a) to (E) in example 1 were changed as shown in table 3, and various evaluations were performed.
The evaluation results are shown in Table 6.
Examples 18 and 25 and comparative examples 2 and 5
A coloring composition was prepared and evaluated in the same manner as in example 5, except that the kinds and amounts of the components (a) to (E) in example 5 were changed as shown in table 3.
The evaluation results are shown in Table 6.
Example 19 and comparative examples 3 and 6
A coloring composition was prepared and evaluated in the same manner as in example 7, except that the kinds and amounts of the components (a) to (E) in example 7 were changed as shown in table 3.
The evaluation results are shown in Table 6.
Examples 26, 27, 33 and 34 and comparative examples 7, 8, 11 and 12
Coloring compositions were prepared and evaluated in the same manner as in example 1, except that the kinds and amounts of the components (a) to (E) in example 1 were changed as shown in table 4.
The evaluation results are shown in Table 7.
Examples 30 to 32, 35 and 36 and comparative examples 10, 13 and 14
A coloring composition was prepared and evaluated in the same manner as in example 5, except that the kinds and amounts of the components (a) to (E) in example 5 were changed as shown in table 4.
The evaluation results are shown in Table 7.
Examples 28 and 29 and comparative example 9
A coloring composition was prepared and evaluated in the same manner as in example 7, except that the kinds and amounts of the components (a) to (E) in example 7 were changed as shown in table 4.
The evaluation results are shown in Table 7.
TABLE 2
TABLE 3
TABLE 4
The meanings of the components in tables 2 to 4 are as follows.
[ (C) radically polymerizable Compound ]
C-1: KAYARAD DPHA (trade name, product of Nippon Chemicals Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
[ (D) photoradical generators ]
D-1: IRGACURE 369 (trade name, BASF corporation, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1)
D-2: ADEKA arc Luz NCI-831 (trade name, O-acyloxime compound, product of ADEKA Co.)
[ (E) Compound ]
E-1-1: the compound represented by the above formula (E-1-1)
E-2-1: a compound represented by the above formula (E-2-1)
E-2-2: a compound represented by the above formula (E-2-2)
E-3-1: a compound represented by the above formula (E-3-1)
E-4-1: a compound represented by the above formula (E-4-1)
E-4-2: a compound represented by the above formula (E-4-2)
E-4-3: a compound represented by the above formula (E-4-3)
E-4-4: a compound represented by the above formula (E-4-4)
E-4-5: a compound represented by the above formula (E-4-5)
E-5-1: the compound represented by the above formula (E-5-1)
[ other Compounds ]
R-1: a compound represented by the following formula (R-1)
[ chemical formula 12 ]
The compounds represented by the above formula (R-1) used in comparative examples 1 to 3 do not belong to the compound (E) specified in the present invention, but are shown in Table 3 in the column of the compound (E) for convenience.
TABLE 5
TABLE 6
TABLE 7
Claims (17)
1. A negative-type coloring composition comprising:
(A) a colorant,
(B) A binder resin,
(C) A radically polymerizable compound,
(D) Photo radical generator, and
(E) at least one compound selected from the group consisting of compounds represented by the following formulae (E-1) to (E-3) and (E-5),
[ chemical formula 1 ]
[ chemical formula 2 ]
In the formulae (E-1) to (E-3) and (E-5),
e0 are each independently a group represented by the following formula (E0):
＊－(CRII 2)x－O－RI(E0)
in the case of the formula (E0),
RIis a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
RIIeach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
x is 1 or 2, and the compound is,
"＊" represents a bond directly to an aromatic ring;
z independently represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms or an acyloxy group having 2 to 6 carbon atoms,
r independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
a independently represents a single bond or-CR2-, formula-CR2In which R is synonymous with the aforementioned,
c1, c2, d1 and d2 each independently represent an integer of 0 to 5, and satisfy the conditions that c1+ d1 is 0 to 5 and c2+ d2 is 0 to 5, and at least 1 of c1 and c2 is not 0;
e 1-e 3 and f 1-f 3 each independently represent an integer of 0-5, and satisfy the conditions that e1+ f1 is 0-5, e2+ f2 is 0-5, and e3+ f3 is 0-5, and at least 1 of e 1-e 3 is not 0;
g 1-g 4 and h 1-h 4 each independently represent an integer of 0-5, and satisfy the conditions that g1+ h1 is 0-5, g2+ h2 is 0-5, g3+ h3 is 0-5, and g4+ h4 is 0-5, and at least 1 of g 1-g 4 is not 0;
k1, k2, L1 and L2 each independently represent an integer of 0 to 5,
k3 and L3 each independently represent an integer of 0 to 4, and satisfy the conditions that k1+ L1 is 0 to 5, k2+ L2 is 0 to 5, and k3+ L3 is 0 to 4, and at least 1 of k1 to k3 is not 0;
m is an integer of 1 to 5.
2. The negative-type coloring composition according to claim 1, wherein the content ratio of the compound represented by the formulae (E-1) to (E-3) and (E-5) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (B).
3. The negative-type coloring composition according to claim 1, wherein d1, d2, f1 to f3, h1 to h4, and L1 to L3 are each 0 or 1.
4. A negative-type coloring composition comprising:
(A) a colorant,
(B) A binder resin,
(C) A radically polymerizable compound,
(D) Photo radical generator, and
(E) at least one compound selected from the group consisting of the compounds represented by the following formulae (E-1) to (E-5),
[ chemical formula 3 ]
[ chemical formula 4 ]
In the formulae (E-1) to (E-5),
e0 are each independently a group represented by the following formula (E0):
＊－(CRII 2)x－O－RI(E0)
in the case of the formula (E0),
RIis a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
RIIeach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
x is 1 or 2, and the compound is,
"＊" represents a bond directly to an aromatic ring;
z independently represents an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms or an acyloxy group having 2 to 6 carbon atoms,
r independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
a independently represents a single bond or-CR2-, formula-CR2In which R is synonymous with the aforementioned,
c1, c2, d1 and d2 each independently represent an integer of 0 to 5, and satisfy the conditions that c1+ d1 is 0 to 5 and c2+ d2 is 0 to 5, and at least 1 of c1 and c2 is not 0;
e 1-e 3 and f 1-f 3 each independently represent an integer of 0-5, and satisfy the conditions that e1+ f1 is 0-5, e2+ f2 is 0-5, and e3+ f3 is 0-5, and at least 1 of e 1-e 3 is not 0;
g 1-g 4 and h 1-h 4 each independently represent an integer of 0-5, and satisfy the conditions that g1+ h1 is 0-5, g2+ h2 is 0-5, g3+ h3 is 0-5, and g4+ h4 is 0-5, and at least 1 of g 1-g 4 is not 0;
i 1-i 3 and j 1-j 3 independently represent an integer of 0-5,
i4 and j4 each independently represent an integer of 0 to 4, and satisfy the conditions that i1+ j1 is 0 to 5, i2+ j2 is 0 to 5, i3+ j3 is 0 to 5, and i4+ j4 is 0 to 4, and at least 1 of i1 to i4 is not 0;
k1, k2, L1 and L2 each independently represent an integer of 0 to 5,
k3 and L3 each independently represent an integer of 0 to 4, and satisfy the conditions that k1+ L1 is 0 to 5, k2+ L2 is 0 to 5, and k3+ L3 is 0 to 4, and at least 1 of k1 to k3 is not 0;
m is an integer of 1 to 5.
5. The negative-type coloring composition according to claim 4, wherein the content ratio of the compound represented by the formulae (E-1) to (E-5) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (B).
6. The negative-type coloring composition according to any one of claims 1 to 5, wherein the (D) photo-radical generator contains an O-acyloxime compound.
7. A negative-type coloring composition comprising:
(A) a colorant,
(B) A binder resin,
(C) A radically polymerizable compound,
(D) O-acyloximes and
(E) a compound represented by the following formula (E-4),
[ chemical formula 5 ]
In the formula (E-4),
e0 are each independently a group represented by the following formula (E0):
＊－(CRII 2)x－O－RI(E0)
in the case of the formula (E0),
RIis a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
RIIeach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
x is 1 or 2, and the compound is,
"＊" represents a bond directly to an aromatic ring;
z independently represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms or an acyloxy group having 2 to 6 carbon atoms,
r independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
i1 to i3 each independently represent an integer of 0 to 5, j1 to j3 each represent 0 or 1,
the i4 and the j4 each independently represent an integer of 0 to 4, and satisfy the conditions that i1+ j1 is 0 to 5, i2+ j2 is 0 to 5, i3+ j3 is 0 to 5, and i4+ j4 is 0 to 4, and at least 1 of i1 to i4 is not 0.
8. The negative-type coloring composition according to claim 7, wherein j1 to j3 are each 0.
9. A negative-type coloring composition according to claim 7, wherein said compound represented by formula (E-4) is a compound represented by the following formula (E-4-3), (E-4-5), (E-4-6), (E-4-7) or (E-4-8),
10. the negative-type coloring composition according to claim 7, wherein j1 to j3 each represent 1.
11. A negative-type coloring composition according to claim 7, wherein said compound represented by formula (E-4) is a compound represented by the following formula (E-4-1) or (E-4-2),
12. the negative-type coloring composition according to claim 7, wherein the content ratio of the compound represented by the formula (E-4) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (B).
13. The negative-type coloring composition according to any one of claims 1 to 5 and 7 to 12, wherein the content of the (a) colorant is 15 to 45% by mass based on the total solid content of the coloring composition.
14. The negative-type coloring composition according to any one of claims 1 to 5 and 7 to 12, wherein the (a) colorant contains a dye.
15. A colored cured film formed using the negative-type colored composition according to any one of claims 1 to 14.
16. The colored cured film according to claim 15, which is a pixel, a black matrix, or a black spacer.
17. A display element characterized by having the colored cured film according to claim 15 or 16.
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| JP6607054B2 (en) * | 2016-01-20 | 2019-11-20 | 三菱ケミカル株式会社 | Photosensitive resin composition, cured product, black matrix, and image display device |
| KR102247840B1 (en) | 2016-03-18 | 2021-05-03 | 제이에스알 가부시끼가이샤 | Substrate for display device, manufacturing method of the substrate for display device, and display device |
| KR20230136739A (en) * | 2021-01-28 | 2023-09-26 | 도레이 카부시키가이샤 | Colored resin composition, colored film, decorative substrate |
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2014
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- 2014-12-11 TW TW103143197A patent/TWI665514B/en active
- 2014-12-12 KR KR1020140178999A patent/KR102435805B1/en active IP Right Grant
- 2014-12-16 CN CN201410781873.0A patent/CN104714367B/en active Active
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- 2021-05-11 JP JP2021080144A patent/JP7136268B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI665514B (en) | 2019-07-11 |
| JP7136268B2 (en) | 2022-09-13 |
| JP2020126265A (en) | 2020-08-20 |
| KR102435805B1 (en) | 2022-08-25 |
| CN104714367A (en) | 2015-06-17 |
| JP6911971B2 (en) | 2021-07-28 |
| CN111176071A (en) | 2020-05-19 |
| JP2015135476A (en) | 2015-07-27 |
| JP2024109711A (en) | 2024-08-14 |
| JP6699717B2 (en) | 2020-05-27 |
| JP6520091B2 (en) | 2019-05-29 |
| JP2021157181A (en) | 2021-10-07 |
| KR20150070017A (en) | 2015-06-24 |
| JP2022141747A (en) | 2022-09-29 |
| JP2019095797A (en) | 2019-06-20 |
| TW201530258A (en) | 2015-08-01 |
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