CN110618583A - Colored resin composition, color filter, and image display device - Google Patents

Colored resin composition, color filter, and image display device Download PDF

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Publication number
CN110618583A
CN110618583A CN201910879050.4A CN201910879050A CN110618583A CN 110618583 A CN110618583 A CN 110618583A CN 201910879050 A CN201910879050 A CN 201910879050A CN 110618583 A CN110618583 A CN 110618583A
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mass
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meth
pigment
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CN110618583B (en
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大村直也
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Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0069—Non aqueous dispersions of pigments containing only a solvent and a dispersing agent
    • C09B67/007—Non aqueous dispersions of phthalocyanines containing only a solvent and a dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/002—Pigment pastes, e.g. for mixing in paints in organic medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Electroluminescent Light Sources (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention provides a colored resin composition which has high coloring power and high solubility of a dry film in a solvent and can inhibit the generation of attached foreign matters, a color filter and an image display device using the colored resin composition, and a pigment dispersion liquid used in the colored resin composition. The colored resin composition of the present invention contains: (A) the pigment composition comprises a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator, wherein the pigment (A) comprises a zinc halide phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more, and the solvent (C) comprises a high-boiling solvent having a boiling point of 150 ℃ or more at 1013.25 hPa.

Description

Colored resin composition, color filter, and image display device
The present application is a divisional application of the application having a filing date of 2016, 24/3, an application number of 201680016741.6, and an invention name of "colored resin composition, color filter, and image display device".
Technical Field
The invention relates to a colored resin composition, a color filter and an image display device. More particularly, the present invention relates to a colored resin composition containing a specific zinc halide phthalocyanine pigment and a specific high boiling point solvent, a color filter having pixels produced using the colored resin composition, and an image display device having the color filter.
Background
Conventionally, as a method for manufacturing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known. Among them, the pigment dispersion method having well-balanced excellent characteristics is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, accuracy, and the like.
In recent years, color filters are required to have higher transmittance, higher brightness, higher contrast, and higher color gamut. As the color material for determining the color of the color filter, pigments are generally used from the viewpoint of heat resistance, light resistance, and the like, and among them, it is preferable to use a color material having a specific transmission absorption spectrum matching the spectrum of the phosphor of the backlight in the visible light wavelength range. For example, as a green pixel formation use, a combination of a copper halide phthalocyanine green pigment and various yellow pigments has been used.
As for the enhancement of the brightness of green pixels, for example, novel zinc halide phthalocyanine green pigments having a specific hue as described in patent documents 1 to 3 have been proposed, and the enhancement of the brightness has been achieved as compared with conventional copper halide phthalocyanine green pigments. Patent documents 1 to 3 describe an example in which a zinc halide phthalocyanine pigment is combined with a photopolymerization initiator such as bisimidazole or α -aminoalkylbenzophenone.
In recent years, it has been found that a coloring composition containing c.i. pigment green 58 as a green pigment of zinc phthalocyanine halide and propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, etc. as a solvent can improve aggregated foreign matter and surface roughness on a coated substrate as described in patent document 4.
Further, as described in patent document 5, it has been found that the use of a zinc halide phthalocyanine green pigment in combination with a photopolymerization initiator containing a specific oxime ester compound can suppress the generation of foreign substances during the production and storage of the colored resin composition, and also can suppress the generation of precipitates when the colored resin composition is brought into contact with N-methylpyrrolidone. Patent documents 6 to 11 also describe an example in which a zinc halide phthalocyanine green pigment is combined with a photopolymerization initiator containing an oxime ester compound.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-70342
Patent document 2: japanese patent laid-open publication No. 2004-70343
Patent document 3: japanese patent laid-open publication No. 2009-52010
Patent document 4: japanese patent laid-open publication No. 2011-028219
Patent document 5: japanese patent laid-open publication No. 2009-271502
Patent document 6: japanese patent laid-open No. 2010-84119
Patent document 7: japanese patent application laid-open No. 2010-97172
Patent document 8: japanese patent laid-open publication No. 2011-99974
Patent document 9: japanese patent laid-open publication No. 2011-145668
Patent document 10: japanese patent laid-open No. 2012-53278
Patent document 11: japanese patent laid-open No. 2012-172003
Disclosure of Invention
Problems to be solved by the invention
The present inventors have studied on a colored resin composition containing c.i. pigment green 58 (hereinafter, simply referred to as "G58") as a zinc halide phthalocyanine pigment described in patent documents 1 to 11, and have found that it is necessary to increase the thickness of a coating film in order to reduce the coloring power and achieve a certain chroma.
Accordingly, as a result of intensive studies to obtain a colored resin composition which can achieve a certain chroma while increasing the coloring power by reducing the thickness of the coating film, it has been found that the above object can be achieved by using a specific zinc halide phthalocyanine pigment. On the other hand, as a result of studies on a colored resin composition containing the pigment, it was found that a dried film formed using the composition had low solubility in a solvent, and therefore, there was a new problem that foreign matters adhering to the tip of a dispenser nozzle in a dry manner were adhered as foreign matters on the surface of the coating film when the composition was coated by a die coating method, which was not present in the case of G58.
The present invention has been made in view of the above problems, and an object thereof is to provide a colored resin composition having a high coloring power and a high solubility of a dried film in a solvent, and capable of suppressing the occurrence of adhering foreign matters, a color filter having pixels formed using the colored resin composition, an image display device having the color filter, and a pigment dispersion liquid used in the colored resin composition.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a specific zinc halide phthalocyanine green pigment and a specific high boiling point solvent, and have completed the present invention. That is, the gist of the present invention is as follows.
[1] A colored resin composition comprising: (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator,
the pigment (A) contains a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more,
the (C) solvent contains a high-boiling solvent having a boiling point of 150 ℃ or higher at 1013.25 hPa.
[2] The colored resin composition according to [1] above, wherein the solvent (C) further comprises a low boiling point solvent having a boiling point of less than 150 ℃ at 1013.25 hPa.
[3] The colored resin composition according to [1] or [2], wherein the content ratio of the (C) solvent to the colored resin composition is 50% by mass or more.
[4] The colored resin composition according to any one of the above [1] to [3], wherein the content ratio of the high-boiling solvent to the (C) solvent is 0.5% by mass or more.
[5] The colored resin composition according to any one of the above [1] to [4], wherein the vapor pressure of the high-boiling solvent at 20 ℃ is 400Pa or less.
[6] The colored resin composition according to any one of the above [1] to [5], wherein the dispersant (B) comprises a block copolymer having a functional group containing a nitrogen atom.
[7] The colored resin composition according to any one of the above [1] to [6], wherein the photopolymerization initiator (E) comprises an oxime ester compound.
[8] A color filter having a pixel produced using the colored resin composition according to any one of [1] to [7 ].
[9] An image display device having the color filter according to [8 ].
[10] A pigment dispersion comprising: (A) a pigment, (B) a dispersant, and (C) a solvent, wherein,
the pigment (A) contains a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more,
the (C) solvent contains a high-boiling solvent having a boiling point of 150 ℃ or higher at 1013.25 hPa.
[11] The pigment dispersion liquid according to [10], wherein the solvent (C) further comprises a low-boiling solvent having a boiling point of less than 150 ℃ at 1013.25 hPa.
[12] The pigment dispersion liquid according to [10] or [11], wherein a content ratio of the (C) solvent to the pigment dispersion liquid is 50% by mass or more.
[13] The pigment dispersion liquid according to any one of [10] to [12], wherein a content ratio of the high-boiling solvent to the (C) solvent is 1% by mass or more.
[14] The pigment dispersion liquid according to any one of the above [10] to [13], wherein the vapor pressure of the high-boiling solvent at 20 ℃ is 400Pa or less.
[15] The pigment dispersion liquid according to any one of the above [10] to [14], wherein the dispersant (B) comprises a block copolymer having a functional group containing a nitrogen atom.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a colored resin composition having a high coloring power and a high solubility of a dried film in a solvent and capable of suppressing the generation of foreign matter adhering thereto, a color filter having a pixel formed using the colored resin composition, an image display device having the color filter, and a pigment dispersion liquid used in the colored resin composition can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element having a color filter of the present invention.
FIG. 2 is a mass spectrum of green pigment A.
FIG. 3 is a mass spectrum of green pigment B.
FIG. 4 is a measurement profile of the film surface evaluation of example 8.
Fig. 5 is a measurement profile of the film surface evaluation of comparative example 2.
Fig. 6 is a measurement profile of the film surface evaluation of comparative example 4.
Fig. 7 is a measurement profile of the film surface evaluation of comparative example 3.
Description of the symbols
100 organic EL element
10 transparent support substrate
20 pixels
30 organic protective layer
40 inorganic oxide film
50 transparent anode
Detailed Description
The present invention will be described in detail with reference to the constituent elements thereof, but the following description is only an example of the embodiment of the present invention, and the present invention is not limited to these.
In addition, "(meth) acryloyl group", "meth (acrylate)" and the like mean "acryloyl group and/or methacryloyl group", "acrylate ester and/or methacrylate ester" and the like, for example, "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid". The "total solid content" indicates all components contained in the pigment dispersion liquid or the colored resin composition except for a solvent component described later.
In the present invention, "weight average molecular weight" means a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) and converted to polystyrene.
In the present invention, unless otherwise specified, "amine number" represents an amine number in terms of an effective solid content, and is a value represented by a KOH mass corresponding to an amount of the base per 1g of the solid content of the dispersant.
In the present specification, all percentages and parts by mass have the same meaning as percentages and parts by weight.
[1] Colored resin composition and constituent of pigment dispersion
The respective constituent components of the colored resin composition and the pigment dispersion liquid of the present invention are explained below. The colored resin composition of the present invention comprises (a) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator as essential components, and if necessary, other additives than the above components may be added. The pigment dispersion liquid of the present invention contains (a) a pigment, (B) a dispersant and (C) a solvent as essential components, and if necessary, other additives than the above components may be added.
In the colored resin composition according to embodiment 1 of the present invention, (a) the pigment comprises a zinc halide phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more, and (C) the solvent comprises a high boiling point solvent having a boiling point of 150 ℃ or more at 1013.25 hPa. In the pigment dispersion liquid according to embodiment 2, (a) the pigment includes a zinc halide phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more, and (C) the solvent includes a high boiling point solvent having a boiling point of 150 ℃ or more at 1013.25 hPa.
On the other hand, in the colored resin composition according to embodiment 3 of the present invention, (a) the pigment comprises a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more, and (E) the photopolymerization initiator comprises an oxime ester compound.
The respective constituent components are explained below. Hereinafter, unless otherwise specified, the 1 st to 3 rd embodiments will be described in combination.
[1-1] (A) pigment
The pigment (a) used in the colored resin composition and the pigment dispersion liquid of the present invention includes a zinc halide phthalocyanine pigment (hereinafter, may be referred to as "green pigment a"). The average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more.
Thus, it is considered that the inclusion of the green pigment a as the (a) pigment can achieve both high coloring and high brightness. The detailed mechanism is not clear, but is presumed as follows: the change in the transmission spectrum due to the large amount of hydrogen atoms contained makes the half-value width of the peak narrow, and the transmitted red and blue light can be effectively blocked, thereby achieving high coloring and high brightness.
A general zinc phthalocyanine has 16 hydrogen atoms in one molecule, and a substance obtained by substituting a part of these hydrogen atoms with a halogen atom is a halogenated zinc phthalocyanine pigment used in the present invention. In particular, zinc bromide chloride phthalocyanine pigments are preferable from the viewpoint of high coloring and high brightness.
The method for determining the average number of hydrogen atoms in the molecule of the pigment 1 is not particularly limited, and a method of calculating the average number of halogen atoms by using an X-ray fluorescence analysis basic parameter method (FP method), a method of measuring by Laser Desorption/Ionization (LDI) -Mass Spectrometry (Mass Spectrometry, MS), and the like are exemplified, and the FP method is preferable from the viewpoint of simplicity and accuracy.
In the method of calculation using the FP method, first, the average number of halogen atoms is measured by the FP method, and since 16 sites are occupied by halogen atoms and hydrogen atoms in the halogenated zinc phthalocyanine, the average number of hydrogen atoms can be obtained by calculating the remaining sites not occupied by halogen atoms. The measurement and calculation are preferably performed by using the apparatus and conditions used in the examples. Specifically, the average number of halogen atoms corresponding to1 zinc atom was determined from the mass ratio of zinc atoms to halogen atoms measured by the FP method, and the average number of halogen atoms was subtracted from 16 to obtain the average number of hydrogen atoms.
On the other hand, in the method of measurement by the LDI-MS method, the intensity with respect to the molecular weight (m/z value) is measured by the LDI-MS method. In general, in the green pigment a, a mixture of molecules having different numbers of hydrogen atoms, chlorine atoms, and bromine atoms is formed, the mixture is measured by the above-described method to obtain the intensity of each molecule, the numbers of hydrogen atoms, chlorine atoms, and bromine atoms contained in each molecule are calculated from the intensity, and the average value of the numbers of hydrogen atoms, chlorine atoms, and bromine atoms contained in one molecule can be calculated by averaging the numbers. The measurement and calculation are preferably performed by using the apparatus and conditions used in the examples.
In detail, zinc bromide chloride phthalocyanine molecules (H) corresponding to the respective peaks are obtained based on the molecular weights of the main peaks in the mass spectrum16-x-yZnC32N8BrxCly) The average number of atoms in the sample is obtained by calculating the average value of a plurality of peaks (molecules) having a peak intensity of a certain value or more.
The average number of hydrogen atoms contained in one molecule of the green pigment a is usually 2 or more, preferably 3 or more, more preferably 4 or more, and further preferably 5 or more, and is preferably 16 or less, more preferably 14 or less, further preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, stability of the dispersion tends to be improved.
The average number of chlorine atoms contained in one molecule of the green pigment a is preferably 0.5 or more, more preferably 1 or more, and even more preferably 1.5 or more, and is preferably 14 or less, more preferably 13 or less, and even more preferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high luminance tends to be obtained.
The average number of bromine atoms contained in one molecule of the green pigment a is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, and is preferably 14 or less, more preferably 13 or less, and further preferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, high luminance tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high coloring tends to be obtained.
The ratio of the average number of chlorine atoms contained in one molecule of the green pigment a to the average number of bromine atoms contained in one molecule is preferably 0.1 or more, more preferably 0.15 or more, and further preferably 0.2 or more, and is preferably 7 or less, preferably 3 or less, more preferably 1 or less, and particularly preferably 0.5 or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high luminance tends to be obtained.
On the other hand, the average number of hydrogen atoms contained in one molecule of the green pigment a calculated by the FP method is usually 2 or more, preferably 3 or more, more preferably 3.5 or more, further preferably 4.0 or more, further preferably 4.2 or more, particularly preferably 4.5 or more, and preferably 12 or less, more preferably 10 or less, further preferably 8 or less, further preferably 6 or less, particularly preferably 5.5 or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, stability of the dispersion tends to be improved.
The average number of chlorine atoms contained in one molecule of the green pigment a as measured by the FP method is preferably 0.5 or more, more preferably 1 or more, and still more preferably 1.5 or more, and is preferably 14 or less, more preferably 12 or less, still more preferably 10 or less, still more preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high luminance tends to be obtained.
The average number of bromine atoms contained in one molecule of the green pigment a as measured by the FP method is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, further preferably 6 or more, particularly preferably 7 or more, and most preferably 8 or more, and is preferably 14 or less, more preferably 13 or less, further preferably 12 or less, further preferably 11 or less, and particularly preferably 10 or less. When the lower limit value is not less than the above-mentioned lower limit value, high luminance tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high coloring tends to be obtained.
The ratio of the average number of chlorine atoms contained in one molecule to the average number of bromine atoms contained in one molecule of the green pigment a measured by the FP method is preferably 0.1 or more, more preferably 0.15 or more, further preferably 0.2 or more, and is preferably 7 or less, more preferably 3 or less, further preferably 1 or less, and particularly preferably 0.5 or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high luminance tends to be obtained.
The green pigment a preferably contains 3.5% by mass or more, more preferably 4.0% by mass or more, further preferably 4.3% by mass or more, and particularly preferably 4.5% by mass or more of chlorine atoms, and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 6% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, high coloring tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high luminance tends to be obtained.
The content of chlorine atoms and bromine atoms contained in the green pigment a can be measured by combustion ion chromatography, in which the pigment is dissolved in ethyl benzoate, and then the resultant is combusted in a combustion apparatus, and the combustion gas is absorbed in a hydrogen peroxide absorbing solution, and then ions in the absorbing solution are measured.
The content of bromine atoms in the green pigment a measured by the above analytical method is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and particularly preferably 50% by mass or more, and the content of bromine atoms is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 55% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, high luminance tends to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, high coloring tends to be obtained.
Such zinc phthalocyanine bromide chloride pigment can be produced by a known production method disclosed in Japanese patent application laid-open No. 50-130816 or the like. Examples thereof include a method of synthesizing a pigment by using phthalic acid or phthalonitrile obtained by substituting a part or all of hydrogen atoms of an aromatic ring with halogen atoms such as bromine and chlorine as a starting material. In this case, a catalyst such as ammonium molybdate may be used as necessary.
Another method is a method of brominating zinc phthalocyanine by bromine gas in a molten material of about 110 to 170 ℃ formed of a mixture of aluminum chloride, sodium bromide, etc. In this method, the ratio of each zinc phthalocyanine bromide having a different bromine content is arbitrarily controlled by adjusting the ratio of chloride to bromide in the molten salt, or by changing the amount of chlorine introduced or the reaction time.
After the reaction is completed, when the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid, the produced zinc phthalocyanine bromide precipitates. Then, post-treatments such as filtration, washing, drying, etc. are performed to obtain zinc bromide phthalocyanine.
The zinc chloride bromide phthalocyanine pigment thus obtained is subjected to dry milling in a mill such as an attritor, a ball mill, a vibration mill, or a vibration ball mill as necessary, and then is subjected to pigmenting by a solvent salt milling (solvent salt milling) method, a solvent boiling method (solvent decorating) method, or the like, whereby a zinc chloride bromide phthalocyanine pigment having high transmittance and contrast and showing green color is obtained. The pigment-forming method is not particularly limited, and the solvent salt milling treatment is preferably used in view of easily obtaining pigment particles having a large specific surface area and suppressed crystal growth.
The solvent salt milling means that the crude pigment immediately after synthesis, inorganic salt and organic solvent are kneaded and milled. Specifically, a crude pigment, an inorganic salt, and an organic solvent which does not dissolve them are fed to a mixer, and mixing and grinding are carried out therein. As the kneading machine in this case, for example, a kneader, a mixer-mill, a planetary mixer, or a continuous kneading machine having a pulverization space formed by a gap portion between an annular fixed disk and a concentric rotating disk as described in japanese patent application laid-open No. 2006-77062 is preferably used.
As the inorganic salt, a water-soluble inorganic salt can be preferably used, and for example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate, or the like is preferably used. Further, it is more preferable that the average particle diameter of these inorganic salts is 0.5 to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing a general inorganic salt.
As the green pigment a, G59 manufactured by DIC was used.
The pigment (A) may contain other green pigments in addition to the green pigment a. Examples of the other green pigment include c.i. pigment green 7, c.i. pigment green 36, and c.i. pigment green 58.
The content of the green pigment a contained in the green pigment is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, further preferably 50% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less. When the amount of the pigment is not less than the lower limit, the effect of the pigment tends to be more obtained.
The content of the green pigment contained in the pigment (a) is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and particularly preferably 45% by mass or more, and is usually 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting the lower limit value or more, the color gamut tends to be widened, and by setting the upper limit value or less, the platemaking property tends to be optimized.
The content of the pigment (a) in the colored resin composition of the present invention is usually 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 45% by mass or less, based on the total solid content. When the amount is within the above range, the dispersion stability is good, and the effect of the green pigment tends to be more obtained.
The content of the pigment (a) in the pigment dispersion liquid of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more, and is preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total solid content. In the case where the amount is within the above range, the dispersion stability is good, and the effect of the green pigment tends to be more obtained.
The content of the green pigment in the pigment dispersion liquid of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, based on the total solid content. In the case where the amount is within the above range, the dispersion stability is good, and the effect of the green pigment tends to be more obtained.
The average primary particle diameter of the green pigment containing the green pigment a is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and usually 0.005 μm or more. When the average primary particle diameter is within the above range, deterioration of the depolarization characteristic and decrease in transmittance tend to be suppressed.
The average primary particle size of the pigment can be determined by the following method. That is, the pigment was ultrasonically dispersed in chloroform, dropped on a web to which a collodion film was adhered and dried, and observed by a Transmission Electron Microscope (TEM) to obtain a primary particle image of the pigment. In the case of an organic pigment, the particle diameters of the respective pigment particles are converted into diameters of circles having the same area, and the diameters of the circles are determined as area-equivalent circle diameters, respectively, for the plurality of pigment particles, and the number average value is calculated as shown in the following calculation formula, thereby determining the average particle diameter.
Particle diameter of each pigment particle:
X1、X2、X3、X4、....、Xi、......Xmaverage particle diameter ═ Σ Xi/m
In addition, the (a) pigment may contain a yellow pigment for hue adjustment. Examples of the yellow pigment include: pigment yellow (P.Y.)1, 1:1, 2,3,4,5,6, 9,10, 12, 13, 14,16, 17, 20, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62:1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 169, 166, 167, 168, 170, 172, 182, 147, 176, 183, 188, 193, 185, 188, 185, 193, 194, 185, 189, 194, 199, 185, 189, 194, 185, 194, 199, 185, 189, 194, 199, 185, 194, 199, 197, 185, 189, 185, 194, 199, 185, 199, 197, and 21, 200. 202, 203, 204, 205, 206, 207, 208, and a compound in which another compound is inserted into a complex compound of azobarbituric acid represented by the following formula (I) and nickel in a ratio of 1:1 or a tautomer thereof (hereinafter, referred to as "nickel azo complex compound represented by the formula (I)").
[ chemical formula 1]
In addition, examples of the other compounds include compounds represented by the following formula (II).
[ chemical formula 2]
Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and the nickel azo complex compound represented by formula (I) are preferable, and c.i. pigment yellow 83, 138, 139, 180 and the nickel azo complex compound represented by formula (I) are more preferable.
The average primary particle diameter of these yellow pigments is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. In the case of micronization of the pigment, the above-mentioned method of grinding the solvent salt is preferably used.
(A) The content ratio of the yellow pigment contained in the pigment is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, particularly preferably 70% by mass or less, and most preferably 60% by mass or less, and is usually 0% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more. When the amount is less than the above upper limit, the effect of the green pigment a tends to be more obtained.
The colored resin composition and the pigment dispersion liquid of the present invention may contain a dye in addition to the pigment (a). In particular, from the viewpoint of brightness, it is preferable to contain a yellow dye.
[1-2] (B) dispersant
The colored resin composition and the pigment dispersion liquid of the present invention contain (B) a dispersant for stably dispersing (a) a pigment. Among these, the use of a polymeric dispersant is preferable because it is excellent in dispersion stability with time.
Examples of the polymeric dispersant include: urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. Specific examples of the dispersant include EFKA (registered trademark, manufactured by BASF corporation), DisperbYK (registered trademark, manufactured by BYK-Chemie corporation), Disparlon (registered trademark, manufactured by Nanguzhi Kabushiki Kaisha), SOLSPERSE (registered trademark, manufactured by Zeneca corporation), KP (registered trademark, manufactured by shin-Etsu chemical industry Co., Ltd.), Polyflow (registered trademark, manufactured by Kyoho chemical Co., Ltd.), and the like.
Among the polymer dispersants, from the viewpoint of dispersibility and storage stability, a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer is more preferable.
As the block copolymer having a functional group containing a nitrogen atom, an A-B block copolymer and/or a B-A-B block copolymer composed of an A block having a quaternary ammonium salt group and/or an amino group in a side chain and a B block having no quaternary ammonium salt group and/or an amino group is preferable.
The functional group containing a nitrogen atom includes a 1 to 3-stage amino group and a quaternary ammonium salt group, and preferably has a 1 to 3-stage amino group, and more preferably has a 3-stage amino group, from the viewpoint of dispersibility and storage stability.
The structure of the repeating unit having a 3-stage amino group in the block copolymer is not particularly limited, and a repeating unit represented by the following general formula (1) is preferable from the viewpoint of dispersibility and storage stability.
[ chemical formula 3]
In the above formula (1), R1And R2Each independently is a hydrogen atom, optionally having a substituentAlkyl group of substituent, aryl group optionally having substituent, or aralkyl group optionally having substituent, R1And R2Optionally bonded to each other to form a cyclic structure, R3Is a hydrogen atom or a methyl group, and X is a linking group having a valence of 2.
In the formula (1), the number of carbon atoms of the alkyl group which may have a substituent is not particularly limited, but is usually 1 or more, and is preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. Further, it may be either straight or branched. Further, the cyclic structure may include a cyclohexyl group, a cyclohexylmethyl group, or the like.
In the formula (1), the number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.
In the formula (1), the number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 9 or less. Specific examples of the aralkyl group include a phenylmethylene, a phenylethylene, a phenylpropylene, a phenylbutylene, and a phenylisopropylene, and among these, a phenylmethylene, a phenylethylene, a phenylpropylene, and a phenylbutylene are preferable, and a phenylmethylene or a phenylethylene are more preferable.
Among these, R is preferable from the viewpoint of dispersibility, storage stability, electrical reliability and developability1And R2Each independently an alkyl group optionally having a substituent, more preferably a methyl groupA radical or an ethyl radical.
Examples of the substituent optionally contained in the alkyl group, aralkyl group or aryl group in the formula (1) include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
In the above formula (1), R is1And R2Examples of the cyclic structure formed by bonding to each other include a monocyclic ring of a 5 to 7-membered ring nitrogen-containing heterocycle or a condensed ring in which 2 of these rings are condensed. The nitrogen-containing heterocycle is preferably one having no aromatic character, and more preferably a saturated ring. Specific examples thereof include the following cyclic structure (IV).
[ chemical formula 4]
These cyclic structures may further have a substituent.
In the formula (1), examples of the 2-valent linking group X include: alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 12 carbon atoms, -CONH-R13-radical, -COOR14-radical [ wherein, R13And R14A single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms, etc., preferably-COO-R14-a radical.
The content ratio of the repeating unit represented by the formula (1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, most preferably 25 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. When the amount is within the above range, dispersion stability and high luminance tend to be compatible.
In addition, from the viewpoint of improving the compatibility of the dispersant with respect to a binder component such as a solvent and the like, and thereby improving dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (2).
[ chemical formula 5]
In the above formula (2), R10Is ethylene or propylene, R11Is an alkyl group optionally having a substituent, R12Is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.
R of the above formula (2)11The number of carbon atoms of the alkyl group which may have a substituent is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. Further, it may be either straight or branched. Further, the cyclic structure may include a cyclohexyl group, a cyclohexylmethyl group, or the like.
In addition, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent.
The content ratio of the repeating unit represented by the formula (2) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be both satisfied.
In addition, from the viewpoint of improving the compatibility of the dispersant with respect to a binder component such as a solvent and the like, and thereby improving dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (3).
[ chemical formula 6]
In the above formula (3), R8Is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent. R9Is a hydrogen atom or a methyl group.
R in the above formula (3)8The number of carbon atoms of the alkyl group optionally having a substituent is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. Further, it may be either straight or branched. Further, the cyclic structure may include a cyclohexyl group, a cyclohexylmethyl group, or the like.
R in the above formula (3)8In (b), the number of carbon atoms of the aryl group optionally having a substituent is not particularly limited, and is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.
R in the above formula (3)8In (b), the number of carbon atoms of the aralkyl group optionally having a substituent is not particularly limited, and is usually 7 or more, and preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene, a phenylethylene, a phenylpropylene, a phenylbutylene, and a phenylisopropylene, and among these, a phenylmethylene, a phenylethylene, a phenylpropylene, and a phenylbutylene are preferable, and a phenylmethylene or a phenylethylene are more preferable.
TheseAmong them, R is from the viewpoint of solvent compatibility and dispersion stability8Preferably an alkyl or aralkyl group, more preferably a methyl, ethyl or phenylmethylene group.
As R8Examples of the substituent optionally contained in the alkyl group in (1) include a halogen atom and an alkoxy group. Examples of the substituent optionally contained in the aryl group or the aralkyl group include a chain alkyl group, a halogen atom, an alkoxy group, and the like. In addition, R8The chain alkyl group includes any of straight-chain and branched-chain.
The content ratio of the repeating unit represented by the formula (3) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% or more, and is preferably 80 mol% or less, and more preferably 70 mol% or less. When the amount is within the above range, dispersion stability and high luminance tend to be compatible.
The block copolymer may further have a repeating unit other than the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). Examples of such repeating units include repeating units derived from the following monomers: styrene monomers such as styrene and alpha-methylstyrene; (meth) acrylate monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; n-methacryloylmorpholine and the like.
From the viewpoint of further improving the dispersibility, a block copolymer having an a block having a repeating unit represented by the above general formula (1) and a B block having no repeating unit represented by the above general formula (1) is preferable. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. More preferably, the B block has a repeating unit represented by the above general formula (2) and a repeating unit represented by the above general formula (3).
Further, a repeating unit other than the repeating unit represented by the above general formula (1) may be contained in the a block, and examples of such a repeating unit include a repeating unit derived from the above-mentioned (meth) acrylate-based monomer. The content of the repeating unit other than the repeating unit represented by the above general formula (1) in the a block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably such a repeating unit is not contained in the a block.
The repeating unit represented by the above general formula (2) and the repeating unit other than the repeating unit represented by the above general formula (3) may be contained in the B block, and examples of such repeating units include repeating units derived from: styrene monomers such as styrene and alpha-methylstyrene; (meth) acrylate monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; n-methacryloylmorpholine and the like. The content of the repeating unit represented by the general formula (2) and the repeating unit other than the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably such a repeating unit is not contained in the B block.
From the viewpoint of dispersibility, the block copolymer preferably has a low acid value, and more preferably has an acid value of 0 mgKOH/g. The acid value here means the mg number of KOH required for neutralizing 1g of the solid content of the dispersant.
Further, from the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 70mgKOH/g or more, still more preferably 90mgKOH/g or more, particularly preferably 100mgKOH/g or more, most preferably 110mgKOH/g or more, and preferably 150mgKOH/g or less, more preferably 130mgKOH/g or less. The amine number here means an amine number converted into an effective solid content, and is a value corresponding to the amount of base in the solid content per 1g of the dispersant and expressed by the mass of KOH.
The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in terms of a weight average molecular weight (hereinafter, sometimes referred to as "Mw") of polystyrene. In the case where the amount is within the above range, the dispersion stability is improved, and when the slit nozzle method is used for coating, dry foreign matter tends to be less likely to be generated.
The block copolymer can be produced by a known method, for example, by living polymerization of a monomer to be introduced into each of the repeating units. As the living polymerization method, Japanese patent application laid-open Nos. 9-62002, 2002-31713, and P.Lutz, P.Masson et al, Polym.Bull.12,79 (1984); anderson, g.d. andrews et al, Macromolecules,14,1601 (1981); K.Hatada, K.Ute, et al, Polym.J.,17,977 (1985); K.Hatada, K.Ute, et al, Polym.J.,18,1037 (1986); right-handed Haoyi, or Hazu field-cultivated, polymer processing, 36, 366 (1987); dongcun Mingyuan, Zebenguan Men, high molecular corpus, 46,189 (1989); m.kuroki, t.aida, j.am.chem.soc,109,4737 (1987); zhangtianzhuo, shangxianping, organic synthetic chemistry, 43,300 (1985); known methods described in D.Y.Sogoh, W.R.Hertler et al, Macromolecules,20,1473(1987), etc.
The content of the dispersant (B) in the colored resin composition and the pigment dispersion liquid of the present invention is not particularly limited, and is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass or less with respect to 100 parts by mass of the pigment (a). When the amount is within the above range, a colored resin composition having excellent dispersion stability and high brightness tends to be obtained.
[1-3] Dispersion auxiliary
The colored resin composition and the pigment dispersion liquid of the present invention may further contain a pigment derivative or the like as a dispersion aid in order to improve the dispersibility of the pigment and to improve the dispersion stability. Examples of the pigment derivative include: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, bisquinoneAzines, anthraquinones, indanthrones, perylenes, perinones, diketopyrrolopyrrolesDerivatives of azines and the like. Examples of the substituent of the pigment derivative include: sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be bonded directly to the pigment skeleton or through an alkyl group, aryl group, heterocyclic group, and the like, are preferably sulfonamide groups and quaternary salts thereof, sulfonic acid groups, and sulfonic acid groups are more preferably used. These substituents may be substituted in plural on one pigment skeleton, or may be a mixture of compounds having different substitution numbers. Specific examples of the pigment derivative include: sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, bis (pyrrole) pigmentsSulfonic acid derivatives of oxazine pigments, and the like.
Among these, a pigment derivative which is less involved in the hue of the green pigment is preferable, and a sulfonic acid derivative of pigment yellow 138, a sulfonic acid derivative of pigment yellow 139, and a sulfonic acid derivative of pigment blue 15 are more preferable.
The amount of the pigment derivative used is usually 0.1 part by mass or more and usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less, relative to 100 parts by mass of the (a) pigment.
[1-4] Dispersion resin
The pigment dispersion liquid of the present invention may contain a part or all of a resin selected from binder resins described later. Specifically, in the dispersion treatment step for preparing a pigment dispersion liquid described later, it is preferable to contain a part or all of the above-mentioned dispersant and binder resin because the synergistic effect of the binder resin and the dispersant contributes to the dispersion stability of the pigment and as a result, the amount of the dispersant to be added can be reduced. The resin used in the dispersion treatment step is sometimes referred to as a dispersion resin.
[1-5] (C) solvent
(C) The solvent has a function of adjusting the viscosity by dissolving or dispersing the pigment, the dispersant, and other components in the colored resin composition and the pigment dispersion liquid of the present invention.
The solvent (C) may be any solvent capable of dissolving or dispersing the respective components.
In the colored resin composition according to embodiment 1 and the pigment dispersion according to embodiment 2 of the present invention, the solvent (C) contains a high boiling point solvent having a boiling point of 150 ℃ or higher at 1013.25hPa (hereinafter, simply referred to as "high boiling point solvent"). By containing the high-boiling solvent in this way, it is considered that the re-solubility is improved, and the occurrence of foreign matter on the surface of the cured film due to the re-solubility of the colored resin composition, which occurs specifically when a specific zinc bromophthalocyanine green pigment is used, can be suppressed.
The boiling point (hereinafter, simply referred to as "boiling point" unless otherwise specified) of the high-boiling solvent at 1013.25hPa is usually 150 ℃ or higher, preferably 170 ℃ or higher, more preferably 190 ℃ or higher, and still more preferably 210 ℃ or higher, and is preferably 340 ℃ or lower, more preferably 300 ℃ or lower, and still more preferably 280 ℃ or lower. When the lower limit value is not less than the above-mentioned lower limit value, the re-solubility tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the VCD (reduced pressure drying) efficiency in the color filter production process tends to be improved.
The vapor pressure of the high boiling point solvent at 20 ℃ is not particularly limited, but is preferably 1Pa or more, more preferably 10Pa or more, and further preferably 100Pa or more, and is preferably 2000Pa or less, more preferably 1000Pa or less, further preferably 500Pa or less, and particularly preferably 400Pa or less. When the lower limit value is not less than the lower limit value, VCD (reduced pressure drying) efficiency in a color filter production process tends to be improved, and when the upper limit value is not more than the lower limit value, resolubility tends to be improved.
Specific examples of the high boiling point solvent include: glycol ethers such as ethylene glycol diacetate (boiling point: 191 ℃ C.), ethylene glycol mono-n-butyl ether (boiling point: 171 ℃ C.), propylene glycol mono-n-butyl ether (boiling point: 170 ℃ C.), diethylene glycol diethyl ether (boiling point: 188 ℃ C.), diethylene glycol monoethyl ether (boiling point: 202 ℃ C.), glycol mono-n-butyl ether acetate (boiling point: 192 ℃ C.), diethylene glycol monoethyl ether acetate (boiling point: 217 ℃ C.), diethylene glycol mono-n-butyl ether acetate (boiling point: 247 ℃ C.), ethyl 3-ethoxypropionate (boiling point: 170 ℃ C.), 3-methoxybutyl acetate (boiling point: 171 ℃ C.), and glycol diacetate such as 1, 3-butanediol diacetate (boiling point: 232 ℃ C.), from the viewpoint of solubility of the colored resin composition, acetates and glycol ethers are preferable, and glycol alkyl ether acetates are more preferable.
In the colored resin composition according to embodiment 1 and the pigment dispersion according to embodiment 2 of the present invention, the solvent (C) preferably contains a low boiling point solvent having a boiling point of less than 150 ℃ at 1013.25hPa (hereinafter, simply referred to as "low boiling point solvent"). By containing the low boiling point solvent in this way, VCD (reduced pressure drying) efficiency in the color filter production process tends to be improved.
The boiling point (hereinafter, simply referred to as "boiling point" unless otherwise specified) of the low-boiling solvent at 1013.25hPa is usually less than 150 ℃, preferably 140 ℃ or less, more preferably 130 ℃ or less, further preferably 120 ℃ or less, and preferably 80 ℃ or more, more preferably 90 ℃ or more, further preferably 100 ℃ or more. When the upper limit value is less than the upper limit value, VCD (reduced pressure drying) efficiency in a color filter production process tends to be improved, and when the lower limit value is more than the lower limit value, resolubility tends to be improved.
Specific examples of the low boiling point solvent include: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, ethyl pyruvate, methyl-3-methoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, dibutyl ether, ethyl pyruvate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, methyl-3-methoxyisobutyl ester, methyl glycolate, methyl propoxide, methyl-2-hydroxyisobutyl ester, 2-methoxyethyl acetate, ethylene glycol methyl ether acetate, dibutyl ether, cycloheptanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, methyl-2-hydroxy-butyl acetate, ethyl-acetate, ethyl glycol methyl ether acetate, 2-heptanone, 3-heptanone, 4-heptanone, 1-methoxy-2-propanol, and the like.
The content of the solvent (C) in the colored resin composition according to embodiment 1 of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 75% by mass or more, most preferably 80% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less. When the lower limit is not less than the above-mentioned lower limit, the storage stability of the coloring composition tends to be improved, and when the upper limit is not more than the above-mentioned upper limit, the film thickness at the time of coating tends to be constant or less.
In the colored resin composition according to embodiment 1 of the present invention, the content of the high boiling point solvent with respect to the solvent (C) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 15% by mass or more, and most preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the solubility of the dried film in the solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the drying time of the coated film after coating tends to be shortened.
In the colored resin composition according to embodiment 1 of the present invention, the content of the low-boiling solvent with respect to the solvent (C) is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and particularly preferably 80% by mass or more, and is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, and particularly preferably 95% by mass or less. When the lower limit value is not less than the upper limit value, the drying time of the coating film after coating tends to be shortened, and when the upper limit value is not more than the lower limit value, the solubility of the dried film in the solvent tends to be improved.
The content of the solvent (C) in the pigment dispersion liquid according to embodiment 2 of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. When the lower limit is not less than the above-mentioned lower limit, the storage stability of the pigment dispersion liquid tends to be improved, and when the upper limit is not more than the above-mentioned upper limit, the ratio of the solvent entering the coloring composition tends to be reduced.
In the pigment dispersion liquid according to embodiment 2 of the present invention, the content ratio of the high boiling point solvent to the solvent (C) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 40% by mass or more, and most preferably 60% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the solubility of the dried film in the solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the drying time of the coated film after coating tends to be shortened.
In the pigment dispersion liquid according to embodiment 2 of the present invention, the content ratio of the low-boiling solvent to the solvent (C) is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 95% by mass or less, and particularly preferably 90% by mass or less. When the lower limit value is not less than the upper limit value, the drying time of the coating film after coating tends to be shortened, and when the upper limit value is not more than the lower limit value, the solubility of the dried film in the solvent tends to be improved.
On the other hand, in the colored resin composition according to embodiment 3 of the present invention, the solvent may be used without particular limitation, and for example, the following solvents can be used.
Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;
alkyl acetates such as cyclohexyl acetate;
ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;
ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;
monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
linear or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;
alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile.
Examples of the commercially available solvent corresponding to the above include: mineral spirits (Mineral spirits), Varsol #2, Apco #18solvent, Apco trinner, Socal solvent Nos. 1 and 2, Solvesso #150, ShellTS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (digle) (all of which are trade names), and the like. These solvents may be used alone or in combination of 2 or more.
When a pixel of a color filter is formed by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 200 ℃ (under the condition of pressure 1013.25[ hPa ], the boiling points are the same below). More preferably a solvent having a boiling point of 120 to 170 ℃.
Among the above solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like and high solubility of the constituent components in the composition.
In addition, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. The organic solvent used in combination is particularly preferably a glycol monoalkyl ether. Among these, propylene glycol monomethyl ether is particularly preferable in view of solubility of the constituent components in the composition. The glycol monoalkylethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate easily and the storage stability of the colored resin composition obtained thereafter tends to be lowered, for example, the viscosity increases, and therefore the proportion of the glycol monoalkylethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
In addition, it is also preferable to use a solvent having a boiling point of 150 ℃ or higher in combination. By using such a high boiling point solvent in combination, the colored resin composition is not easily dried, but the mutual relationship of the pigment dispersion liquid is not easily broken by rapid drying. The content of the high-boiling solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass, based on the solvent. If the amount of the high boiling point solvent is too small, foreign matter defects may be caused by precipitation and solidification of a color material component or the like at the tip of the slit nozzle, and if the amount of the high boiling point solvent is too large, the drying rate of the composition becomes slow, and problems such as defective tact (タ ク ト) in the reduced pressure drying step and needle marks in the prebaking (pre-cake) may occur in the color filter manufacturing step described later.
The solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the solvent having a boiling point of 150 ℃ or higher may not be additionally contained.
In the case of forming a pixel of a color filter by an ink jet method, a solvent having a boiling point of usually 130 ℃ or higher and 300 ℃ or lower, preferably 150 ℃ or higher and 280 ℃ or lower is suitable as the solvent. If the boiling point is too low, the uniformity of the obtained coating film tends to be poor, whereas if the boiling point is too high, the drying-inhibiting effect of the curable resin composition is high as described later, but a large amount of residual solvent is present in the coating film after thermal baking, which may cause problems in quality, such as a long drying time in vacuum drying, and an increase in tact time.
In addition, from the viewpoint of uniformity of the obtained coating film, a solvent having a vapor pressure of usually 10mmHg or less, preferably 5mmHg or less, more preferably 1mmHg or less may be used.
In the case of manufacturing a color filter by the ink jet method, since the ink discharged from the nozzle is very fine and several to several tens pL, the solvent evaporates before the ink lands on the periphery of the nozzle opening or in the pixel array, and the ink tends to be concentrated and dried. In order to avoid this, the solvent preferably has a high boiling point, and specifically, the solvent preferably contains a solvent having a boiling point of 180 ℃ or higher, more preferably contains a solvent having a boiling point of 200 ℃ or higher, and particularly preferably contains a solvent having a boiling point of 220 ℃ or higher. The high boiling point solvent having a boiling point of 180 ℃ or higher is preferably 50 mass% or higher, more preferably 70 mass% or higher, and most preferably 90 mass% or higher of all the solvents contained in the pigment dispersion liquid and/or the colored resin composition described later. When the high-boiling point solvent is less than 50% by mass, the effect of preventing evaporation of the solvent in the droplets may not be sufficiently exhibited.
Preferable high boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butylene glycol diacetate, 1, 6-hexanediol diacetate, triacetin, and the like among the above solvents.
In addition, it is also effective to contain a solvent having a partial boiling point of less than 180 ℃ in order to adjust the viscosity of the pigment dispersion liquid and the colored resin composition described later and to adjust the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Among them, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexyl acetate and the like are particularly preferable.
On the other hand, if the solvent contains an alcohol, the ejection stability of the ink jet method may be deteriorated. Therefore, the content of the alcohol in all the solvents is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
In the 3 rd aspect of the present invention, the content of the solvent in the entire colored resin composition is not particularly limited, and the upper limit thereof is usually 99 mass% or less, preferably 90 mass% or less, and more preferably 85 mass% or less. When the solvent exceeds the above upper limit, the amount of the pigment, dispersant, etc. is too small, and the coating film may not be formed properly. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in view of viscosity suitable for coating and the like.
[1-6] (D) Binder resin
The colored resin composition of the present invention contains (D) a binder resin. By containing the binder resin (D), film curability by photopolymerization and solubility by a developer can be both achieved.
The binder resin (D) is cured by any method to form a colored resin composition, and the preferred resins tend to be different. In the case of the photopolymerizable resin composition, known polymer compounds described in, for example, Japanese patent application laid-open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118 and 2003-233179 can be used as the binder resin. The following resins are preferably listed:
[1-6-1]: a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups formed by the addition reaction
[1-6-2] straight-chain alkali-soluble resin having carboxyl group in main chain
[1-6-3] A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the carboxyl group-containing resin
[1-6-4] (meth) acrylic resin
[1-6-5] an epoxy (meth) acrylate resin having a carboxyl group, and the like.
These various resins will be described below.
[1-6-1] A resin obtained by adding an unsaturated monobasic acid to at least a part of epoxy groups contained in a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of hydroxyl groups generated by the addition reaction of the unsaturated monobasic acid to a copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer
One of particularly preferable resins is "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of epoxy groups contained in a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of hydroxyl groups generated by the addition reaction".
The epoxy group-containing (meth) acrylate is used. Examples may be given of: glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among them, glycidyl (meth) acrylate is preferable. These epoxy group-containing (meth) acrylates may be used singly or in combination of 2 or more.
As the other radical polymerizable monomer to be copolymerized with the epoxy group-containing (meth) acrylate, a mono (meth) acrylate having a structure represented by the following general formula (V) is preferable.
[ chemical formula 7]
In the formula (V), R91～R98Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R is96And R98Or R95And R97May be connected to each other to form a ring.
In the formula (V), R96And R98Or R95And R97The ring formed by the linkage is preferably an aliphatic ring, which may be saturated or unsaturated, and the number of carbon atoms is preferably 5 to 6.
Among them, as the structure represented by the general formula (V), a structure represented by the following formula (Va), (Vb), or (Vc) is preferable.
When the colored resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored resin composition can be improved or the strength of a pixel formed by using the colored resin composition can be increased by incorporating the above-described structure into a binder resin.
The mono (meth) acrylate having a structure represented by the general formula (V) may be used alone or in combination of 2 or more.
[ chemical formula 8]
As the mono (meth) acrylate having the structure represented by the above general formula (V), various known mono (meth) acrylates having the structure can be used, and compounds represented by the following general formula (VI) are particularly preferable.
[ chemical formula 9]
In the formula (VI), R89Represents a hydrogen atom or a methyl group, R90Represents the structure of the general formula (V).
In the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (VI) is preferably contained in an amount of 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol% in the repeating unit derived from the "other radically polymerizable monomer".
The "other radically polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited. Specifically, examples thereof include: vinyl aromatic compounds such as styrene, and α -, o-, m-or p-alkyl groups, nitro groups, cyano groups, amide groups, and ester groups of styrene; dienes such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, isopropyl, Anthryl (meth) acrylate, anthraquinone (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meth) acrylates such as cresyl (meth) acrylate, 1,1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-N-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (meth) acrylamides such as (meth) acrylamide, N-dimethylamide (meth) acrylate, N-diethylamide (meth) acrylate, N-dipropylamide (meth) acrylate, N-diisopropylamide (meth) acrylate, and anthracylamide (meth) acrylate; vinyl compounds such as (meth) acryloylaniline, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate; unsaturated dicarboxylic diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; monoimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; n- (meth) acryloyl fumarimides, and the like.
In these "other radical polymerizable monomers", one or more monomers selected from styrene, benzyl (meth) acrylate, and monomaleimide may be used in order to impart excellent heat resistance and strength to the colored resin composition. In particular, the content of the repeating unit derived from one or more monomers selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide in the repeating unit derived from the "other radical polymerizable monomer" is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
In the copolymerization reaction of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer, a known solution polymerization method can be used. The solvent used is not particularly limited as long as it is a solvent that is not active in radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include: ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate, and the like; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; 1, 4-diEthers such as alkane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha and the like; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide, N-methylpyrrolidone, and the like. These solvents may be used alone, or 2 or more of them may be used in combination.
The amount of the solvent used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the copolymer obtained. When the amount of the solvent used is outside this range, it is difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate the radical polymerization reaction. A commonly used organic peroxide catalyst or azo compound catalyst may be used. Examples of the organic peroxide catalyst include known organic peroxide catalysts classified into ketone peroxides, peroxyketals, hydrogen peroxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
Specific examples thereof include: benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl (2-ethylhexanoate) peroxide, tert-hexyl peroxy (2-ethylhexanoate), 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexyl-3, 3-isopropylhydroperoxide, tert-butylhydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, acetyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3, 5-trimethylhexanoyl peroxide, lauryl peroxide (laurylperoxide), 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, and the like.
Further, as the azo compound catalyst, there can be mentioned: azobisisobutyronitrile, azobisformamide (azobiscarboamide), and the like.
Among them, one or more than 2 kinds of radical polymerization initiators having an appropriate half-life may be used depending on the polymerization temperature. The amount of the radical polymerization initiator used is 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers used in the copolymerization reaction.
The copolymerization reaction may be carried out by dissolving the monomer and the radical polymerization initiator used in the copolymerization reaction in a solvent and heating the solution while stirring, or by adding the monomer to which the radical polymerization initiator is added dropwise to the solvent heated and stirred. Further, a radical polymerization initiator may be added to the solvent, and the monomer may be added dropwise thereto while raising the temperature. The reaction conditions can be freely changed depending on the target molecular weight.
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer is preferably composed of 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate and 10 to 95 mol% of repeating units derived from the other radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and particularly preferably composed of 30 to 70 mol% of the former and 70 to 30 mol% of the latter.
When the amount of the epoxy group-containing (meth) acrylate is too small, the amount of the polymerizable component added to the alkali-soluble component described later may be insufficient, while when the amount of the epoxy group-containing (meth) acrylate is too large and the amount of the other radical polymerizable monomer is too small, the heat resistance and strength may be insufficient.
Next, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component) are reacted with an epoxy group portion of a copolymer of an epoxy resin-containing (meth) acrylate and another radically polymerizable monomer.
As the "unsaturated monoacid" added to the epoxy group, known unsaturated monoacids can be used, and examples thereof include: unsaturated carboxylic acids having an ethylenically unsaturated double bond.
As specific examples, there may be mentioned: (meth) acrylic acid; butenoic acid; o-, m-, or p-vinylbenzoic acid; monocarboxylic acids such as (meth) acrylic acid substituted at the α -position with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, or the like. Among them, (meth) acrylic acid is preferable. One of them may be used alone, or 2 or more of them may be used in combination.
Addition of such a component can impart polymerizability to the binder resin used in the present invention.
These unsaturated monoacids are added to 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol% of the epoxy groups in the copolymer. When the addition ratio of the unsaturated monobasic acid is too small, the residual epoxy group may adversely affect the stability of the colored resin composition with time. As a method for adding an unsaturated monoacid to an epoxy group of the copolymer, a known method can be used.
As the "polybasic acid anhydride" to be added to the hydroxyl group formed when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used.
Examples thereof include: dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and hexachloronadic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride, and other anhydrides of three or more acids. Among them, tetrahydrophthalic anhydride and/or succinic anhydride are preferable. These polybasic acid anhydrides may be used alone or in combination of 2 or more.
Addition of such a component can impart alkali solubility to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the hydroxyl groups formed when the unsaturated monobasic acid is added to the epoxy groups of the copolymer. When the addition ratio is too large, the residual film ratio during development may be lowered, and when it is too small, the solubility may be insufficient. As a method for adding a polybasic acid anhydride to the hydroxyl group, a known method can be used.
In addition, in order to improve the photosensitivity, after the addition of the polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the generated carboxyl groups.
In addition, in order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group.
Alternatively, the two may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include: glycidyl ether compounds having a phenyl group or an alkyl group, and the like. Examples of commercially available products include: trade names "Denacol (registered trademark, the same applies hereinafter)" EX-111 "," Denacol EX-121 "," Denacol EX-141 "," Denacol EX-145 "," Denacol EX-146 "," Denacol EX-171 ", and" Denacol EX-192 "manufactured by Nagase Kasei corporation.
The structure of such a resin is described in, for example, Japanese patent application laid-open Nos. 8-297366 and 2001-89533, and is already known.
The weight average molecular weight (Mw) of the binder resin measured by GPC and converted to polystyrene is preferably 3000 to 100000, and particularly preferably 5000 to 50000. When the molecular weight is less than 3000, heat resistance and film strength may be deteriorated, and when it exceeds 100000, solubility in a developer tends to be insufficient. Further, the ratio of the weight average molecular weight (Mw)/number average molecular weight (Mn) is preferably 2.0 to 5.0 as a criterion of the molecular weight distribution.
[1-6-2] straight-chain alkali-soluble resin having carboxyl group in main chain
The straight-chain alkali-soluble resin having a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and is usually obtained by polymerizing a polymerizable monomer having a carboxyl group.
Examples of the carboxyl group-containing polymerizable monomer include: (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl adipate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl succinate, 2- (meth) acryloyloxypropyl adipate, 2- (meth) acryloyloxypropyl maleate, 2- (meth) acryloyloxypropyl hydrogenated phthalate, 2- (meth) acryloyloxypropyl succinate, 2- (meth) acryloyloxybutyl adipate, itaconic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl phthalate, Vinyl monomers such as 2- (meth) acryloyloxybutyl maleate, 2- (meth) acryloyloxybutyl hydrogenphthalate, and 2- (meth) acryloyloxybutyl phthalate; monomers obtained by adding lactones such as e-caprolactone, β -propiolactone, γ -butyrolactone and δ -valerolactone to acrylic acid; and monomers obtained by adding an acid or an acid anhydride such as succinic acid, maleic acid, phthalic acid, or an acid anhydride thereof to a hydroxyalkyl (meth) acrylate. A plurality of such carboxyl group-containing polymerizable monomers may be used.
Among them, preferred are (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinate, and more preferred is (meth) acrylic acid.
In addition, the linear alkali-soluble resin having a carboxyl group in the main chain may be obtained by copolymerizing another polymerizable monomer having no carboxyl group with the above-mentioned carboxyl group-containing polymerizable monomer.
The other polymerizable monomers are not particularly limited, and include: (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate; vinyl aromatic compounds such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; n-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide; macromonomers such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer and polycaprolactone macromonomer, and the like. These other polymerizable monomers may be used in combination of plural kinds.
Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide.
The linear alkali-soluble resin having a carboxyl group in the main chain may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. By copolymerizing these monomers with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.
Specific examples of the linear alkali-soluble resin having a carboxyl group in the main chain include: copolymers of (meth) acrylic acid with a polymerizable monomer having no hydroxyl group such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexylmaleimide, and a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; copolymers of (meth) acrylic acid with (meth) acrylic acid esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-hydroxyethyl methacrylate; copolymers of (meth) acrylic acid and styrene; copolymers of (meth) acrylic acid with styrene and alpha-methylstyrene; copolymers of (meth) acrylic acid and cyclohexylmaleimide, and the like.
From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.
The acid value of the straight chain alkali-soluble resin having a carboxyl group in the main chain of the present invention is usually 30 to 500KOHmg/g, preferably 40 to 350KOHmg/g, and more preferably 50 to 300 KOHmg/g.
The weight average molecular weight of the polystyrene measured by GPC is usually 2000 to 80000, preferably 3000 to 50000, and more preferably 4000 to 30000. When the weight average molecular weight is too small, the stability of the colored resin composition tends to be poor, and when the weight average molecular weight is too large, the solubility in a developer tends to be poor when used for a color filter or a liquid crystal display device described later.
[1-6-3] the resin according to [1-6-2] wherein an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin
In particular, a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the above-mentioned linear alkali-soluble resin having a carboxyl group in the main chain is preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
Examples thereof include: epoxy group-containing acyclic unsaturated compounds such as glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl- α -ethylacrylate, crotonyl glycidyl ether, (meth) butenoic acid glycidyl ether, N- (3, 5-dimethyl-4-glycidyl) benzyl acrylamide, and 4-hydroxybutyl (meth) acrylate glycidyl ether, but epoxy group-containing alicyclic unsaturated compounds are preferred from the viewpoint of heat resistance and pigment dispersibility described later.
Examples of the alicyclic epoxy group of the epoxy group-containing alicyclic unsaturated compound include: 2, 3-epoxycyclopentyl, 3, 4-epoxycyclohexyl, 7, 8-epoxy [ tricyclo [5.2.1.0] decan-2-yl ] yl and the like. The ethylenically unsaturated group is preferably an ethylenically unsaturated group derived from a (meth) acryloyl group, and the preferable epoxy-containing alicyclic unsaturated compound includes compounds represented by the following general formulae (5a) to (5 m).
[ chemical formula 10]
In the formulae (5a) to (5m), R21Represents a hydrogen atom or a methyl group, R22Represents an alkylene group, R23Represents a valence of 2M is an integer of 1 to 10. In the formula, 2R's are present21、R22May be the same or different.
In the general formulae (5a) to (5m), R22The alkylene group of (2) is preferably an alkylene group having 1 to 10 carbon atoms. Specifically, methylene, ethylene, propylene, butylene, and the like can be exemplified, and methylene, ethylene, propylene, and the like are preferable. In addition, as R23The hydrocarbon group of (3) is preferably a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include an alkylene group and a phenylene group.
These epoxy group-containing alicyclic unsaturated compounds may be used alone or in combination of 2 or more.
Among them, the compound represented by the general formula (5c) is preferable, and 3, 4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
The epoxy group-containing unsaturated compound can be added to the carboxyl group portion of the resin described in [1-6-2] above by a known method. For example, in tertiary amines such as triethylamine and benzylmethylamine; quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the like; the carboxyl group-containing unsaturated compound can be introduced into the carboxyl group of the resin by reacting the carboxyl group-containing resin with the epoxy group-containing unsaturated compound in an organic solvent at a reaction temperature of 50 to 150 ℃ for several to several tens of hours in the presence of a catalyst such as pyridine or triphenylphosphine.
The carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced has an acid value of usually 10 to 200KOHmg/g, preferably 20 to 150KOHmg/g, and more preferably 30 to 150 KOHmg/g.
The weight average molecular weight of the polystyrene measured by GPC is usually 2000 to 100000, preferably 4000 to 50000, and more preferably 5000 to 30000.
[1-6-4] (meth) acrylic resin
The (meth) acrylic resin is a polymer obtained by polymerizing (meth) acrylic acid and/or (meth) acrylic acid ester as a monomer component. Preferred (meth) acrylic resins include, for example: a polymer obtained by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate, and a polymer obtained by polymerizing monomer components including a compound represented by the following general formula (6) and/or (7) as an essential component.
[ chemical formula 11]
In the formula (6), R1aAnd R2aEach independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.
[ chemical formula 12]
In the formula (7), R1bRepresents a hydrogen atom or an alkyl group optionally having a substituent, L3Represents a 2-valent linking group or a direct bond, and X represents a group represented by the following formula (8) or an optionally substituted adamantyl group. L is3Can be reacted with R in the following formula (8)3bOr R4bBonded to form a ring.
[ chemical formula 13]
In the formula (8), R2b、R3b、R4bEach independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an amino group or an organic group, L1、L2Represents a 2-valent linking group, represents a bonding position, L1、L2And L in the above formula (7)32 or more of them may be bonded to each other to form a ring.
[1-6-4a ] A polymer obtained by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate
From the viewpoint of high affinity with the pigment, it is preferable to use a polymer obtained by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate.
The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, and the (meth) acrylic acid in the whole monomer component is usually 10 to 90 mass%, preferably 15 to 80 mass%, and more preferably 20 to 70 mass%. The benzyl (meth) acrylate is usually 5 to 90 mass%, preferably 15 to 80 mass%, and more preferably 20 to 70 mass% of the total monomer components. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be rough during development, and if the amount of (meth) acrylic acid is too small, development may not be possible. In addition, when the amount of benzyl (meth) acrylate is too large or too small, dispersion tends to be difficult.
[1-6-4b ] A polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (6) and/or (7) as an essential component
First, the compound of the general formula (6) will be explained.
In the ether dimer represented by the general formula (6), R is1aAnd R2aThe hydrocarbon group having 1 to 25 carbon atoms which may be optionally substituted is not particularly limited, and examples thereof include: a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a tert-pentyl group, a stearyl group, a lauryl group, or a 2-ethylhexyl group; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkyl groups substituted with an alkoxy group such as 1-methoxyethyl group and 1-ethoxyethyl group; alkyl substituted with aryl such as benzyl; and so on. Among these, from the viewpoint of heat resistance, a substituent of a primary carbon or a secondary carbon which is not easily removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group, is particularly preferable. In addition, R is1aAnd R2aThe substituent may be the same substituent or different substituents.
Specific examples of the ether dimer include: dimethyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, diethyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-n-propyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, diisopropyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-n-butyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, diisobutyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-tert-butyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, mixtures thereof, and mixtures thereof, Di-tert-amyl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, distearyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, dilauryl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, bis (2-ethylhexyl) -2, 2' - [ oxybis (methylene) ] bis-2-acrylate, bis (1-methoxyethyl) -2,2 '- [ oxybis (methylene) ] bis-2-acrylate, bis (1-ethoxyethyl) -2, 2' - [ oxybis (methylene) ] bis-2-acrylate, dibenzyl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, bis (2, 2' - [ oxybis (methylene) ] bis-2-acrylate, bis (methylene) ] bis, Diphenyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, dicyclohexyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, di (tert-butylcyclohexyl) -2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di (dicyclopentadienyl) -2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di (tricyclodecyl) -2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di (isobornyl) -2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, diamantyl-2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, bis (adamantyl) -2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, bis (2-acrylate), bis (2, 2 ' - [ oxybis (methylene) ] bis-2-acrylate, bis (, Bis (2-methyl-2-adamantyl) -2, 2' - [ oxybis (methylene) ] bis-2-acrylate, and the like.
Among them, dimethyl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, diethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, dicyclohexyl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, and dibenzyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate are particularly preferable. These ether dimers may be used singly or in combination of 2 or more.
The proportion of the ether dimer in the monomer component in obtaining the acrylic resin is not particularly limited, and is usually 2 to 60% by weight, preferably 5 to 55% by weight, and more preferably 5 to 50% by weight in the total monomer component. If the amount of the ether dimer is too large, it may be difficult to obtain a resin having a low molecular weight or it may be easily gelled during polymerization, while if the amount of the ether dimer is too small, the film properties such as transparency and heat resistance may be insufficient.
Next, the compound of the general formula (7) will be described.
In the general formula (7), R1bPreferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (8), R is2b、R3b、R4bThe organic group of (A) may be, for example, independently an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group or an acyloxy group, and preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom or an acyloxy group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.
As R2b、R3b、R4bAmong them, preferred substituents are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L1、L2Provided that it is a 2-valent linking group, L3The linking group is not particularly limited as long as it is a 2-valent linking group or a direct bond, but preferably at least L1Or L2Any of them is a linking group having 1 or more carbon atoms. In addition, L is preferred1、L2、L3Each independently is a direct bond, an alkylene group having 1 to 15 carbon atoms, -O-, -S-, -C (═ O) -, an alkenylene group having 1 to 15 carbon atoms, a phenylene group, or a combination thereof.
As L1、L2、L3Preferred combinations of (A) and (B), L3Is a direct bond, an alkylene group having 1 to 5 carbon atoms, or a group with R3bOr R4bA ring formed by bonding, L1、L2Is an alkylene group having 1 to 5 carbon atoms.
Further, preferable examples of the compound of the general formula (8) include compounds represented by the following general formula (9).
[ chemical formula 14]
In the formula (9), R2b、R3b、R4b、L1、L2And is synonymous with in formula (8), R5b、R6bEach independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an amino group or an organic group.
In the general formula (9), as R5b、R6bThe organic group of (A) may be, for example, independently an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group or an acyloxy group, and preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom or an acyloxy group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.
R5b、R6bAmong them, preferred substituents are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, R1bAlkyl of R2b、R3b、R4bEach organic group of (1), L1、L2、L3The connecting group having a valence of 2 in (b) and the adamantyl group in (X) may each independently have a substituent, and specific examples thereof include the following substituents.
A halogen atom; a hydroxyl group; a nitro group; a cyano group; a C1-18 straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a tert-octyl group, etc.; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group, a hexenyl group, or the like; carbon of cyclopentenyl group, cyclohexenyl group, etcA cycloalkenyl group having 3 to 18 atoms; a linear or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, a tert-octyloxy group, etc.; linear or branched alkylthio groups having 1 to 18 carbon atoms such as a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a tert-pentylthio group, a n-hexylthio group, a n-heptylthio group, a n-octylthio group, and a tert-octylthio group; phenyl, tolyl, xylyl,An aryl group having 6 to 18 carbon atoms such as a phenyl group; aralkyl groups having 7 to 18 carbon atoms such as benzyl group and phenethyl group; a linear or branched alkenyloxy group having 2 to 18 carbon atoms such as an vinyloxy group, a propenyloxy group, a hexenyloxy group, or the like; linear or branched alkenylthio groups having 2 to 18 carbon atoms such as vinylthio group, propenylthio group, hexenylthio group and the like; -COR17An acyl group represented by the formula; a carboxyl group; -OCOR18An acyloxy group represented by; -NR19R20An amino group represented by; -NHCOR21An acylamino group represented by; -NHCOOR22A carbamate group of the formula; -CONR23R24A carbamoyl group represented by; -COOR25A carboxylic acid ester group represented by; -SO3NR26R27A sulfamoyl group represented by; -SO3A sulfonate group represented by R28; 2-thienyl, 2-pyridyl, furyl,Azolyl, benzoSaturated or unsaturated aromatic heterocyclic groups such as an oxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholinyl group, a pyrrolidinyl group, and a tetrahydrothienyl group dioxide; trialkylsilyl groups such as trimethylsilyl group, and the like.
In addition, R is17～R28Each represents a hydrogen atom, an alkyl group optionally having a substituentAn alkenyl group, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent.
The positional relationship of the substituents is not particularly limited, and when a plurality of substituents are present, they may be the same or different.
Specific examples of the compound represented by the general formula (7) include the following.
[ chemical formula 15]
[ chemical formula 16]
The proportion of the general formula (7) in the monomer components constituting the polymer of [1-6-4b ] of the present invention is not particularly limited, and is usually 0.5 to 60 mass%, preferably 1 to 55 mass%, more preferably 5 to 50 mass% in the whole monomer components. If the proportion of the general formula (7) is too large, the dispersion stability of the dispersion may be lowered when used as a dispersant, while if the proportion of the general formula (7) is too small, the plate surface offset suitability may be lowered.
The (meth) acrylic resin of [1-6-4] in the present invention preferably has an acid group including the polymers of [1-6-4a ] and [1-6-4b ]. By having an acid group, the resulting colored resin composition can be: a colored resin composition which can be cured by a crosslinking reaction in which an acid group reacts with an epoxy group to form an ester bond (hereinafter, simply referred to as acid-epoxy curing), or a composition which can develop an uncured portion with an alkali developing solution. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and an acid anhydride group. These acid groups may be one kind or 2 or more kinds.
The acid group can be introduced into the (meth) acrylic resin using, for example, a monomer having an acid group and/or a "monomer capable of imparting an acid group after polymerization" (hereinafter sometimes simply referred to as "monomer for introducing an acid group") as a monomer component. When "a monomer capable of imparting an acid group after polymerization" is used as a monomer component, a treatment for imparting an acid group as described later is necessary after polymerization.
Examples of the monomer having an acid group include: monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; and monomers having an acid anhydride group such as maleic anhydride and itaconic anhydride, and among these, (meth) acrylic acid is particularly preferable.
Examples of the monomer capable of imparting an acid group after polymerization include: a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate; and monomers having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate.
These monomers for introducing an acid group may be only one type, or may be 2 or more types.
When the monomer component for obtaining the (meth) acrylic resin also includes the above-mentioned monomer for introducing an acid group, the content ratio thereof is not particularly limited, and is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on the whole monomer component.
The [1-6-4] (meth) acrylic resin may have a radical polymerizable double bond.
In order to introduce a radical polymerizable double bond into the (meth) acrylic resin, for example, after "a monomer capable of imparting a radical polymerizable double bond after polymerization" (hereinafter, also referred to as "a monomer for introducing a radical polymerizable double bond") is polymerized as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be performed.
Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include: monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having an acid anhydride group such as maleic anhydride and itaconic anhydride; epoxy group-containing monomers such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing a radical polymerizable double bond may be only one type, or may be 2 or more types.
When the monomer component for obtaining the (meth) acrylic resin of [1-6-4] also includes the above-mentioned monomer for introducing a radical polymerizable double bond, the content ratio thereof is not particularly limited, and is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on the whole monomer component.
When the (meth) acrylic resin of the present invention is a polymer containing the compound of the above general formula (6) as an essential monomer component as described in [1-6-4a ], it preferably has an epoxy group.
In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter, also referred to as "monomer for introducing an epoxy group") may be polymerized as a monomer component.
Examples of the monomer having an epoxy group include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These epoxy group-introducing monomers may be used alone or in combination of 2 or more.
When the monomer component for obtaining the (meth) acrylic resin of [1-6-4] also includes the above-mentioned monomer for introducing an epoxy group, the content ratio thereof is not particularly limited, and is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on the whole monomer component.
The monomer component for obtaining the (meth) acrylic resin of [1-6-4] may contain, in addition to the above-mentioned essential monomer components, other copolymerizable monomers as required.
Examples of other copolymerizable monomers include: (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; aromatic vinyl compounds such as styrene, vinyltoluene and α -methylstyrene; n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate.
Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat deterioration. These other copolymerizable monomers may be used alone or in combination of 2 or more.
In particular, when a part or all of the (meth) acrylic resin is used as a dispersant as described later, benzyl (meth) acrylate is preferably used, and the content thereof is usually 1 to 70% by mass, preferably 5 to 60% by mass, based on the total monomer components.
When the monomer component for obtaining the (meth) acrylic resin also contains the other copolymerizable monomer, the content thereof is not particularly limited, and is preferably 95% by mass or less, more preferably 85% by mass or less.
Next, a method for producing (meth) acrylic resin (polymerization method) according to [1-6-4] will be described.
The method of polymerizing the monomer component is not particularly limited, and various conventionally known methods can be used, and the solution polymerization method is particularly preferably used. The polymerization temperature and the polymerization concentration (polymerization concentration [ total mass of monomer components/(total mass of monomer components + solvent mass) ] × 100) differ depending on the kind and ratio of the monomer components used and the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ℃ and more preferably 60 to 130 ℃. The polymerization concentration is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
When a solvent is used in the polymerization, a general radical polymerization reaction may be usedThe solvent used is only needed. Specific examples thereof include: tetrahydrofuran, diEthers such as alkane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethylsulfoxide, and the like. These solvents may be used alone, or 2 or more kinds may be used in combination.
When the monomer component is polymerized, a polymerization initiator may be used as needed. The polymerization initiator is not particularly limited, and examples thereof include: organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, dilauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, and t-hexyl peroxy-2-ethylhexanoate; azo compounds such as 2,2 '-azobisisobutyronitrile, 1' -azobis (cyclohexanecarbonitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), and 2, 2' -azobis (methyl 2-methylpropionate). These polymerization initiators may be used alone, or 2 or more kinds may be used in combination.
The amount of the initiator to be used is not particularly limited, and may be suitably set depending on the combination of monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total monomer components, from the viewpoint that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained without causing gelation.
In addition, a chain transfer agent may be added for the purpose of adjusting the molecular weight. Examples of the chain transfer agent include: mercaptan chain transfer agents such as n-dodecanethiol, thioglycolic acid and methyl thioglycolate; preferred examples of the monomer include n-dodecyl mercaptan and thioglycolic acid, which have a good chain transfer effect, can reduce residual monomers, and are easily available. When a chain transfer agent is used, the amount thereof to be used may be appropriately set depending on the combination of monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, but is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total monomer components, from the viewpoint that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained without causing gelation.
When the compound of the general formula (6) is used as an essential monomer component, the cyclization reaction of the ether dimer is considered to proceed simultaneously in the above polymerization reaction, but the cyclization ratio of the ether dimer in this case is not necessarily 100 mol%.
When an acid group is introduced by using the monomer capable of imparting an acid group as a monomer component in obtaining the acrylic resin, it is necessary to perform a treatment for imparting an acid group after polymerization. This treatment varies depending on the kind of the monomer used, and for example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, or maleic anhydride may be added. When an epoxy group-containing monomer such as glycidyl (meth) acrylate is used, a hydroxyl group may be formed by adding a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol, or by first adding an acid such as (meth) acrylic acid, and then an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, or maleic anhydride may be added to the hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added thereto.
When the radical polymerizable double bond is introduced by using the monomer capable of imparting a radical polymerizable double bond as described above as a monomer component in obtaining the (meth) acrylic resin of [1-6-4], it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization.
The treatment varies depending on the kind of the monomer used, and for example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, a compound having an epoxy group and a radical polymerizable double bond such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, or the like may be added. When a monomer having an acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate can be added. When an epoxy group-containing monomer such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, a compound having an acid group and a radical polymerizable double bond such as (meth) acrylic acid may be added.
The weight average molecular weight of the (meth) acrylic resin of [1-6-4] is not particularly limited, but is preferably 2000 to 200000, more preferably 4000 to 100000, as measured by GPC and converted to polystyrene. When the weight average molecular weight is more than 200000, the viscosity becomes too high, and it may be difficult to form a coating film, while when the weight average molecular weight is less than 2000, it tends to be difficult to exhibit sufficient heat resistance.
When the (meth) acrylic resin has an acid group, the acid value is preferably 30 to 500mg KOH/g, more preferably 50 to 400mg KOH/g. When the acid value is less than 30mgKOH/g, the application to alkali development may be difficult, and when the acid value exceeds 500mgKOH/g, the viscosity becomes too high, and the coating film tends to be difficult to form.
In the (meth) acrylic resin component, the polymer of which the compound represented by the general formula (6) is an essential monomer component is a known compound per se, and examples thereof include those described in Japanese patent laid-open Nos. 2004-300203 and 2004-300204.
[1-6-5] epoxy (meth) acrylate resin having carboxyl group
The epoxy (meth) acrylate resin was synthesized as follows: an α, β -unsaturated monocarboxylic acid ester having a carboxyl group in an α, β -unsaturated monocarboxylic acid or ester moiety is added to an epoxy resin, and further reacted with a polybasic acid anhydride. The reaction product is not limited to "(meth) acrylate" since it has substantially no epoxy group in its chemical structure, and epoxy resin is used as a raw material and "(meth) acrylate" is a typical example, and is thus named as usual.
As the epoxy resin as a raw material, for example, bisphenol A type epoxy resins (for example, "Epikote (registered trademark, the same shall apply hereinafter)" 828 "," Epikote1001 "," Epikote1002 "," Epikote1004 "manufactured by Mitsubishi chemical corporation), epoxides obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example," NER-1302 "(epoxy equivalent 323, softening point 76 ℃ manufactured by Mitsubishi chemical corporation), bisphenol F type epoxy resins (for example," Epikote 807 "," EP-4001 "," EP-4002 "," EP-4004 and the like manufactured by Mitsubishi chemical corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" (epoxy equivalent 350, softening point 66 ℃ manufactured by Mitsubishi chemical corporation), bisphenol S type epoxy resins, and the like can be preferably used, Biphenyl glycidyl ether (for example, "YX-4000" manufactured by mitsubishi chemical corporation), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by mitsubishi chemical corporation, "EP-152" and "EP-154" manufactured by mitsubishi chemical corporation, "DEN-438" manufactured by Dow chemical corporation)), (o-, m-and p-) cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same shall apply hereinafter) — 102S", "EOCN-1020" and "EOCN-104S" manufactured by mitsubishi chemical corporation), "triglycidyl isocyanurate (for example," TEPIC (registered trademark) "manufactured by nippon chemical corporation), trisphenolic methane type epoxy resin (for example," EPPN (registered trademark, the same shall apply hereinafter) "501", "manufactured by mitsubishi chemical corporation, "EPN-502", "EPPN-503"), a fluorene epoxy resin (for example, Cardo type epoxy resin "ESF-300" manufactured by new hitachi chemical company), "an alicyclic epoxy resin (for example," Celloxide (registered trademark, the same hereinafter) 2021P "and" Celloxide EHPE "manufactured by cellosolve chemical industry co., ltd.), a dicyclopentadiene type epoxy resin obtained by glycidating a phenol resin produced by the reaction of dicyclopentadiene and phenol (for example," XD-1000 "manufactured by japan chemical company," EXA-7200 "manufactured by japan ink company, and" NC-3000 "and" NC-7300 "manufactured by japan chemical company), and an epoxy resin represented by the following structural formula (see japanese patent application laid-open No. 4-355450).
[ chemical formula 17]
These epoxy resins may be used alone or in combination of 2 or more.
As another example of the epoxy resin, a copolymer type epoxy resin can be given. Examples of the copolymer epoxy resin include: a copolymer obtained by reacting glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide, or the like (hereinafter referred to as "component 1 of the copolymerized epoxy resin") with an ethylenically unsaturated group-containing monofunctional compound other than these (hereinafter referred to as "component 2 of the copolymerized epoxy resin"), for example, one or 2 or more species selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α -methylstyrene, glycerol mono (meth) acrylate, and a compound represented by the following general formula (10).
[ chemical formula 18]
In the formula (10), R61Represents a hydrogen atom or an ethyl group, R62Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10. Examples of the compound of the general formula (10) include: polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylateBase) acrylates; alkoxy polyethylene glycol (meth) acrylates such as methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and methoxy tetraethylene glycol (meth) acrylate.
The molecular weight of the above-mentioned copolymerized epoxy resin is preferably about 1000 to 200000. The amount of the component 1 of the copolymerized epoxy resin is preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably 70% by mass or less, particularly preferably 50% by mass or less, based on the component 2 of the copolymerized epoxy resin.
Specific examples of such a copolymer epoxy resin include "CP-15", "CP-30", "CP-50", "CP-20 SA", "CP-510 SA", "CP-50S", "CP-50M" and "CP-20 MA", manufactured by Nikkiso K.K.
The molecular weight of the raw material epoxy resin is usually 200 to 20 ten thousand, preferably 300 to 100000, in terms of weight average molecular weight of polystyrene measured by GPC. When the weight average molecular weight is less than the above range, a problem in film formability may occur in many cases, whereas when the weight average molecular weight exceeds the above range, gelation may easily occur at the time of addition reaction of the α, β -unsaturated monocarboxylic acid, and the production may become difficult.
The α, β -unsaturated monocarboxylic acid includes itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, and the like, and acrylic acid and methacrylic acid are preferable, and acrylic acid having excellent reactivity is particularly preferable.
Examples of the α, β -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include: 2-succinyloxyethyl acrylate, 2-maleyloxyethyl acrylate, 2-phthaloyloxyethyl acrylate, 2-hexahydrophthaloyloxyethyl methacrylate, 2-succinyloxyethyl methacrylate, 2-maleyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, 2-succinyloxyethyl crotonate and the like, with 2-maleyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate being preferred, and 2-maleyloxyethyl acrylate being particularly preferred. These α, β -unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety may be used singly or in combination of 2 or more.
The addition reaction of the α, β -unsaturated monocarboxylic acid or ester thereof with the epoxy resin can be carried out by a known method, for example, by a reaction at a temperature of 50 to 150 ℃ in the presence of an esterification catalyst. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine and the like; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like.
The amount of the α, β -unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, based on 1 equivalent of the epoxy group in the raw epoxy resin. When the amount of the α, β -unsaturated monocarboxylic acid or its ester to be used is too small, the amount of the unsaturated group to be introduced becomes insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. In addition, it is disadvantageous that a large amount of epoxy groups remain. On the other hand, when the amount is too large, the α, β -unsaturated monocarboxylic acid or its ester remains as an unreacted product. In either case, the curing properties tend to deteriorate.
Examples of the polybasic acid anhydride to which an α, β -unsaturated carboxylic acid or an ester thereof is further added to an epoxy resin include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, nadic anhydride, hexachloronorbornenic dianhydride, methyltetrahydrophthalic anhydride, biphenyl tetracarboxylic dianhydride, and the like. Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and biphenyltetracarboxylic dianhydride are preferred, and tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride are particularly preferred compounds. These polybasic acid anhydrides may be used alone or in combination of 2 or more.
The addition reaction of the polybasic acid anhydride can be carried out by a known method, and can be carried out by continuing the reaction under the same conditions as the addition reaction of the α, β -unsaturated monocarboxylic acid or the ester thereof.
The amount of the polybasic add anhydride is preferably such an amount that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150mgKOH/g, and particularly preferably in the range of 20 to 140 mgKOH/g. If the acid value of the resin is too small, the alkali developability is deteriorated, and if the acid value of the resin is too large, the curability tends to be deteriorated.
Examples of the epoxy acrylate resin having a carboxyl group include: a naphthalene-containing resin described in Japanese patent laid-open No. 6-49174; fluorene-containing resins described in Japanese patent application laid-open Nos. 2003-89716, 2003-165830, 2005-325331, and 2001-354735; resins described in, for example, Japanese patent laid-open Nos. 2005-126674, 2005-55814 and 2004-295084.
Further, a commercially available epoxy acrylate resin having a carboxyl group may be used, and examples of the commercially available product include "ACA-200M" manufactured by Daiiluo corporation.
Further, as the binder resin, for example, an acrylic binder described in japanese patent application laid-open No. 2005-154708 and the like can be used.
Among the above-mentioned binder resins, the "resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of the copolymer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction" of [1-6-1] is particularly preferable.
As the binder resin in the present invention, one of the above-mentioned various binder resins may be used alone, or 2 or more kinds may be used in combination.
The above-mentioned binder resins contribute to dispersion stability by a synergistic effect due to the combined use with the above-mentioned dispersant and the like, and as a result, the amount of the dispersant to be added can be reduced, so that the following effects can be exhibited: the developability is improved, and specifically, it is preferable to form a high-density color pixel which has excellent adhesion to a substrate and in which undissolved matter does not remain in a non-image portion on the substrate.
Specifically, a part of the binder resin is used in the dispersion treatment step described later together with the dispersant, the dispersion aid, and the like described above. In this case, the binder resin is preferably used in an amount of about 5 to 200 mass%, more preferably about 10 to 100 mass%, based on the total amount of the pigment in the pigment dispersion liquid.
As described above, the binder resin used in the dispersion treatment step may be any of the resins described above, and particularly preferred are [1-6-4] (meth) acrylic resins, and among them, most preferred is a polymer obtained by polymerizing a monomer component containing a compound represented by the above general formula (6) as an essential component.
When used in the dispersion treatment step together with a dispersant, the acid value of the binder resin is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, most preferably 50mgKOH/g or more, and is preferably 500mgKOH/g or less, more preferably 300mgKOH/g or less, most preferably 200mgKOH/g or less. If the acid value is too high, the viscosity tends to be high, making synthesis difficult, and if the acid value is too low, the application to alkali development may be difficult.
When the binder resin is used in the dispersion treatment step together with a dispersant, the weight average molecular weight of the binder resin measured by GPC and converted to polystyrene is preferably 1000 or more, more preferably 1500 or more, and most preferably 2000 or more, and is preferably 200000 or less, more preferably 50000 or less, and most preferably 30000 or less. If the molecular weight is too large, it tends to be difficult to apply to alkali development, and if it is too small, dispersion stability may be lowered.
In the colored resin composition of the present invention, the content ratio of the binder resin in the total solid content is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less. When the lower limit is not less than the above-mentioned lower limit, a strong film can be obtained, and the adhesion to the substrate tends to be excellent. When the upper limit value is less than or equal to the above upper limit value, the permeability of the developer to the exposed portion is low, and the deterioration of the surface smoothness and sensitivity of the pixel tends to be suppressed.
[1-7] (E) photopolymerization initiator
The colored resin composition of the present invention contains (E) a photopolymerization initiator. By containing (E) a photopolymerization initiator, film curability can be obtained by photopolymerization.
(E) The photopolymerization initiator is usually used in the form of a mixture (photopolymerization initiator system) with an accelerator and an additive such as a sensitizing dye added as needed. The photopolymerization initiation system is a component having a function of directly absorbing light, or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
Examples of the photopolymerization initiator that can be used in the colored resin composition according to embodiment 1 of the present invention include: metallocene compounds containing titanocene compounds described in Japanese patent laid-open Nos. 59-152396 and 61-151197, hexaarylbisimidazole derivatives described in Japanese patent laid-open No. 10-39503, halomethyl s-triazine derivatives, N-aryl-alpha-amino acids such as N-phenylglycine, radical activators such as N-aryl-alpha-amino acid salts and N-aryl-alpha-amino acid esters, alpha-aminoalkylphenol compounds, oxime ester initiators described in Japanese patent laid-open No. 2000-80068, and the like.
Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
Halomethyl s-triazine derivatives such as 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine and the like;
2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-Diazole, 2-trichloromethyl-5-furyl-1, 3,4-Halomethylation of diazoles and the likeAn oxadiazole derivative;
imidazole derivatives such as 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, and (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer;
benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether;
anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone;
benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone;
acetophenone derivatives such as 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α -hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) methanone, 1-hydroxy-1- (p-dodecylphenyl) methanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and 1,1, 1-trichloromethyl (p-butylphenyl) methanone;
thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;
phenazine derivatives such as 9, 10-dimethylbenzylphenylazine (9, 10-dimethyllbenzphenazine);
anthrone derivatives such as benzanthrone;
bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) bis (2,3,4,5, 6-pentafluoro-1-yl) titanium, bis (cyclopentadienyl) bis (2,3,5, 6-tetrafluorophenyl-1-yl) titanium, bis (cyclopentadienyl) bis (2,4, 6-trifluoro-1-yl) titanium, bis (cyclopentadienyl) -2, 6-difluorophenyl-1-yl titanium, bis (cyclopentadienyl) -2, 4-difluorophenyl-1-yl titanium, bis (methylcyclopentadienyl) bis (2,3,4,5, 6-pentafluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl-1-yl) titanium, titanium oxide, Titanocene derivatives such as bis (cyclopentadienyl) -2, 6-difluoro-3- (pyrrol-1-yl) phen-1-yl titanium (ジ - シ ク ロ ペ ン タ ジ エ ニ ル -Ti-2, 6- ジ - フ ル オ ロ -3- (ピ ル -1- イ ル) - フ ェ ニ ー 1- イ ル);
2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminoacetate, 4-diethylaminoacetophenone, 4-dimethylaminopropyl ketone, 2-ethylhexyl 1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and mixtures thereof, Alpha-aminoalkylphenones such as 4- (diethylamino) chalcone;
oxime ester compounds such as 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime) and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime).
Among these, oxime ester compounds are preferable from the viewpoint of sensitivity.
As the accelerator constituting the photopolymerization initiation system, for example, alkyl N, N-dialkylaminobenzoate such as ethyl N, N-dimethylaminobenzoate, 2-mercaptobenzothiazole and the like can be usedHeterocyclic mercapto compounds such as oxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
These photopolymerization initiators and accelerators may be used alone or in combination of 2 or more.
Specific photopolymerization initiation system components include, for example: dialkylacetophenones, benzoin and thioxanthone derivatives described in FINE CHEMICAL (1991, 3/1/day, vol.20 and No.4) pages 16 to 26, hexaarylbisimidazoles, halomethyl-s-triazines described in Japanese patent laid-open No. 58-403023, Japanese patent laid-open No. 45-37377, titanocene described in Japanese patent laid-open No. 4-221958, Japanese patent laid-open No. 4-219756, etc., a system in which a xanthene dye, an ethylenically unsaturated double bond-containing compound having an amino group or a urethane group and capable of addition polymerization, and the like are combined.
The blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 1.5% by mass or more, and is 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, in the entire solid content of the colored resin composition of the present invention. When the lower limit value is set to the upper limit value or more, there is a tendency that sensitivity to exposure light can be sufficiently secured, and when the upper limit value is set to the lower limit value or less, a decrease in solubility of an unexposed portion to a developer can be suppressed, and thus, development failure can be prevented.
On the other hand, the colored resin composition according to the 3 rd aspect of the present invention is characterized in that the (E) photopolymerization initiator contains an oxime ester compound.
When the known zinc halide phthalocyanine pigments described in patent documents 1 to 11 are used, the photopolymerization initiator can be appropriately selected and used according to the use of the colored resin composition, and sufficient photocuring can be performed by using bisimidazole, α -aminoalkylbenzophenone, or the like.
However, when a zinc halide phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more is used, high coloration is obtained due to a change in transmission spectrum caused by the inclusion of a large number of hydrogen atoms, but on the other hand, the absorption of the coating film in a low wavelength region is enhanced and the exposure amount is attenuated, so that when bisimidazole, α -aminoalkylphenone, or the like is used, photocuring cannot be sufficiently performed, and it tends to be difficult to form a fine pattern. On the other hand, it is considered that by using an oxime ester compound having a larger absorption in a low wavelength region as a photopolymerization initiator, photocuring can be sufficiently performed, and a fine pattern can be formed.
Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in combination in its structure, the sensitivity is high even in a small amount, and the oxime ester compound is stable against thermal reaction, and a photosensitive resin composition having high sensitivity can be designed in a small amount. In particular, from the viewpoint of light absorption with respect to i-rays (365nm) of an exposure light source, oxime ester compounds containing a carbazole ring optionally having a substituent are preferable.
Examples of the oxime ester compounds include compounds represented by the following general formula (I-1).
[ chemical formula 19]
In the above formula (I-1), R21aRepresents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
R21bRepresents an optional substituent comprising an aromatic ring or a heteroaromatic ring.
R22aRepresents an alkanoyl group optionally having a substituent, or an aroyl group optionally having a substituent.
R21aThe number of carbon atoms of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity to exposure. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
Examples of the substituent optionally contained in the alkyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group, an N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
As R21aExamples of the aromatic ring group in (3) include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. From the viewpoint of developability, the amount is preferably 30 or less, more preferably 20 or less, still more preferably 12 or less, and particularly preferably 8 or less.
Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like, and among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent optionally contained in the aromatic ring group include a hydroxyl group, an alkyl group optionally containing a substituent, an alkoxy group optionally containing a substituent, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group and the like, and from the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. Examples of the substituent of the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group and a halogen atom.
Of these, R is preferable from the viewpoint of developability21aIs optionally substitutedThe alkyl group of the group is more preferably an unsubstituted alkyl group, and still more preferably a methyl group.
In addition, R21bFrom the viewpoint of solubility in a solvent and sensitivity to exposure, preferable examples of the substituent include a carbazolyl group optionally having a substituent, a thioxanthone group optionally having a substituent, and a diphenylsulfide group optionally having a substituent. Of these, carbazolyl groups optionally having a substituent are preferable from the viewpoint of light absorption with respect to i-ray (365nm) of an exposure light source.
In addition, R22aThe number of carbon atoms of the alkanoyl group in (b) is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the alkanoyl group include an acetyl group, a propionyl group, a butyryl group and the like.
Examples of the substituent optionally contained in the alkanoyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
In addition, R22aThe number of carbon atoms of the aroyl group in (2) is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the aroyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent optionally contained in the aroyl group include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
Among the compounds represented by the above general formula (I-1), compounds represented by the following general formula (I-2) can be mentioned from the viewpoint of light absorption with respect to I-rays (365nm) of an exposure light source.
[ chemical formula 20]
In the above formula (I-2), R21aAnd R22aIs synonymous with the above general formula (I-1).
R23aRepresents an alkyl group optionally having a substituent.
R24aRepresents an alkyl group optionally having a substituent, an aroyl group optionally having a substituent, a heteroaroyl group optionally having a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a fused aromatic ring.
R23aThe number of carbon atoms of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably not 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.
Examples of the substituent optionally contained in the alkyl group include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
R23aThe number of carbon atoms of the aroyl group in (2) is not particularly limited, and is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 9 or less, from the viewpoint of solubility in a solvent. Specific examples of the aroyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent optionally contained in the aroyl group include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like, and an ethyl group is preferable from the viewpoint of ease of synthesis.
R23aThe number of carbon atoms of the heteroaroyl group in (b) is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, further preferably 20 or less, from the viewpoint of solubility in a solventAnd 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group and a bromonaphthoyl group.
Examples of the substituent optionally contained in the heteroaroyl group include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
Among these, as R23aFrom the viewpoint of solubility in a solvent and ease of synthesis, an alkyl group is preferable, and an ethyl group is more preferable.
The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a fused aromatic ring.
Examples of commercially available oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF corporation, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qiangli corporation, and NCI-831 manufactured by ADEKA corporation.
Specific examples of the oxime ester compounds include the following compounds, but are not limited to these compounds.
[ chemical formula 21]
[ chemical formula 22]
[ chemical formula 23]
The colored resin composition according to embodiment 3 of the present invention may contain an oxime ester compound as the photopolymerization initiator (E), or may contain a photopolymerization initiator other than the oxime ester compound. Examples thereof include: metallocene compounds containing titanocene compounds described in Japanese patent application laid-open Nos. 59-152396 and 61-151197, hexaarylbisimidazole derivatives described in Japanese patent application laid-open No. 10-39503, halomethyl s-triazine derivatives, N-aryl-alpha-amino acids such as N-phenylglycine, radical activators such as N-aryl-alpha-amino acid salts and N-aryl-alpha-amino acid esters, and alpha-aminoalkylphenone compounds.
As the accelerator constituting the photopolymerization initiation system, for example, alkyl N, N-dialkylaminobenzoates such as ethyl N, N-dimethylaminobenzoate, 2-mercaptobenzothiazole and 2-mercaptobenzothiazole can be usedHeterocyclic mercapto compounds such as oxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
These photopolymerization initiators and accelerators may be used alone or in combination of 2 or more.
In the colored resin composition according to embodiment 3 of the present invention, the proportion of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 2.0% by mass or more, and is usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, of the total solid content of the colored resin composition of the present invention. By setting the lower limit value or more, it is possible to sufficiently secure sensitivity to exposure light, and by setting the upper limit value or less, it is possible to suppress a decrease in solubility of an unexposed portion in a developer, and it is possible to prevent a development failure.
On the other hand, in the photopolymerization initiation system component, a sensitizing dye corresponding to the wavelength of the image exposure light source may be blended as necessary in order to improve the sensitivity. Examples of such sensitizing dyes include xanthene dye disclosed in Japanese patent application laid-open No. 4-221958, Japanese patent application laid-open No. 4-219756, coumarin dye having a heterocyclic ring disclosed in Japanese patent application laid-open No. 3-239703, coumarin dye having a heterocyclic ring disclosed in Japanese patent application laid-open No. 5-289335, 3-oxocoumarin compound disclosed in Japanese patent application laid-open No. 3-239703, 3-oxocoumarin compound disclosed in Japanese patent application laid-open No. 5-289335, methylenepyrrole dye disclosed in Japanese patent application laid-open No. 6-19240, and Japanese patent application laid-open No. 47-2528, Japanese patent application laid-open No. 54-155292, Japanese patent application laid-open No. 45-37377, Japanese patent application laid-open No. 48-84183, Japanese patent application laid-open No. 52-112681, Japanese patent application laid-open No. 58-15503, Japanese patent application laid-open, And pigments having a dialkylaminobenzene skeleton as described in Japanese patent laid-open Nos. 59-56403, 2-69, 57-168088, 5-107761, 5-210240, and 4-288818.
Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are benzophenone-based compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoAzole, 2- (p-diethylaminophenyl) benzoAzole, 2- (p-dimethylaminophenyl) benzo [4, 5]]Benzo (b) isAzole, 2- (p-dimethylaminophenyl) benzo [6, 7]]Benzo (b) isOxazole, 2, 5-bis (p-diethylaminophenyl) -1,3,4-Azole, 2- (p-dimethylamino)P-dialkylaminophenyl group-containing compounds such as phenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine. Among them, the most preferable is 4, 4' -dialkylaminobenzophenone.
The sensitizing dye may be used alone or in combination of 2 or more.
The compounding ratio of the sensitizing dye in the colored resin composition of the present invention is usually 0 mass% or more, preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and is usually 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less, of the total solid content of the colored resin composition.
[1-8] other solid ingredients
If necessary, solid components other than the above components may be blended in the colored resin composition of the present invention. Examples of such components include photopolymerizable monomers, organic carboxylic acids, organic carboxylic acid anhydrides, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protectants, adhesion improvers, development improvers, dyes, and the like.
[1-8-1] photopolymerizable monomer
The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, and is preferably an addition polymerizable compound having at least one olefinic double bond (hereinafter referred to as "olefinic compound"). The olefinic compound is a compound having an olefinic double bond which is addition-polymerized and cured by the action of a photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with active light. The term "monomer" as used herein refers to a concept of a polymer substance and includes a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.
Examples of the olefinic compound include: unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification of unsaturated carboxylic acids and polycarboxylic acids with the previously described aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds and other polyhydroxy compounds, olefinic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound, and the like.
Examples of the ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid include: acrylic esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Examples of the acrylic acid ester include methacrylic acid esters obtained by replacing an acrylic acid moiety with a methacrylic acid moiety, itaconic acid esters obtained by replacing an itaconic acid moiety, crotonic acid esters obtained by replacing a crotonic acid moiety, and maleic acid esters obtained by replacing a maleic acid moiety.
Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include: hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, 1,2, 3-benzenetriol triacrylate, and the like.
The esters obtained by esterification of unsaturated carboxylic acids and polycarboxylic acids with polyhydroxy compounds need not be a single substance but may be mixtures. Typical examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; a condensate of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerol, and the like.
The urethane skeleton-containing olefinic compound obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxyl compound includes, for example: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; a reaction product of an aromatic diisocyanate such as benzylidene diisocyanate or diphenylmethane diisocyanate and a (meth) acryloyl group-containing hydroxyl compound such as 2-hydroxyethyl acrylate, 2-hydroxyacetic acid methacrylate, 3-hydroxy (1,1, 1-triacryloxymethyl) propane, or 3-hydroxy (1,1, 1-trimethylacryloyloxymethyl) propane.
Further, as the olefinic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate and the like are also useful.
In addition, the olefinic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid, and a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydric compound is preferable, and in the ester, the aliphatic polyhydric compound is pentaerythritol and/or dipentaerythritol.
These monomers may be used alone, but since it is difficult to use a single compound in the preparation, 2 or more kinds may be mixed and used. Further, a polyfunctional monomer having no acid group as a monomer may be used in combination with a polyfunctional monomer having an acid group as needed.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the polyfunctional monomer is too low, the development dissolution property is lowered, and if the acid value of the polyfunctional monomer is too high, the production and handling become difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be deteriorated. Therefore, when 2 or more kinds of different acid groups of the polyfunctional monomer are combined, or when a polyfunctional monomer having no acid group is combined, it is preferable to adjust the acid groups as the entire polyfunctional monomer to fall within the above range.
In the present invention, a more preferable polyfunctional monomer having an acid group is a monomer commercially available as TO1382 from east asia synthetic company, and is a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate as a main component. A combination of polyfunctional monomers other than the polyfunctional monomer may also be used. Furthermore, the polyfunctional monomers described in Japanese patent application laid-open Nos. 2013-140346 [0056] and [0057] may be used.
In the present invention, the polymerizable monomer described in jp 2013 a 195971 is preferable from the viewpoint of improving the chemical resistance of the pixel and the linearity of the pixel edge. From the viewpoint of achieving both sensitivity of the coating film and shortening of the development time, the polymerizable monomer described in jp 2013-195974 a is preferred.
The content of these photopolymerizable monomers is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less, of the total solid content of the colored resin composition of the present invention. The ratio to 100 parts by mass of the pigment (a) is usually 0 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more, and is usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.
[1-8-2] organic carboxylic acid, organic carboxylic acid anhydride
The colored resin composition of the present invention may contain an organic carboxylic acid and/or an organic carboxylic acid anhydride having a molecular weight of 1000 or less.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic maleic acid, and fumaric acid, and tricarboxylic acids such as tricarballylic acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids having a carboxyl group directly bonded to a phenyl group, such as benzoic acid and phthalic acid, and carboxylic acids having a carboxyl group bonded to a phenyl group via a carbon bond. Among these, organic carboxylic acids having a molecular weight of 600 or less, particularly 50 to 500, are particularly preferable, and specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.
Examples of the organic carboxylic acid anhydride include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides, and specific examples thereof include aliphatic carboxylic acid anhydrides such as acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1, 2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride. Examples of the aromatic carboxylic acid anhydride include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like. Among these, organic carboxylic acid anhydrides having a molecular weight of 600 or less, particularly 50 to 500, are particularly preferable, and specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.
The amount of the organic carboxylic acid and/or the organic carboxylic acid anhydride added is usually 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, of the total solid content.
By adding these organic carboxylic acids and/or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, the remaining undissolved matter of the colored resin composition can be further reduced while maintaining high pattern adhesion.
[1-8-3] surfactant
As the surfactant, various surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used, and a nonionic surfactant is preferably used in view of low possibility of exerting an adverse effect on each property. The concentration range of the surfactant is usually 0.001 mass% or more, preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and most preferably 0.03 mass% or more, and usually 10 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, and most preferably 0.3 mass% or less, based on the total solid content.
[1-8-4] thermal polymerization inhibitor
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2, 6-t-butyl-p-cresol, and β -naphthol. The amount of the thermal polymerization inhibitor is preferably 3% by mass or less based on the total solid content of the composition.
[1-8-5] plasticizer
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetin. The amount of these plasticizers to be blended is preferably within a range of usually 10% by mass or less based on the total solid content of the composition.
[2] Preparation of colored resin composition
Next, a method for producing the colored resin composition (hereinafter, may be referred to as a resist) of the present invention will be described.
First, a pigment dispersion liquid is prepared by weighing a given amount of each of a pigment, a solvent and a dispersant, and dispersing the pigment containing a zinc bromide phthalocyanine pigment in a dispersion treatment step. In the dispersion treatment step, a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the color material is finely pulverized, and therefore, the coating properties of the colored resin composition are improved, and the transmittance of the pixels in the color filter substrate of the product is improved.
In the dispersion treatment of the pigment, as described above, it is preferable to use a dispersion aid, a dispersion resin, or the like in combination as appropriate.
Further, the pigment is required to contain a pigment containing the above-mentioned zinc bromide phthalocyanine pigment, but when used for toning, other pigments may be mixed and dispersed.
In the case of performing the dispersion treatment using a sand mill, glass beads or zirconia beads having a particle diameter of 0.1 to several mm are preferably used. The temperature at the time of the dispersion treatment is usually 0 ℃ or higher, preferably room temperature or higher, and usually 100 ℃ or lower, preferably 80 ℃ or lower. The dispersion time varies depending on the composition of the pigment dispersion, the size of the sand mill, and the like, and therefore, the dispersion time needs to be adjusted as appropriate.
The pigment dispersion liquid obtained by the dispersion treatment is mixed with a solvent, a binder resin, a photopolymerization initiator, and, if necessary, a predetermined amount of a photopolymerizable monomer and other components to prepare a uniform dispersion solution. In the dispersion treatment step and the mixing step, fine dust may be mixed, and therefore, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.
[3] Fabrication of color filter substrates
Next, the color filter of the present invention will be explained.
The color filter of the present invention has pixels formed using the colored resin composition.
[3-1] transparent substrate (support)
The material of the transparent substrate for the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of the material include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among them, glass or a heat-resistant resin is preferable from the viewpoint of heat resistance.
In order to improve surface properties such as adhesiveness, the transparent substrate and the black matrix-forming substrate may be subjected to corona discharge treatment, ozone treatment, film formation treatment with various resins such as a silane coupling agent and a urethane resin, or the like, as necessary. The thickness of the transparent substrate is usually set to 0.05mm or more, preferably 0.1mm or more, and usually 10mm or less, preferably 7mm or less. In addition, when a thin film forming process of various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and is usually 10 μm or less, preferably 5 μm or less.
[3-2] Black matrix
The color filter of the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green, and blue colors in general. In the red, green and blue pixels, the colored resin composition is used as a coating liquid for forming green pixels (resist patterns). Using this green resist, a pixel image is formed by performing processes of coating, heat drying, image exposure, development, and heat curing on a resin black matrix formation surface formed on a transparent substrate or a metal black matrix formation surface formed using another light-shielding metal material such as a chromium compound.
A black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, nickel, a tungsten alloy, or the like can be used, and these can be laminated in a multilayer form.
These metal light-shielding films are generally formed by a sputtering method, and after a desired pattern is formed in a film shape using a positive photoresist, chromium is etched using an etching solution in which ammonium ceric nitrate and perchloric acid and/or nitric acid are mixed; for other materials, etching is performed using an etching solution corresponding to the material, and finally, the positive photoresist is stripped with a dedicated stripper, whereby a black matrix can be formed.
In this case, first, a thin film of these metals or metal/metal oxides is formed on a transparent substrate by vapor deposition, sputtering, or the like. Next, after a coating film of the colored resin composition is formed on the film, the coating film is exposed and developed using a photomask having a repeating pattern such as a stripe, a mosaic, a triangle, or the like, to form a resist image. Then, the coating film may be subjected to etching treatment to form a black matrix.
When the photosensitive colored resin composition for a black matrix is used, the black matrix is formed using a colored resin composition containing a black color material. For example, a Black matrix can be formed by using a colored resin composition containing one or more Black color materials such as carbon Black, graphite, iron Black, aniline Black, Cyanine Black (blue), and titanium Black, or a Black color material obtained by mixing red, green, and blue colors selected as appropriate from inorganic or organic pigments and dyes, in the same manner as the method for forming red, green, and blue pixels described later.
[3-3] formation of pixels
The method of forming the pixel differs depending on the type of the colored resin composition used, and a case where a photopolymerizable composition is used as the colored resin composition will be described as an example.
A colored resin composition of one of red, green, and blue colors is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is superimposed on the coating film, image exposure and development are performed through the photomask, and a pixel image is formed by thermal curing or photo curing as necessary, thereby producing a colored layer. This operation is performed for the colored resin compositions of the three colors of red, green, and blue, respectively, whereby a color filter image can be formed.
The color filter colored resin composition can be applied by spin coating, Wire bar coating, flow coating, die coating, roll coating, spray coating, or the like. Among these, if the die coating method is employed, the amount of the coating liquid used can be greatly reduced, and the effect of fogging or the like which is attached when the coating is performed by the spin coating method is not caused at all, and the generation of foreign matter or the like can be suppressed, which is preferable from the overall viewpoint.
When the thickness of the coating film is too large, pattern development becomes difficult, and it is sometimes difficult to adjust the gap in the step of forming a liquid crystal cell, while when the thickness of the coating film is too small, it is difficult to increase the pigment concentration, and it may not be possible to develop a desired color. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and is usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less in terms of the film thickness after drying.
[3-4] drying of coating film
The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR Oven, or a Convection Oven (Convection Oven). Usually, after the preliminary drying, the coating film is dried by heating again. The conditions for the preliminary drying may be appropriately selected depending on the kind of the solvent component, the performance of the dryer used, and the like. The drying temperature and the drying time are selected depending on the kind of the solvent component, the performance of the dryer used, and the like, and specifically, the drying temperature is usually 40 ℃ or more, preferably 50 ℃ or more, and usually 80 ℃ or less, preferably 70 ℃ or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or more, preferably 3 minutes or less.
The temperature condition for the reheating drying is preferably higher than the temperature for the preliminary drying, and specifically, is usually 50 ℃ or higher, preferably 70 ℃ or higher, and is usually 200 ℃ or lower, preferably 160 ℃ or lower, and particularly preferably 130 ℃ or lower. The drying time is generally 10 seconds or more, preferably 15 seconds or more, and generally 10 minutes or less, preferably 5 minutes or less, although it depends on the heating temperature. The higher the drying temperature is, the more the adhesiveness to the transparent substrate is improved, but if it is too high, the binder resin is decomposed to cause thermal polymerization, and development failure may occur. As the drying step of the coating film, a reduced pressure drying method of drying in a reduced pressure chamber without raising the temperature may be used.
[3-5] Exposure Process
Image exposure was performed as follows: a negative matrix pattern is superimposed on a coating film of the colored resin composition, and a light source for irradiating ultraviolet rays or visible rays through the matrix pattern is provided. In this case, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer and then exposed as necessary. The light source used for the image exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; or a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium-cadmium laser, or a semiconductor laser. When light of a specific wavelength is used for irradiation, an optical filter may be used.
[3-6] developing step
The color filter of the present invention can be produced by image-exposing a coating film using the colored resin composition of the present invention to light using the light source, and then developing the resulting coating film using an organic solvent or an aqueous solution containing a surfactant and a basic compound to form an image on a substrate. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
Examples of the basic compound include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogencarbonate, potassium hydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, and ammonium hydroxide; organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of 2 or more.
Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglycerol alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; amphoteric surfactants such as alkylbetaines and amino acids.
Examples of the organic solvent include: isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions of the development treatment are not particularly limited, and the development temperature is preferably in the following range: usually 10 ℃ or higher, preferably 15 ℃ or higher, more preferably 20 ℃ or higher, and usually 50 ℃ or lower, preferably 45 ℃ or lower, more preferably 40 ℃ or lower. The developing method may be any of a dip developing method, a spray developing method, a brush developing method, an ultrasonic developing method, and the like.
[3-7] Heat curing treatment
The developed color filter is subjected to a heat curing treatment. As the conditions for the heat curing treatment at this time, the temperature is selected within the following range: usually 100 ℃ or higher, preferably 150 ℃ or higher, and usually 280 ℃ or lower, preferably 250 ℃ or lower; the time is selected from the range of 5 minutes to 60 minutes. Through the series of steps, image formation of a pattern of one color is completed. This process is repeated in this order to pattern black, red, green, and blue, thereby forming a color filter. The order of forming the four color patterns is not limited to the above order.
The color filter of the present invention can be produced by the following method (1) in addition to the above-described production method: (1) a method of forming a pixel image by an etching method, which comprises applying a curable colored resin composition containing a solvent, a zinc bromide chloride phthalocyanine pigment as a coloring material, and a polyimide resin as a binder resin onto a substrate. Further, there may be enumerated: (2) a method of forming a pixel image directly on a transparent substrate using a printing press using a colored resin composition containing a zinc bromide chloride phthalocyanine pigment as a coloring ink; (3) a method of using a colored resin composition containing a zinc chloride bromide phthalocyanine pigment as an electrodeposition liquid, immersing a substrate in the electrodeposition liquid, and depositing a colored film on an ITO electrode patterned into a predetermined pattern, and the like. Mention may also be made of: (4) a method in which a film coated with a colored resin composition containing a zinc chloride bromide phthalocyanine pigment is pasted on a transparent substrate, and peeling, image exposure, and development are performed to form a pixel image; and (5) a method of forming a pixel image by ink jet printing using a colored resin composition containing a zinc bromide chloride phthalocyanine pigment as a coloring ink. The color filter can be produced by a method suitable for the composition of the colored resin composition.
[3-8] formation of transparent electrode
The color filter of the present invention can be used as a part of a member of a color display, a liquid crystal display device, or the like by forming a transparent electrode such as ITO on an image as it is, but a surface coating layer of polyamide, polyimide, or the like may be provided on the image as necessary for the purpose of improving surface smoothness and durability. In some applications such as an in-plane alignment driving method (IPS mode), a transparent electrode may not be formed.
[4] Image display device (Panel)
Next, the image display device of the present invention will be explained. The image display device of the present invention has the color filter described above. Hereinafter, a liquid crystal display device and an organic el (electroluminescence) display device, which are image display devices, will be described in detail.
[4-1] liquid crystal display device
A method for manufacturing a liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention is generally completed by forming an alignment film on the color filter of the present invention, distributing spacers on the alignment film, bonding the alignment film to a counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and connecting the liquid crystal cell to a counter electrode. The alignment film is preferably a resin film such as polyimide. In the formation of the alignment film, the thickness of the alignment film is set to several 10nm by gravure printing and/or flexographic printing. After the alignment film is cured by heat baking, the alignment film is subjected to surface treatment by ultraviolet irradiation or rubbing treatment to adjust the tilt of the liquid crystal.
The spacer may have a size corresponding to the gap between the substrates, and is preferably 2 to 8 μm. A Photosensitive Spacer (PS) of a transparent resin film is formed on the color filter substrate using a photolithography method, and is used instead of the spacer. As the counter substrate, an array substrate is generally used, and a TFT (thin film transistor) substrate is particularly preferably used.
The gap between the counter substrate and the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected from the range of 2 μm to 8 μm. After the liquid crystal is bonded to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sheet is cured by UV irradiation and/or heating, and the liquid crystal cell is sealed around.
After the liquid crystal cell sealed at the periphery is disconnected from the panel unit, the pressure in the vacuum container is reduced, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal leaks into the container, whereby the liquid crystal is injected into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1X 10-2Pa or more, preferably 1X 10-3Pa or more, and usually 1X 10-7Pa or less, preferably 1X 10- 6Pa or less. The liquid crystal cell is preferably heated at a temperature of usually 30 ℃ or more, preferably 50 ℃ or more, and usually 100 ℃ or less, preferably 90 ℃ or less, while the pressure is reduced.
The heating and holding time under reduced pressure is usually set to a range of 10 minutes to 60 minutes, and then the liquid crystal is immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is cured by the UV curable resin to seal the liquid crystal injection port, thereby completing the liquid crystal display device (panel).
The type of the liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, lyotropic liquid crystals, thermotropic liquid crystals, and the like. Known thermotropic liquid crystals are: the nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like may be any.
[4-2] organic EL display device
In order to produce an organic EL display having the color filter of the present invention, for example, as shown in fig. 1, pixels 20 are formed on a transparent support substrate 10 using the colored resin composition of the present invention, and an organic light emitting body 500 is laminated on a blue color filter on which the pixels 20 are formed, with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween, thereby producing a multicolor organic EL element.
As a lamination method of the organic light emitting body 500, there can be mentioned: a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter; a method of bonding the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40. The organic EL element 100 thus fabricated can be applied to a passive-drive organic EL display device as well as an active-drive organic EL display device.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples, "parts" means "parts by mass".
< Green pigment >
In the examples and comparative examples, green pigments a and B described in table 1 were used.
The average chlorine number and the average bromine number in table 1 are values measured by the fluorescent X-ray basic parameter method (FP method), and are average values of the chlorine number and the bromine number occupied in 16 substitution sites of 1 molecule of zinc phthalocyanine. The zinc bromochloride phthalocyanine is obtained by substituting 16 hydrogen atoms contained in 1 molecule of zinc phthalocyanine by chlorine atoms and bromine atoms, and the average hydrogen atom number can be calculated by subtracting the sum of the average chlorine atom number and the average bromine atom number from 16. The average number of chlorine atoms and the average number of bromine atoms can be calculated as a relative value corresponding to1 zinc atom from the mass ratio of zinc atoms, chlorine atoms and bromine atoms measured by FP. The fluorescent X-ray evaluation apparatus used RIX-3000 manufactured by RIKO MOTOR INDUSTRIAL CO., LTD, and the X-ray tube was measured in a vacuum atmosphere with a measurement diameter of 30 mm.phi.using Rh50kV/50 mA. The amount of the sample was measured and used at 2g after press molding (30 mm. phi., 200 kN). The average number of chlorine atoms and the average number of bromine atoms in 1 molecule were defined as the average values of the whole measurement sample. Other specific conditions set on the screen of RIX-3000 are shown in Table 2. The green pigment B was c.i. pigment green 58.
[ Table 1]
[ Table 2]
Optical spectrum Slit Spectroscopic crystal Detector Primary optical filter Attenuator
Br Kb1 COARSE LIF1 Scintillation counter OUT 1/1
Zn Ka COARSE LIF1 Scintillation counter OUT 1/1
C Ka 5S RX60 Proportional counter OUT 1/1
N Ka 5S RX40 Proportional counter OUT 1/1
Cl Ka FINE GE Proportional counter OUT 1/1
Further, in Table 3, the content ratio of chlorine atoms and the content ratio of bromine atoms measured by combustion ion chromatography with respect to the green pigments A and B as in Table 1 are shown. Specifically, each pigment was dissolved in ethyl benzoate, and the resultant was combusted in a combustion apparatus to absorb the combustion gas in a hydrogen peroxide absorbing solution, and the ions in the absorbing solution were measured by ion chromatography.
The average number of hydrogen atoms contained in one molecule of the green pigments a and B described in table 3 is a value measured by Laser Desorption/Ionization (LDI) -mass spectrometry (MassSpectrometry, MS). After dissolving 1 to 3mg of the pigment in 100mg of THF (tetrahydrofuran) or NMP (N-methylpyrrolidone) and applying ultrasonic waves, several μ L of the solution was fixed on a plate, and the resultant was measured in a reflection mode, a Positive mode, and a laser power: the measurement is carried out under the conditions of about 40% to 60%, 500shots × 3, and m/z of 300 to 3000. The mass spectrum of green pigment a is shown in fig. 2, and the mass spectrum of green pigment B is shown in fig. 3. The average number of hydrogen atoms contained in one molecule was measured in the following order.
First, the maximum peak intensity in the mass spectrum is used as a reference, and the 40% intensity thereof is used as a threshold. Next, the peak equal to or larger than the threshold is set as a peak to be calculated, the number of hydrogen atoms is calculated from the molecular weight of the peak value of each peak, and the average number of hydrogen atoms is calculated by averaging these.
[ Table 3]
< Dispersion resin A >
The dispersion resin a was synthesized in the following order.
First, a separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was added thereto, nitrogen gas was replaced, and the reaction vessel was heated to 90 ℃ with stirring in an oil bath.
On the other hand, 30 parts by mass of dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of t-butyl peroxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were charged into a monomer tank, 5.2 parts by mass of n-dodecylmercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into a chain transfer agent tank, and after the temperature in the reaction tank was stabilized at 90 ℃, dropwise addition from the monomer tank and the chain transfer agent tank was started to start polymerization. The temperature was maintained at 90 ℃ and the dropwise addition was carried out over 135 minutes, and 60 minutes after the completion of the dropwise addition, the temperature was raised to 110 ℃.
After keeping at 110 ℃ for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen (5/95 (v/v)) was started. Then, 39.6 parts by mass of glycidyl methacrylate, 0.4 part by mass of 2, 2' -methylenebis (4-methyl-6-tert-butylphenol), and 0.8 part by mass of triethylamine were added to the reaction vessel, and the reaction was carried out at 110 ℃ for 9 hours.
After cooling to room temperature, a polymer solution having a weight average molecular weight of 8000 and an acid value of 101mgKOH/g as the dispersion resin A was obtained.
< dispersant A: dispersant "BYK-LPN 6919" >, manufactured by BYK-Chemie
A methacrylic AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having solventropic properties, which has repeating units represented by the following formulae (2B) and (3B) but does not have a repeating unit represented by the following formula (1B), and which has an amine value of 120mgKOH/g and an acid value of 1mgKOH/g or less.
The content of the following formula (2B) in the total repeating units of the a block was 100 mol%, and the content of the following formula (3B) in the total repeating units of the B block was 11 mol%.
[ chemical formula 24]
< adhesive resin A >
The binder resin a was synthesized in the following order.
The mixture was stirred while replacing 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, and the temperature was raised to 120 ℃. To this solution, 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., Ltd.) were added dropwise, and further stirring was continued at 120 ℃ for 2 hours. Subsequently, the inside of the reaction vessel was changed to air replacement, and 0.7 parts by mass of tris (dimethylaminomethyl) phenol and 0.12 parts by mass of hydroquinone were added to 27 parts by mass of acrylic acid, and the reaction was continued at 120 ℃ for 6 hours. Then, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 part by mass of triethylamine were added thereto, and the mixture was reacted at 120 ℃ for 3.5 hours. The weight average molecular weight Mw of the binder resin a thus obtained was about 15000 as measured by GPC and converted to polystyrene.
< photopolymerization initiator 1 >
In examples and comparative examples, [ 9-ethyl-6- (1-acetoxyimino-4-methoxycarbonylbutyl) carbazol-3-yl ] (2-methylphenyl) ketone having the following structure was used as a photopolymerization initiator.
[ chemical formula 25]
"Me" in the above structural formula represents a methyl group.
< surfactant A >
Megafac F-559 (fluorine-based surfactant, available from DIC Co., Ltd.)
Examples 1 to 5 and comparative examples 1 to 3
Green pigment and solvent were used in the kinds and amounts described in table 4, dispersant a was used as a dispersant in an amount of 4.0 parts by mass in terms of solid content, dispersion resin a was used as a dispersion resin in an amount of 4.0 parts by mass in terms of solid content, and zirconia beads 225 parts by mass having a diameter of 0.5mm were used, and these were filled in a stainless steel container and dispersed for 6 hours by a paint shaker to prepare green pigment dispersions of examples 1 to 5 and comparative examples 1 to 3. In Table 4, the boiling point is a value of 1013.25hPa and the vapor pressure is a value of 20 ℃. The amount of solvent 1 added in table 4 is the total amount contained in the green pigment dispersion liquid.
[ Table 4]
DEGEA: diethylene glycol monoethyl ether acetate
DEGBEA: diethylene glycol monobutyl ether acetate
1, 3-BGDA: 1, 3-butanediol diacetate
EEP: 3-Ethoxypropionic acid ethyl ester
MBA: 3-Methoxybutyl acetate
BA: butyl acetate (butyl acetate)
PGMEA: propylene glycol monomethyl ether acetate
< preparation of colored resin composition >
The other components shown in table 5 were mixed with each of the above pigment dispersions to prepare colored resin compositions. In table 5, the amount of the binder resin and the photopolymerizable monomer blended is a value converted into a solid content, and the amount of the solvent blended is a value including the amount of the solvent contained in the binder resin and the photopolymerizable monomer.
[ Table 5]
< evaluation of adhesion >
Evaluation was carried out in accordance with [ coating suitability evaluation method (I) ] described in examples of Japanese patent laid-open No. 2007-270147.
The colored resin composition obtained in the above-described procedure was subjected to the following evaluations (1) to (4), and at this time, a test piece was attached to the arm of the regulator, and a control device was used which automatically operated to repeat the movement of the tip of the test piece into and out of the colored resin composition filled in the bottle.
(1) A glass test piece 100mm in length, 5mm in width, and 0.6mm in thickness was immersed at 20mm in the longitudinal front end portion thereof in the colored resin composition at a speed of 12.5 mm/sec at an atmospheric temperature of 23 ℃ and then held for 4 seconds.
(2) The glass test piece was taken out from the colored resin composition at a speed of 12.5 mm/sec, and the tip of the glass test piece was held vertically downward, followed by drying for 56 seconds under conditions of an atmospheric temperature of 23 ℃, a humidity of 55%, and a wind speed of 0.5. + -. 0.2 m/sec.
(3) The steps (1) and (2) were repeated a total of 120 times, and deposits derived from the colored resin composition were formed on the glass test piece.
(4) The deposits on the glass sheets were observed with a microscope, and the results are shown in table 6. The evaluation criteria for the deposit are as follows. In table 6 (), the value represents the ratio (%) of the area covered with the deposit to the total immersion area of the glass sheet.
O: the proportion of the area covered with the adherent was 0% with respect to the total impregnated area of the glass sheet
And (delta): the proportion of the area covered with the adherent is more than 0% and less than 10% with respect to the total impregnated area of the glass sheet
X: the ratio of the area covered with the adherent substance to the total immersion area of the glass sheet is 10% or more
[ Table 6]
As is clear from Table 6, in example 1 in which the green pigment A was used and DEGEA having a boiling point of 217 ℃ was used and in example 2 in which DEGBEA having a boiling point of 247 ℃ was used, substantially no deposit was observed on the glass sheet, and the results were very good. Further, example 3 using 1,3-BGDA having a boiling point of 232 ℃, example 4 using EEP having a boiling point of 170 ℃ and example 5 using MBA having a boiling point of 171 ℃ showed only very few deposits on the glass sheet, and were also good. It is considered that, by using a high boiling point solvent having a boiling point of 150 ℃ or higher, the glass flake is not easily dried and easily kept in a wet state at the time of drying for 56 seconds in the step (2) of evaluating the deposit, and is easily dissolved again by the colored resin composition at the time of immersion for 4 seconds in the step (1) to be performed next, and the amount of the deposit remaining on the glass flake is reduced.
On the other hand, in comparative example 1 using BA having a boiling point of 126 ℃ and comparative example 2 using PGMEA alone having a boiling point of 146 ℃, a very large amount of deposits were observed on the glass sheet.
In comparative example 3 using the green pigment B, although the solvent having a high boiling point of 150 ℃ or higher was not contained, it was confirmed that substantially no deposit was observed on the glass sheet. The reason for this is not clear, but it is considered that the average number of hydrogen atoms contained in one molecule of the green pigment B is very small, the wettability and the adsorption of the pigment are good, the dispersant and the dispersion resin released from the pigment are small, the surface of the pigment is sufficiently covered, and the solubility in the solvent is good.
In summary of the results in Table 6, when the green pigment A was used, the colored resin compositions of examples 1 to 5 using a solvent having a high boiling point tended to have less deposits on glass flakes and were considered to have very high coating properties, as compared with the colored resin compositions of comparative examples 1 and 2 using a solvent having a low boiling point.
(examples 6 to 11)
Green pigment dispersions of examples 6 to 11 were prepared in the same manner as in example 1, except that the green pigment and the solvent were used in the kinds and amounts shown in Table 7. In Table 7, the boiling point is a value of 1013.25hPa and the vapor pressure is a value of 20 ℃. The amount of solvent 1 added in table 7 is the total amount contained in the green pigment dispersion liquid.
[ Table 7]
< preparation of colored resin composition >
The other components shown in table 8 were mixed with each of the pigment dispersions in table 7 to prepare colored resin compositions. In table 8, the amount of the binder resin and the photopolymerizable monomer blended is a value converted into a solid content, and the amount of the solvent blended is a value including the amount of the solvent contained in the binder resin and the photopolymerizable monomer.
[ Table 8]
Subsequently, the evaluation of the deposit was performed in the same manner as in example 1 by the method described above. The results are shown in table 9 together with the results of example 3 and example 5.
[ Table 9]
As is clear from comparison of examples 3, 6 and 7 and comparison of examples 5, 8 and 9 in table 9, the proportion of the area covered with the deposit tends to be small by increasing the content of the high boiling point solvent. Further, from comparison among examples 6, 10 and 11, it was confirmed that there was no difference in the area ratio covered with the adhered matter between the case where one high boiling point solvent was used and the case where 2 or more high boiling point solvents were used.
< evaluation of film wrinkling after high-temperature treatment >
Next, evaluation of film wrinkles after high temperature treatment was performed using the colored resin compositions of example 8 and comparative examples 2,3, and 4. Comparative example 4 was obtained in the same manner as in example 8, except that the green pigment type was changed to the green pigment B.
First, 50mm square and 0.6mm thickThe colored resin composition was applied to a glass substrate (manufactured by Asahi glass company, Inc., AN100) by a spin coater, and then dried at 80 ℃ for 3 minutes. The coating film thickness was set so that the chromaticity (sx, sy) after post-baking was (0.250, 0.580) under a C light source. Next, a 2kW high-pressure mercury lamp was used at 40mJ/cm2The exposure amount of (2) is an exposure treatment to the whole surface. Then, post-baking was performed in an oven at 230 ℃ for 30 minutes.
The film surface of the high-temperature-treated substrate thus obtained was measured for Sq (root mean square deviation roughness, nm), Sa (arithmetic mean roughness, nm), and Sz (maximum height of roughness, nm) by Micromap (manufactured by mitsubishi corporation, three-dimensional non-contact surface shape measurement system). The measurement was performed in a field of view of 12800nm × 6400nm in Focus mode using a 50-fold optical lens. The results of Sq, Sa, and Sz calculations based on ISO 25178 are shown in table 10.
The profiles obtained by the measurement are shown in fig. 4 (example 8), fig. 5 (comparative example 2), fig. 6 (comparative example 4), and fig. 7 (comparative example 3). In the profiles of FIGS. 4-7, the lateral width is 12800nm and the depth is 6400 nm. The several tens of irregularities seen in each figure correspond to membrane wrinkles.
[ Table 10]
The following results are confirmed from table 10: in example 8 using the green pigment a and a high boiling point solvent, the values of Sq, Sa, and Sz were all small, and film wrinkle was effectively suppressed. In particular, since the difference between Sq and Sa is small and the value of Sz is small, it was confirmed that there are few surface irregularities due to wrinkles and there is no unevenness of wrinkles in the measurement field of view. With recent increase in color gamut, the pigment concentration in color filters has increased, and thus film wrinkles tend to occur. If the film wrinkles occur, color unevenness occurs due to the wrinkles, and a problem such as a disconnection defect occurs when a panel is formed. The following teaching is therefore given: by using the colored resin composition and the pigment dispersion liquid of the present invention, the occurrence of film wrinkles can be suppressed even in the case of a wider color gamut, and further, color unevenness, disconnection failure in forming a panel, and the like can be effectively suppressed.
On the other hand, in comparative example 2 in which the green pigment a was used and no high boiling point solvent was used, the values of Sq, Sa, and Sz were all large, and it was confirmed that film wrinkles occurred. In particular, it was confirmed that wrinkles occurred on the entire measurement field of view due to the small difference between Sq and Sa and the large Sz value.
On the other hand, in comparative examples 4 and 3 in which the green pigment B was used, the values of Sq, Sa, and Sz were all extremely large, and it was confirmed that film wrinkles occurred. In particular, the following results were confirmed: although the values of Sq and Sa are improved by the use of the high boiling point solvent, the value of Sz is large regardless of the use of the high boiling point solvent, and thus, although the film wrinkle is partially improved by the use of the high boiling point solvent, a large film wrinkle remains partially.
The difference in the above results is considered to be due to the following reasons: as described later, since the coloring power of the green pigment a is higher than that of the green pigment B, the green pigment a can be made thinner in film thickness necessary for obtaining a film of the same chromaticity, so that the amount of a solvent as a volatile component can be relatively reduced, and the amount of a component such as a binder resin as a component contributing to thermal deformation can be relatively reduced. In addition, the reason why the value of Sz is greatly improved by using a high boiling point solvent in the case of using the green pigment a as compared with the green pigment B is not clear, but it is considered that the reason is as follows: since the average hydrogen number of the green pigment a is a predetermined value or more as compared with the green pigment B, the green pigment a has a high affinity for the solvent, the high-boiling solvent is likely to be uniformly present over the entire film, evaporation of the volatile component can be suppressed over the entire film, and as a result, generation of wrinkles in the film can be suppressed over the entire film.
< evaluation of tinting strength >
A colored resin composition was prepared in the same manner as in the above < preparation of colored resin composition > except that the green pigment dispersion liquid of comparative example 2 or comparative example 3 shown in table 4 and the yellow pigment dispersion liquid shown below were used and the amount of the pigment dispersion liquid used was changed to the amount shown in table 11. The amount of the pigment dispersion used was adjusted so that the chromaticity under C light source became sx 0.280 and sy 0.600 when a coating film having a film thickness of 2.00 μm was formed. The pigment concentration shown in table 11 is the content ratio of all pigments in the total solid content of the colored resin composition.
< preparation of yellow pigment Dispersion >
A yellow pigment C was used as a yellow pigment in an amount of 12.0 parts by mass in terms of solid content, a dispersant a was used as a dispersant in an amount of 4.0 parts by mass in terms of solid content, a dispersion resin a was used as a dispersion resin in an amount of 4.0 parts by mass in terms of solid content, propylene glycol monomethyl ether acetate was used as a solvent in an amount of 80.0 parts by mass, and zirconia beads having a diameter of 0.5mm were used in an amount of 225 parts by mass, and these were filled in a stainless steel container and dispersed for 6 hours by a paint shaker to prepare a yellow pigment dispersion.
< yellow pigment C >
As the yellow pigment C, a nickel azo complex compound (E4GN-GT, manufactured by LANXESS) in which a compound represented by the following formula (II) is inserted into a complex compound of azo barbituric acid represented by the following formula (I) and nickel in a ratio of 1:1 or a tautomer thereof is used.
[ chemical formula 26]
[ chemical formula 27]
[ Table 11]
As is clear from table 11, reference example 1 using green pigment a had a low pigment concentration and a high coloring power as compared with reference example 2 using green pigment B. If the pigment concentration is small, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and the like can be used in a larger amount in terms of solid content, and this is advantageous in various properties such as developability and reliability. The detailed reason is not clear, but it is considered to be due to the following reasons: when the transmittance spectra at the same pigment concentration are compared, the half-value width of the peak of the green pigment a is narrower than that of the green pigment B due to the influence of the average number of hydrogen atoms contained in one molecule, and the red and blue transmitted light is effectively blocked.
(Experimental examples 1 to 6, comparative experimental examples 1 to 5)
Green pigment dispersions a and B were prepared by filling a stainless steel container with the green pigment, the yellow pigment C, the dispersant a, the dispersion resin a, the solvent (propylene glycol monomethyl ether acetate), and 225 parts by mass of zirconia beads having a diameter of 0.5mm described in table 12, and dispersing them for 6 hours by a paint shaker. The amounts of components other than "solvent" in the table are values converted into solid components.
[ Table 12]
< preparation of colored resin composition >
The other components shown in table 13 were mixed with each of the pigment dispersions described above to prepare colored resin compositions. The combinations of the green pigment species and the photopolymerization initiator species are shown in table 14.
In table 13, the amounts of the binder resin and the photopolymerizable monomer blended are values converted to solid components, and the amount of the solvent blended is a value including the amounts of the solvent contained in the binder resin and the photopolymerizable monomer.
[ Table 13]
The photopolymerization initiators a to I in table 14 are shown below.
< photopolymerization initiator A > Oxime ester compound having the following chemical structure
[ chemical formula 28]
< photopolymerization initiator B > Irgacure OXE02 (manufactured by BASF corporation)
[ chemical formula 29]
< photopolymerization initiator C > Irgacure OXE03 (manufactured by BASF corporation)
[ chemical formula 30]
< photopolymerization initiator D > Oxime ester compound having the following chemical structure
[ chemical formula 31]
< photopolymerization initiator E > TR-PBG-304 (manufactured by Changzhou Qiangli electronics Co., Ltd.)
[ chemical formula 32]
< photopolymerization initiator F > TR-PBG-314 (manufactured by Changzhou Qiangli electronics Co., Ltd.)
[ chemical formula 33]
< photopolymerization initiator G > 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -Bisimidazole (BCIM)
[ chemical formula 34]
< photopolymerization initiator H > Irgacure 907 (manufactured by BASF Co., Ltd.)
[ chemical formula 35]
< photopolymerization initiator I > Irgacure 369 (manufactured by BASF Co., Ltd.)
[ chemical formula 36]
< evaluation of minimum adhesion >
Each colored resin composition was applied to a glass substrate on which chromium was deposited by spin coating, and prebaked with a hot plate at 80 ℃ for 3 minutes. The rotation speed was adjusted so that the film thickness of the coating film after post-baking became 2.0. mu.m at the time of coating.
Then, a mask pattern having linear openings with a width of 1 to 50 μm (1 to 10 μm: 1 μm apart, 15 to 50 μm: 5 μm apart) was provided with a 150 μm gap, and a sample was irradiated with 40mJ/cm through the mask pattern by a high pressure mercury lamp2After exposure, spray development was performed at a developer temperature of 23 ℃ and a pressure of 0.25MPa using a 0.04 mass% aqueous solution of potassium hydroxide. The time for development was 2 times the previously measured dissolution time of the colored resin composition. For the substrate, after development, rinsing was sufficiently performed with water, and then drying was performed with clean air. Then, post-baking was performed in an oven at 230 ℃ for 30 minutes.
The linear patterns obtained in this order were observed with an optical microscope, and of the linear mask patterns having different widths, the pattern having the smallest opening width of the corresponding mask out of the patterns remaining on the substrate was specified, and the result of minimizing the width of the opening was shown in table 14.
As can be seen from table 14, when the green pigment B was used as in comparative experimental examples 1 and 2, the minimum adhesion was good in both cases where the oxime ester compound was used as the photopolymerization initiator and where an initiator other than the oxime ester compound was used.
On the other hand, when the green pigment a was used as in comparative experimental examples 3 to 5, the minimum adhesion value was large and the adhesion was poor when an initiator other than the oxime ester compound was used as the photopolymerization initiator. On the other hand, when the green pigment a is used as in experimental examples 1 to 6, the minimum adhesion value is small and the adhesion is good by using the oxime ester compound as the photopolymerization initiator.
It is considered that the average hydrogen number of the green pigment a is higher than that of the green pigment B, and the green pigment a tends to be hard to be sufficiently photocured into the inside of the coating film due to the difference in light absorption characteristics caused by the difference, but by using an oxime ester compound having a larger absorption band in a low wavelength region as a photopolymerization initiator, it is possible to be sufficiently photocured into the inside of the coating film, and a fine pattern can be formed with good adhesion.
< evaluation of film thickness and tinting strength >
The colored resin composition was applied to a glass substrate (manufactured by Asahi glass company, Inc., AN100) having a thickness of 0.6mm and a square width of 50mm by a spin coater, and then dried at 80 ℃ for 3 minutes. Next, a 2kW high-pressure mercury lamp was used at 40mJ/cm2The exposure amount of (2) is an exposure treatment to the whole surface.
Then, post-baking was performed in an oven at 230 ℃ for 30 minutes.
The transmission spectrum of the thus obtained coated substrate was measured by a spectrophotometer U-3310 manufactured by Hitachi, Ltd. From the obtained transmission spectrum, a film thickness necessary for obtaining chromaticity under a C light source (sx is 0.240 and sy is 0.580) was calculated, and a pigment concentration necessary for obtaining a film thickness of 2.00 μm (mass% of all pigments relative to all solid contents) was calculated and evaluated as a coloring power, and the results thereof are shown in table 14.
As is clear from Table 14, the pigment concentrations required in examples 1 to 6 using the green pigment A were low and the coloring power was high, compared with comparative examples 1 and 2 using the green pigment B. If the pigment concentration is required to be small, the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the like can be blended in a larger amount in terms of the solid content, and therefore, the pigment is advantageous in various properties such as developability and reliability.
The detailed reason why the difference in coloring power occurs is not clear, but it is considered that the difference is due to the following reasons: when the transmission spectra are compared at the same pigment concentration, the half-value width of the peak of green pigment a is narrowed compared with that of green pigment B, and thus the transmitted light of red and blue is effectively blocked.
[ Table 14]
From the above, it is found that both coloring power and adhesion can be achieved by using a combination of a zinc halide phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of a given amount or more and an oxime ester compound.
The present invention has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present application was completed based on Japanese patent application laid out on day 27 of 2015 (Japanese application 2015-067187), on day 20 of 2015 10, 2015 (Japanese application 2015-206474), on day 21 of 2015 10, 2015 (Japanese application 2015-207298) and on day 11 of 2016 3, 11, the contents of which have been incorporated into the present application by reference.

Claims (15)

1. A colored resin composition comprising: (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator,
the pigment (A) contains a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more,
the (C) solvent contains a high-boiling solvent having a boiling point of 150 ℃ or higher at 1013.25 hPa.
2. The colored resin composition according to claim 1, wherein the (C) solvent further comprises a low-boiling solvent having a boiling point of less than 150 ℃ at 1013.25 hPa.
3. The colored resin composition according to claim 1 or 2, wherein the content ratio of the (C) solvent to the colored resin composition is 50% by mass or more.
4. The colored resin composition according to any one of claims 1 to 3, wherein the content ratio of the high-boiling solvent to the (C) solvent is 0.5% by mass or more.
5. The colored resin composition according to any one of claims 1 to 4, wherein the vapor pressure of the high-boiling solvent at 20 ℃ is 400Pa or less.
6. The colored resin composition according to any one of claims 1 to 5, wherein the dispersant (B) comprises a block copolymer having a functional group containing a nitrogen atom.
7. The colored resin composition according to any one of claims 1 to 6, wherein the (E) photopolymerization initiator comprises an oxime ester compound.
8. A color filter having pixels produced by using the colored resin composition according to any one of claims 1 to 7.
9. An image display device having the color filter according to claim 8.
10. A pigment dispersion comprising: (A) a pigment, (B) a dispersant, and (C) a solvent, wherein,
the pigment (A) contains a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more,
the (C) solvent contains a high-boiling solvent having a boiling point of 150 ℃ or higher at 1013.25 hPa.
11. The pigment dispersion according to claim 10, wherein said (C) solvent further comprises a low boiling point solvent having a boiling point of less than 150 ℃ at 1013.25 hPa.
12. The pigment dispersion liquid according to claim 10 or 11, wherein a content ratio of the (C) solvent to the pigment dispersion liquid is 50% by mass or more.
13. The pigment dispersion liquid according to any one of claims 10 to 12, wherein a content ratio of the high-boiling solvent to the (C) solvent is 1% by mass or more.
14. The pigment dispersion liquid according to any one of claims 10 to13, wherein the vapor pressure of the high-boiling-point solvent at 20 ℃ is 400Pa or less.
15. The pigment dispersion liquid according to any one of claims 10 to 14, wherein the dispersant (B) comprises a block copolymer having a functional group containing a nitrogen atom.
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