CN116917807A - Photosensitive colored resin composition, cured product, color filter and display device - Google Patents

Photosensitive colored resin composition, cured product, color filter and display device Download PDF

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Publication number
CN116917807A
CN116917807A CN202280014044.2A CN202280014044A CN116917807A CN 116917807 A CN116917807 A CN 116917807A CN 202280014044 A CN202280014044 A CN 202280014044A CN 116917807 A CN116917807 A CN 116917807A
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group
general formula
resin composition
mass
meth
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境美嘉
五十岚一贵
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DNP Fine Chemicals Co Ltd
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DNP Fine Chemicals Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

The photosensitive coloring resin composition of the present invention comprises: the color material, alkali-soluble resin, photo-polymerizable compound, photoinitiator and solvent, wherein the photo-polymerizable compound contains 1 molecule of photo-polymerizable compound containing 7 or more unsaturated double bond groups and acidic groups, the molecular weight of the photo-polymerizable compound is 500 or more, and the photoinitiator contains 1 or more selected from the group consisting of compounds represented by the following general formula (A) and compounds represented by the following general formula (B). The symbols of the general formula (A) and the general formula (B) are as described in the specification.

Description

Photosensitive colored resin composition, cured product, color filter and display device
Technical Field
The invention relates to a photosensitive coloring resin composition, a cured product, a color filter and a display device.
Background
In recent years, with the development of personal computers, particularly personal computers for portable use, the demand for liquid crystal displays has increased. The popularity of mobile displays (cellular phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Organic light emitting display devices such as organic EL displays having high visibility due to self-luminescence are also attracting attention as next-generation image display devices.
These liquid crystal display devices or organic light emitting display devices use color filters. For example, in the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored in the color of each pixel constituting the color filter, and the light of these colors is synthesized to form the color image. In addition to conventional cold cathode tubes, organic light emitting elements that emit white light and inorganic light emitting elements that emit white light may be used as the light source in this case. In an organic light emitting display device, a color filter is used for color tone adjustment and the like.
Here, the color filter generally has: a substrate; a coloring layer formed on the substrate and including coloring patterns of three primary colors of red, green and blue; and a light shielding portion formed on the substrate so as to divide each of the coloring patterns.
As a method for forming a colored layer in a color filter, for example, a binder resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion liquid in which a color material is dispersed by a dispersant or the like, the obtained colored resin composition is applied to a glass substrate, dried, exposed to light using a photomask, and developed, thereby forming a colored pattern, and the pattern is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.
In recent years, as the demand for higher brightness of color filters has increased, the concentration of color materials in the colored layers of color filters has increased as compared with the prior art, and therefore, the components required for photopolymerization have decreased relatively, and patterning has become difficult. Further, in order to increase productivity of the color filter, it is required to reduce the cumulative exposure amount required for patterning, and therefore, how to secure curability required for patterning becomes a big issue.
In order to secure curability necessary for patterning of the colored layer, a photoinitiator having a relatively small molecular weight such as Irgacure 907 is used as a photoinitiator having high sensitivity in the colored resin composition for a color filter.
In order to ensure good developability for patterning the colored layer, a 3-functional, 4-functional polyfunctional monomer is used. The reason for this is that there are the following problems: in the 5-functional and 6-functional polyfunctional monomers, the development time becomes long.
On the other hand, patent document 1 discloses a coloring radiation-sensitive composition, which is suitable for XeCl excimer laser exposure and contains a polyfunctional monomer having 7 or more polymerizable unsaturated bonds and a specific α -aminoketone photopolymerization initiator such as Irgacure 907. As the coloring radiation-sensitive composition of patent document 1, it is described that when a coloring layer is formed by XeCl excimer laser exposure, the pattern shape and the residual film ratio are excellent. Patent document 1 shows that: in the case of using a polyfunctional monomer having 7 or more polymerizable unsaturated bonds and the case of using a polyfunctional monomer having 7 or more polymerizable unsaturated bonds without an acidic group, the evaluation results are not different, but in the case of using a polyfunctional monomer having 7 or more polymerizable unsaturated bonds with an acidic group, the film thickness difference becomes large due to the cumulative exposure amount.
Patent document 2 describes a colored resin composition for a color filter, which contains a specific compound having an acidic group and 10 polymerizable unsaturated bonds, in order to provide a colored resin composition for a color filter, which has excellent chemical resistance of the obtained pixel and linearity of the pixel edge.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-26261027
Patent document 2: japanese patent laid-open publication No. 2013-195971
Disclosure of Invention
Problems to be solved by the invention
The present inventors have found that when a colored layer is formed using a conventional colored resin composition containing a high-sensitivity photoinitiator and a 3-functional or 4-functional polyfunctional monomer having good developability, sublimates are easily generated from the colored resin composition in a drying step before exposure.
On the other hand, the development of 5-functional and 6-functional polyfunctional monomers which are less likely to cause sublimates is slow, and both excellent developability and sublimate inhibition are not likely to be achieved.
In addition, the colored resin composition described in patent document 2 still has a problem that sublimates are easily generated and water spots are easily generated. The water spot means a phenomenon that after alkali development, a trace of water spots is generated after washing with pure water. Such water spots disappear after post baking, and therefore there is no problem in using them as products, but they are detected as uneven abnormalities in the visual inspection of the patterned surface after development, resulting in a problem that normal products and abnormal products cannot be distinguished. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, the yield of the final color filter product is lowered as a result, which is a problem.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a photosensitive colored resin composition which suppresses the occurrence of sublimates during drying, is excellent in developability, and is suppressed in the occurrence of water spots, a cured product of the photosensitive colored resin composition, a color filter having a colored layer formed using the photosensitive colored resin composition, and a display device having the color filter.
Means for solving the problems
The photosensitive coloring resin composition of the present invention comprises: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
the photopolymerizable compound contains 1 acid group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and acid groups in the molecule and has a molecular weight of 500 or more,
the photoinitiator contains 1 or more selected from the group consisting of a compound represented by the following general formula (A) and a compound represented by the following general formula (B):
[ chemical 1]
General formula (A)
(in the general formula (A), Z 1 、Z 3 、Z 4 Z is as follows 5 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, each of which may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group; z is Z 2 Represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group. )
[ chemical 2]
General formula (B)
(in the general formula (B), R a R is R b Each independently represents an alkyl group having 2 to 8 carbon atoms. )
The color filter of the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a cured product of the photosensitive colored resin composition of the present invention.
The present invention also provides a display device having the color filter of the present invention.
Effects of the invention
According to the present invention, there can be provided a photosensitive colored resin composition which suppresses the occurrence of sublimates during drying, is excellent in developability and is suppressed in the occurrence of water spots, a cured product of the photosensitive colored resin composition, a color filter having a colored layer formed using the photosensitive colored resin composition, and a display device having the color filter.
Drawings
Fig. 1 is a schematic diagram showing an example of a color filter according to the present invention.
Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
Fig. 3 is a schematic view showing an example of the organic light emitting display device of the present invention.
Detailed Description
The photosensitive colored resin composition, cured product, color filter, and display device of the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible light and non-visible light regions, and radiation including microwaves and electron beams, for example. Specifically, electromagnetic waves having a wavelength of 5 μm or less and electron beams.
In the present invention, (meth) acrylic acid means each of acrylic acid and methacrylic acid, (meth) acrylic acid ester means each of acrylic acid ester and methacrylic acid ester, and (meth) acryl group means each of acryl group and methacryl group.
In the present specification, "to" representing a numerical range "is used to include the numerical values described before and after the numerical value as the lower limit value and the upper limit value.
I. Photosensitive coloring resin composition
The photosensitive coloring resin composition of the present invention comprises: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
the photopolymerizable compound contains 1 acid group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and acid groups in the molecule and has a molecular weight of 500 or more,
the photoinitiator contains 1 or more selected from the group consisting of a compound represented by the following general formula (A) and a compound represented by the following general formula (B).
[ chemical 3]
General formula (A)
(in the general formula (A), Z 1 、Z 3 、Z 4 Z is as follows 5 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, each of which may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group; z is Z 2 Represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group. )
[ chemical 4]
General formula (B)
(in the general formula (B), R a R is R b Each independently represents an alkyl group having 2 to 8 carbon atoms. )
In the conventional colored resin composition, it was found that sublimates generated during drying before exposure are derived from conventional high-sensitivity photoinitiators, 3-functional or 4-functional polyfunctional monomers such as pentaerythritol triacrylate and pentaerythritol tetraacrylate, which have good developability. When sublimates are generated from the colored resin composition during the drying before the exposure, there are cases where the sublimates adhere to an exhaust pipe, a chamber, or the like of a drying apparatus such as a heating plate used in the drying step before the exposure, and progress crystallization. If crystals of the sublimate grown fall to the coating film of the colored resin composition before exposure, defects such as black defects are generated in the colored layer, and this causes deterioration in quality. In addition, if crystallization of sublimates is advanced in the drying apparatus, cleaning of the drying apparatus becomes difficult, and therefore, there is also a problem that production efficiency is lowered due to an increase in cleaning time of the drying apparatus or the like. Therefore, a colored resin composition in which the generation of sublimates is suppressed at the time of drying is demanded.
On the other hand, although 5-functional, 6-functional, polyfunctional monomers such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are less likely to cause sublimates, development is slower and both excellent developability and sublimate inhibition are less likely to be achieved.
Further, the cause of the water spot of the cured film of the photosensitive colored resin composition may be: water is absorbed into the cured film. The reason for this is that the alkali-soluble resin in the cured film has an acidic group such as a carboxyl group, and thus absorbs water easily.
In view of this, the photosensitive colored resin composition of the present invention uses a specific photoinitiator in combination with a specific photopolymerizable compound, that is, an acidic group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and acidic groups in 1 molecule, and a photopolymerizable compound having a molecular weight of 500 or more.
In the present invention, the specific photoinitiator used is not liable to generate sublimates when dried, and has excellent sensitivity. In the present invention, since the specific photopolymerizable compound used contains 1 photopolymerizable compound having 7 or more unsaturated double bond groups and acidic groups in the molecule and has a molecular weight of 500 or more, sublimates are not easily generated during drying, and the photopolymerizable compound is excellent in developability and further excellent in curability.
Since the photopolymerizable compound having an acidic group has an acidic group, it may become a cause of water spotting. However, in the present invention, it is presumed that by combining the above-mentioned photopolymerizable compound containing an acidic group having a large number of functional groups with the above-mentioned specific photoinitiator which is not easily sublimated and remains in the film to effectively function and has high sensitivity, reactivity is increased, the curing degree of the cured film is increased, water absorption is not easily caused, and generation of water spots is suppressed.
Therefore, the photosensitive colored resin composition of the present invention suppresses the generation of sublimates during drying, is excellent in developability, and suppresses the generation of water spots.
Since sublimates are not easily generated during drying before exposure, when a colored layer is formed by using the photosensitive colored resin composition of the present invention, the sublimates can be prevented from adhering to the drying device used in the drying step before exposure. Therefore, defects such as black defects caused by sublimates adhering to the inside of the drying apparatus can be suppressed, and the production efficiency can be improved by simplifying the cleaning of the drying apparatus.
Further, since the photosensitive colored resin composition of the present invention is excellent in curability and developability, the color material concentration in the colored layer becomes high, and therefore, even if the components necessary for photopolymerization are relatively small, a colored layer excellent in patterning property and having a high-definition pattern can be formed.
When the photopolymerizable compound containing an acidic group having 7 or more unsaturated double bond groups and an acidic group in 1 molecule contained in the photosensitive colored resin composition of the present invention is used, it is easy to be thinned by heat shrinkage, and therefore, the photopolymerizable compound is particularly suitable for forming a colored layer in a high fine line pattern.
Further, since the photosensitive colored resin composition of the present invention has good curability, the substrate adhesion of the colored layer is improved.
The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components such as a dispersing agent, within a range that does not impair the effects of the present invention.
The components of the colored resin composition of the present invention will be described in detail below in order from the photoinitiator and photopolymerizable compound which are specific to the present invention.
[ photoinitiator ]
< Compound represented by the general formula (A) >
In the general formula (A), Z is 1 、Z 3 、Z 4 Z is as follows 5 Examples of the linear or branched alkyl group having 1 to 12 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like.
As Z 1 、Z 3 、Z 4 Z is as follows 5 Examples of the cycloalkyl group having 3 to 20 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctadecyl, and the like.
As Z 2 The cycloalkyl group in (a) may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and is preferably a cyclopentyl group or a cyclohexyl group.
As Z 2 The alkyl group having 1 to 20 carbon atoms in (a) may be exemplified by a linear or branched alkyl group having 1 to 12 carbon atoms, as well as the above-mentioned alkyl group having 1 to 12 carbon atoms: n-tetradecyl, n-hexadecyl, n-octadecyl, etc.
In addition, at Z 1 、Z 3 、Z 4 Z is as follows 5 Examples of the halogen atom which may be substituted for the alkyl group, cycloalkyl group and phenyl group include: fluorine atom, chlorine atom, bromine atom, etc.
At Z 1 、Z 3 、Z 4 Z is as follows 5 Examples of the "alkoxy" having 1 to 6 carbon atoms which may be substituted by the alkyl group, cycloalkyl group and phenyl group may include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy and the like.
In the general formula (A), Z is 1 In terms of improving sensitivity, an alkyl group having 1 to 6 carbon atoms or a phenyl group is preferable, a methyl group, an ethyl group, or a phenyl group is more preferable, and a methyl group is still more preferable.
In the general formula (A), Z is 3 、Z 4 Z is as follows 5 In terms of brightness, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferable.
In the general formula (A), Z is 2 In terms of solvent solubility and compatibility, an alkyl group having 1 to 14 carbon atoms substituted with a cycloalkyl group having 5 to 6 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms substituted with a cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a cyclohexylmethyl group or a cyclopentylmethyl group is even more preferable, and a cyclohexylmethyl group is particularly preferable.
Among these photoinitiators represented by the general formula (A), oxime ester compounds represented by the following chemical formula (A-1) are preferable in terms of being less likely to produce sublimates. Examples of the commercial products include: TR-PBG-3057 (manufactured by new materials, powerful electronics, in everstate), and the like.
[ chemical 5]
Chemical formula (A-1)
The photoinitiator represented by the general formula (a) can be synthesized by using diphenyl sulfide or a derivative thereof, and appropriately selecting a solvent, a reaction temperature, a reaction time, a purification method, and the like according to the material used, for example, with reference to japanese patent application publication No. 2012-526185. Further, a commercially available product may be suitably obtained and used.
< Compound represented by the general formula (B) >
The photoinitiator used in the present invention contains a compound represented by the general formula (B).
In the general formula (B), R a R is R b Each independently represents an alkyl group having 2 to 8 carbon atoms. The alkyl group may be any of a linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, methylcyclopentyl, cyclopentylmethyl, cyclohexyl, methylcyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like. Among them, from the viewpoint of suppressing the generation of sublimates and precipitates during drying, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable. The carbon number of the alkyl group is preferably 2 or more and 6 or less, more preferably 3 or more and 5 or less.
R in the general formula (B) a R is R b Can be the same or different, if R a R is R b The two are the same, and are preferable in terms of easy synthesis and excellent productivity.
Preferable specific examples of the compound represented by the general formula (B) include, but are not limited to, the following chemical formula (B-1).
[ chemical 6]
Chemical formula (B-1)
The compound represented by the general formula (B) can be synthesized, for example, by a method comprising:
step 1, reacting fluorene with isobutyryl chloride in the presence of aluminum trichloride to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone;
step 2 of epoxidizing the 2-methyl-1-fluorenyl-2-chloro-1-propanone obtained in the step 1 with sodium methoxide under a nitrogen atmosphere by the catalytic action of calcium oxide, and thereafter, further reacting with morpholine to obtain 2-methyl-1-fluorenyl-2-morpholinyl-1-propanone; and
And step 3 of reacting the 2-methyl-1-fluorenyl-2-morpholinyl-1-propanone obtained in step 2 with an alkyl chloride having 2 to 8 carbon atoms in the presence of tetrabutylammonium bromide (TBAB), thereby obtaining a compound represented by the general formula (B).
In the step 3, R in the general formula (B) can be obtained by using 2 or more kinds of alkyl chlorides a R is R b Compounds different from each other.
[ chemical 7]
Step 1
Step 2
Step 3
In the photosensitive colored resin composition of the present invention, the photoinitiator contains 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B), and it is preferable that the photoinitiator contains 1 or more selected from the group consisting of the compound represented by the general formula (B) in terms of easy line width adjustment and more favorable for high definition of patterns.
< other photoinitiators >
In the colored resin composition of the present invention, the photoinitiator may further contain a photoinitiator different from the compound represented by the general formula (a) and the compound represented by the general formula (B). The other photoinitiators used in the photosensitive colored resin composition of the present invention include photopolymerization initiators and also so-called sensitizers.
The photoinitiator preferably further contains at least 1 selected from the group consisting of an α -aminoketone photoinitiator, an oxime ester photoinitiator having a carbazole skeleton, and a bisimidazole photoinitiator, which have a molecular weight of 300 or more, in terms of curability and substrate adhesion.
The other photoinitiator is more preferably 1 or more selected from the group consisting of α -aminoketone photoinitiators and biimidazole photoinitiators in terms of curability and substrate adhesion.
In terms of developability and adhesion, the total content of 1 or more selected from the group consisting of α -aminoketone photoinitiators is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more, relative to the total amount of the other photoinitiators.
In addition, in terms of suppressing the generation of sublimates during drying, the molecular weight of the other photoinitiator is preferably 300 or more, more preferably 350 or more, and even more preferably 400 or more. The upper limit of the molecular weight of the other photoinitiator is not particularly limited, and is usually 1000 or less, 800 or less, or 600 or less.
Although not particularly limited, the total content of photoinitiators having a molecular weight of 300 or more is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more, with respect to the total amount of the other photoinitiators, in terms of suppressing the generation of sublimates during drying.
The α -aminoketone photoinitiator has a property of allowing intermediate curing from the surface of the coating film and is preferably used because it is easy to suppress deep curability of the coating film, since it tends to improve deep curability of the coating film when it is combined with 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B). Examples of the α -aminoketone photoinitiator having a molecular weight of 300 or more include: 2-benzyl-2- (dimethylamino) -1- (4-morpholinylphenyl) -1-butanone (e.g., irgacure 369, manufactured by BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (Irgacure 379EG, manufactured by BASF), and the like.
Among the α -aminoketone photoinitiators having a molecular weight of 300 or more, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, irgacure 369, manufactured by basf corporation) is preferable in terms of improving substrate adhesion and facilitating pattern shape adjustment and preventing pattern defects from occurring when combined with at least 1 of the compound represented by the general formula (a) and the compound represented by the general formula (B).
The α -aminoketone photoinitiator may be used alone or in combination of 2 or more.
The oxime ester photoinitiator having a carbazole skeleton is preferably used in that it has a high tendency to improve the water spot-inhibiting effect, adhesion and defect-inhibiting effect when it is combined with 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B).
Examples of the oxime ester photoinitiator having a carbazole skeleton include: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetoxime) (e.g., irgacure OXE02, manufactured by BASF corporation), methanone, [8- [ [ (acetoxy) imino ] [2- (2, 3-tetrafluoropropoxy) phenyl ] methyl ] -11- (2-ethylhexyl) -11H-benzo [ a ] carbazol-5-yl ] -, (2, 4, 6-trimethylphenyl) (e.g., manufactured by Irgacure OXE-03, BASF), ethanone, 1- [ 9-ethyl-6- (1, 3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl ] -, O-acetyloxime, 1-propanone, 3-cyclopentyl-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime) (e.g., TR-PB G-304, manufactured by Hemsl Strong electronic New Co., ltd.) 1-propanone, 3-cyclopentyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl ] -,1- (o-acetyloxime), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazol-3-yl ] -,1- (o-acetyloxime), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl ] -,1- (o-acetyloxime), 1-octanone, 1- [4- [3- [1- [ (acetoxy) imino ] ethyl ] -6- [4- [ (4, 6-dimethyl-2-pyrimidinyl) thio ] -2-methylbenzoyl ] -9H-carbazol-9-yl ] phenyl ] -,1- (o-acetyloxime) (e.g., manufactured by EXTA-9, union Chemical) as a commercial product, there may be exemplified: ADEKA OPT-N-1919 (manufactured by ADEKA corporation), adeka Arkles NCI-831 (manufactured by ADEKA corporation), and the like.
As the oxime ester-based photoinitiator having a carbazole skeleton, 2 or more types of photoinitiators may be used alone or in combination, and among them, 1-propanone, 3-cyclopentyl-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime) (for example, TR-PBG-304, manufactured by the company of new powerful electronics, the company of the state), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime) (for example, irgacure OXE02, manufactured by BASF corporation), or methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl ] -, O-acetyloxime) are preferably used in terms of higher sensitivity.
The biimidazole photoinitiator has a property of deeply curing a coating film and is easy to inhibit the surface curability of the coating film, and when it is combined with 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B), the water spot inhibiting effect tends to be improved, and is preferable in this respect.
Examples of the biimidazole photoinitiator include: 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2 '-bis (2-bromophenyl) -4,4',5,5 '-tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4, 6-trichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2-bromophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dibromophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4, 6-tribromophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, and the like.
The biimidazole photoinitiator may be used alone or in combination of 2 or more, and among them, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole is preferably used in terms of improving the water spot-inhibiting effect.
The total content of the photoinitiators used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, and is, for example, preferably in the range of 0.1% by mass to 12.0% by mass, and more preferably in the range of 1.0% by mass to 8.0% by mass, relative to the total amount of solid components of the photosensitive colored resin composition. If the content is not less than the lower limit, the photocuring is sufficiently performed to suppress elution of the exposed portion during development, and if the content is not more than the upper limit, the reduction in brightness due to yellowing of the obtained colored layer can be suppressed.
The solid component means all components except the solvent, and includes a liquid polyfunctional monomer and the like.
The total content of 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B) may be 50% by mass or more, or 100% by mass, relative to the total amount of the photoinitiator.
When the photoinitiator contains 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B), and the other photoinitiator, the total content of 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B) is preferably 20 mass% or more and 98 mass% or less, more preferably 30 mass% or more and 95 mass% or less, still more preferably 40 mass% or more and 95 mass% or less, and particularly preferably 45 mass% or more and 90 mass% or less, with respect to the total amount of the photoinitiator, in terms of forming a high fine line pattern.
[ photopolymerizable Compound ]
The photopolymerizable compound used in the photosensitive colored resin composition of the present invention contains 1 photopolymerizable compound containing an acidic group having 7 or more unsaturated double bond groups and an acidic group in the molecule, and has a molecular weight of 500 or more.
The inventors of the present invention have found that a 3-functional or 4-functional polyfunctional monomer having a relatively low molecular weight and good developability causes sublimates, and that in the case of a photopolymerizable compound, sublimation is likely to occur even if the molecular weight is larger than that of a photoinitiator. In the present invention, since the photopolymerizable compound has a molecular weight of 500 or more, the occurrence of sublimates due to the photopolymerizable compound can be suppressed.
The unsaturated double bond group is not particularly limited as long as it can be polymerized by the photoinitiator, and examples thereof include: vinyl, allyl, acryl, methacryl, and the like. As the unsaturated double bond group, an acryl group or a methacryl group is preferably used among them in terms of ultraviolet curability.
Examples of the acidic group include: carboxyl groups, sulfonic acid groups, phosphoric acid groups, and the like, and among them, carboxyl groups are preferably used in terms of developability.
Among these, carboxyl group-containing polyfunctional (meth) acrylates having 7 or more (meth) acryloyl groups and carboxyl groups are preferable as the acidic group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and acidic groups in 1 molecule.
Examples of the carboxyl group-containing polyfunctional (meth) acrylate having 7 or more (meth) acryloyl groups and carboxyl groups include: an esterified product of a polyfunctional (meth) acrylate having a hydroxyl group and a (meth) acryloyl group and a polycarboxylic acid.
Examples of the polyfunctional (meth) acrylate having a hydroxyl group and a (meth) acryloyl group include: hydroxy-containing multifunctional (meth) acrylates obtained from the esterification of polyols with (meth) acrylic acid. The polycarboxylic acid includes dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, and other acid anhydrides such as tetracarboxylic dianhydride. In the present specification, for example, dicarboxylic acids include dicarboxylic acids and dicarboxylic anhydrides, and tetracarboxylic acids include tetracarboxylic acids and tetracarboxylic dianhydrides.
As the carboxyl group-containing polyfunctional (meth) acrylate having 7 or more (meth) acryloyl groups and carboxyl groups, for example, a polyfunctional (meth) acrylate having 1 hydroxyl group and 7 or more (meth) acryloyl groups and a dicarboxylic acid are exemplified as follows: the carboxyl group-containing monoester obtained by the reaction of 1 may be obtained by reacting a polyfunctional (meth) acrylate having 1 hydroxyl group and 5 (meth) acryloyl groups with a tetracarboxylic acid in an amount of 2: the carboxyl group-containing diester obtained by the reaction of 1 may be a multifunctional (meth) acrylate containing 2 hydroxyl groups and 4 (meth) acryloyl groups, a tetracarboxylic acid, or a multifunctional (meth) acrylate containing 1 hydroxyl group and 5 (meth) acryloyl groups, wherein 1:2:2, a carboxyl group-containing tetraester obtained by the reaction.
The photopolymerizable compound having an acidic group, which has 7 or more unsaturated double bond groups and an acidic group in 1 molecule, is preferably a compound represented by the following general formula (1) in terms of curability.
[ chemical 8]
General formula (1)
(in the general formula (1), Q represents a tetracarboxylic acid residue or a tetracarboxylic dianhydride residue, R independently represents a hydrogen atom or a (meth) acryloyl group, n represents an integer of 1 to 4, m represents an integer of 0 to 4, j represents an integer of 1 or more, n×j+m is an integer of 3 or more, R of each repeating unit may be the same or different when n, m and j are 2 or more, and 7 or more R in 1 molecule are (meth) acryloyl groups.)
The compound represented by the general formula (1) can be obtained by reacting a tetracarboxylic acid with a polyfunctional (meth) acrylate having 1 or more hydroxyl groups so that 1 molecule has 7 or more (meth) acryloyl groups.
Examples thereof include: reaction of tetracarboxylic acids with pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate; reaction of tetracarboxylic acids with dipentaerythritol penta (meth) acrylate; reaction of tetracarboxylic acids with dipentaerythritol tetra (meth) acrylate; reaction of tetracarboxylic acids with tripentaerythritol hepta (meth) acrylate; etc.; they may also be mixtures.
Examples of the tetracarboxylic acids include: pyromellitic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 4 '-oxydiphthalic anhydride, 3,4' -oxydiphthalic anhydride, 4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, 3,4,9, tetracarboxylic dianhydrides having an aromatic ring such as 10-perylene tetracarboxylic dianhydride, 2,3,6, 7-anthracene tetracarboxylic dianhydride, and 1,2,7, 8-phenanthrene tetracarboxylic dianhydride; tetracarboxylic dianhydrides having an aliphatic ring such as cyclohexane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride, and cyclobutane tetracarboxylic dianhydride; and tetracarboxylic acid dianhydride having an aliphatic hydrocarbon group such as 1,2,3, 4-butane tetracarboxylic acid dianhydride, and tetracarboxylic acid of the acid dianhydride.
The polyfunctional (meth) acrylate compound used as a raw material for producing the compound represented by the general formula (1) is preferably a polyfunctional (meth) acrylate compound having a molecular weight of 500 or more so as not to cause sublimates. That is, for example, dipentaerythritol penta (meth) acrylate is preferably used, and pentaerythritol tri (meth) acrylate is not preferably used.
In the compound represented by the general formula (1), n represents an integer of 1 to 4, m represents an integer of 0 to 4, j represents an integer of 1 or more, and nxj+m is an integer of 3 or more.
n is preferably 1 to 3, more preferably 2 to 3, m is preferably 1 to 3, more preferably 2 to 3, and n+m is preferably 4. If the molecular weight is too large, the developability is deteriorated, which is not preferable.
The number of j is not particularly limited as long as the number of n and m is adjusted so that n×j+m is an integer of 3 or more, and n and m are each preferably 2 or less.
Among them, the compound represented by the following general formula (1') is preferable in terms of developability.
[ chemical 9]
General formula (1')
(in the general formula (1), Q represents a tetracarboxylic acid residue or a tetracarboxylic dianhydride residue, R independently represents a hydrogen atom or a (meth) acryloyl group, R of each repeating unit may be the same or different, and 7 or more R in 1 molecule are (meth) acryloyl groups.)
Examples of the compounds represented by the general formula (1) include: the compounds represented by the following formulas (1-1) to (1-3) are not limited thereto. In the following formulae (1-1) to (1-3), Q represents a pyromellitic dianhydride residue, but may be substituted with other residues of the tetracarboxylic acids.
[ chemical 10]
(1-1)
(1-2)
(1-3)
(wherein R independently represents a hydrogen atom or a (meth) acryloyl group, and 7 or more R in 1 molecule are (meth) acryloyl groups.)
Of the compounds represented by the general formulae (1), (1'), (1-1), (1-2) and (1-3), 7 or more of R in 1 molecule are (meth) acryloyl groups, preferably 80% or more of all R contained in 1 molecule are (meth) acryloyl groups, more preferably 90% or more of all R contained in 1 molecule are (meth) acryloyl groups, and still more preferably all R contained in 1 molecule are (meth) acryloyl groups.
The hydroxyl value of the polyfunctional (meth) acrylate containing the polyfunctional (meth) acrylate having a hydroxyl group and a (meth) acryloyl group, which is used in producing an ester of the polyfunctional (meth) acrylate having a hydroxyl group and a (meth) acryloyl group and a polycarboxylic acid, of the compound represented by the general formula (1) is preferably 50mgKOH/g or more, more preferably 90mgKOH/g or more in terms of reactivity, and is advantageous in terms of adjusting the ratio to an acid group, but if the hydroxyl group is too high, there is a possibility that resolubility may be deteriorated, and is preferably 300mgKOH/g or less, more preferably 130mgKOH/g or less in terms of reactivity.
The hydroxyl value here means the mg number of potassium hydroxide equivalent to the hydroxyl group in 1g of the sample, and can be measured according to the method defined in JIS K0070.
The ratio of the raw materials used in producing the ester of the polyfunctional (meth) acrylate having a hydroxyl group and a (meth) acryloyl group and the polycarboxylic acid type containing the compound represented by the general formula (1) may be appropriately adjusted so that the acid value of the obtained carboxyl group-containing polyfunctional (meth) acrylate having 7 or more (meth) acryloyl groups and carboxyl groups is in the following preferred range, and the ratio (B/a) of the carboxyl equivalent of the polycarboxylic acid type (B) to the hydroxyl equivalent of the hydroxyl group-containing polyfunctional (meth) acrylate (a) is preferably 0.20 equivalent or more, more preferably 0.50 equivalent or more, in terms of not excessively lowering the acid value of the obtained compound, preferably 0.90 equivalent or less.
The carboxyl group-containing polyfunctional (meth) acrylate having 7 or more (meth) acryloyl groups and carboxyl groups may be an adduct of a polyfunctional (meth) acrylate having 8 or more (meth) acryloyl groups and a mercapto carboxylic acid. The carboxyl group can be introduced by adding a mercapto group of a mercapto carboxylic acid to an unsaturated double bond group portion of a (meth) acryloyl group.
Here, examples of the polyfunctional (meth) acrylate having 8 or more (meth) acryloyl groups include: and compounds obtained by reacting tripentaerythritol octa (meth) acrylate, dipentaerythritol penta (meth) acrylate and a polyfunctional isocyanate such as isophorone diisocyanate.
Examples of the mercapto carboxylic acid include: thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.
The number of functional groups of unsaturated double bond groups in 1 molecule of the (main) compound having the highest content of the acidic group-containing photopolymerizable compound is preferably 10 or more in terms of curability, water spotting inhibition, and sublimate reduction.
In terms of curability and water spotting inhibition, the photopolymerizable compound containing an acidic group having 10 or more unsaturated double bond groups and an acidic group in 1 molecule is preferably 50% by mass or more, more preferably 70% by mass or more, and also 85% by mass or more, relative to the total amount of the photopolymerizable compound.
The photopolymerizable compound used in the photosensitive colored resin composition of the present invention may contain 1 photopolymerizable compound having an acidic group and having 7 or more unsaturated double bond groups and acidic groups in the molecule, and may contain photopolymerizable compounds having no acidic group, as long as the molecular weight is 500 or more.
As the photopolymerizable compound having no acidic group, those having a molecular weight of 500 or more are also used, and examples thereof include: and compounds obtained by reacting a polyfunctional isocyanate such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, dipentaerythritol penta (meth) acrylate and isophorone diisocyanate.
These polyfunctional (meth) acrylates may be used singly or in combination of 1 or more than 2.
The photopolymerizable compound having an acidic group having 7 or more unsaturated double bond groups and an acidic group in 1 molecule is preferably 60 mass% or more, more preferably 75 mass% or more, still more preferably 90 mass% or more, or 95 mass% or more, or 100 mass% relative to the total amount of the photopolymerizable compound.
The weight average molecular weight of the photopolymerizable compound containing the acidic group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and acidic groups in 1 molecule is preferably 3000 or less, more preferably 2500 or less in terms of developability.
The weight average molecular weight of the photopolymerizable compound was measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard substance (using Shodex GPC System-21H with NMP added with 10mM LiBr as an eluent).
The acid value of the photopolymerizable compound containing an acidic group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and an acidic group in 1 molecule may be 4mgKOH/g or more, preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, still more preferably 25mgKOH/g or more, and in terms of developability and adhesion, 120mgKOH/g or less, more preferably 100mgKOH/g or less, still more preferably 90mgKOH/g or less, and still more preferably 80mgKOH/g or less, in terms of improving the cross-sectional shape of the colored layer.
Here, the acid value may be determined according to JIS K0070: 1992.
The photopolymerizable compound used in the photosensitive colored resin composition of the present invention has a molecular weight of 500 or more and does not substantially contain a photopolymerizable compound having a molecular weight of less than 500, but may contain a decomposed product or the like within a range that does not impair the effects of the present invention. The photopolymerizable compound having a molecular weight of less than 500 is preferably 3 mass% or less, more preferably 1 mass% or less, relative to the total amount of the photopolymerizable compounds.
The content of the photopolymerizable compound having a molecular weight of less than 500 relative to the total amount of the photopolymerizable compound can be analyzed by a liquid chromatography mass spectrometry device (LC-MS) (for example, company LC-30A,Bruker Daltonics, company microotofq 2, shimadzu).
The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but the content of the photopolymerizable compound used in the photosensitive colored resin composition is usually preferably in the range of 5 mass% or more and 60 mass% or less, and more preferably 10 mass% or more and 40 mass% or less, relative to the total amount of solid components of the photosensitive colored resin composition. When the content of the photopolymerizable compound is not less than the lower limit, photocuring proceeds sufficiently, dissolution of the exposed portion during development is easily suppressed, and when the content of the photopolymerizable compound is not more than the upper limit, alkali developability is easily made sufficient.
Regarding the content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive colored resin composition, the total content ratio of the photoinitiators is, for example, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the photopolymerizable compound, in terms of excellent curability and film residue ratio, and further in terms of improvement of electrical reliability.
[ color Material ]
In the present invention, the color material is not particularly limited as long as it can perform a desired color development when forming a colored layer of a color filter, and various organic pigments, inorganic pigments, dispersible dyes, salt-forming compounds of dyes, and the like may be used alone or in combination of 2 or more. Among them, organic pigments are preferably used because of their high color development and high heat resistance. Examples of the organic pigment include: the compounds classified into pigments (Pigment) in the dye index (c.i.; issued by The Society of Dyers and Colourists company) can be specifically exemplified by: the dye index (c.i.) numbers are labeled as described below.
C.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and c.i. pigment yellow 150;
c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C.i. pigment violet 1, 19, 23, 29, 32, 36, 38;
c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 50: 1. 52: 1. 53: 1. 57, 57: 1. 57: 2. 58: 2. 58: 4. 60: 1. 63: 1. 63: 2. 64: 1. 81: 1. 83, 88, 90: 1. 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272, 291:
c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60;
c.i. pigment green 7, 36, 58, 59, 62, 63;
c.i. pigment brown 23, 25;
c.i. pigment black 1, 7.
Further, specific examples of the inorganic pigment include: titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, dark blue, chromium oxide green, cobalt green, umber (amber), titanium black, synthetic iron black, carbon black, and the like.
For example, when the color material dispersion liquid of the present invention is used as the photosensitive colored resin composition described below to form a pattern of a light shielding layer on a substrate of a color filter, a black pigment having a high light shielding property is blended into the ink. As the black pigment having high light-shielding properties, for example, there can be used: inorganic pigments such as carbon black and ferroferric oxide, or organic pigments such as cyanine black.
As the dispersible dye, there may be exemplified: the dye is made dispersible by imparting various substituents to the dye or by use in combination with a solvent having low solubility.
The salt-forming compound of the dye is a compound obtained by forming a salt of the dye with a counter ion, and examples thereof include: salt-forming compounds of basic dyes and acids, acid dyes and bases, and also include the preparation of solvent-insoluble lake pigments from dyes soluble in solvents using known lake (salification) methods.
In the present invention, the dispersibility and dispersion stability of a color material containing at least one selected from the group consisting of dyes and salt-forming compounds of the dyes can be improved by using the color material in combination with the dispersant of the present invention.
The dye may be appropriately selected from conventionally known dyes. Examples of such dyes include: azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, phthalocyanine dyes, and the like.
When the amount of the dye dissolved is 10mg or less per 10g of the solvent (or mixed solvent) as a standard, it can be determined that the dye is dispersible in the solvent (or mixed solvent).
Among them, in the case where the color material contains at least 1 selected from the group consisting of a pyrrolopyrrole dione pigment, a quinophthalone pigment, a copper phthalocyanine pigment, a zinc phthalocyanine pigment, a quinophthalone dye, a coumarin dye, a cyanine dye, and a salt-forming compound of these dyes, the use of the dispersant is preferable in that the effect of suppressing sublimation or precipitation of the color material is high, and a high-brightness colored layer can be formed. Further, the color material preferably contains at least 1 selected from the group consisting of pyrrolopyrrole dione pigment, quinophthalone pigment, copper phthalocyanine pigment, zinc phthalocyanine pigment, and quinophthalone dye.
Examples of the pyrrolopyrroldione pigment include: C.I. pigment Red 254, 255, 264, 272, 291, and a pyrrolopyrroldiketone pigment represented by the following formula (i), among which R is preferably selected from the group consisting of C.I. pigment Red 254, 272, 291, and R in the following formula (i) 21 R is R 22 At least 1 of pyrrolopyrrolidinone pigments, each of which is 4-bromophenyl.
[ chemical 11]
General formula (i)
(in the general formula (i), R 21 R is R 22 Each independently is 4-chlorophenyl, or 4-bromophenyl. )
Examples of quinophthalone pigments include: c.i. pigment yellow 138, etc.
Examples of the copper phthalocyanine pigment include: c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 5. 15:6. c.i. pigment green 7, 36, etc., of which c.i. pigment blue 15 is preferred: 6.
examples of the zinc phthalocyanine pigment include: c.i. pigment green 58, 59, etc.
Examples of quinophthalone dyes include: c.i. disperse yellow 54, 64, 67, 134, 149, 160, c.i. solvent yellow 114, 157, etc., of which c.i. disperse yellow 54 is preferred.
The average primary particle diameter of the color material used in the present invention is not particularly limited as long as the color filter can perform the desired color development when the color filter is used as a colored layer, and is preferably in the range of 10 to 100nm, more preferably 15 to 60nm, depending on the type of the color material used in the present invention. By setting the average primary particle diameter of the color material to the above range, a display device having a color filter manufactured using the photosensitive colored resin composition of the present invention can be made high in contrast and quality.
The average dispersion particle diameter of the color material in the photosensitive colored resin composition varies depending on the type of color material used, and is preferably in the range of 10 to 100nm, more preferably in the range of 15 to 60 nm.
The average dispersion particle diameter of the color material in the photosensitive colored resin composition is the dispersion particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and can be measured by a laser light scattering particle size distribution analyzer. As the measurement of the particle diameter by the laser light scattering particle size distribution analyzer, the photosensitive colored resin composition may be diluted (for example, 1000 times or the like) appropriately with a solvent used in the photosensitive colored resin composition to a concentration that can be measured by the laser light scattering particle size distribution analyzer, and the measurement may be performed at 23 ℃ by a dynamic light scattering method using the laser light scattering particle size distribution analyzer (for example, nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by daily nectar corporation). The average distribution particle diameter herein is a volume average particle diameter.
The color material used in the present invention can be produced by a known method such as recrystallization or solvent salt milling. Further, commercially available color materials may be subjected to a fine process.
In the photosensitive colored resin composition of the present invention, the content of the color material is not particularly limited. Regarding the content of the color material, the content of the color material is usually preferably 3 mass% or more and 65 mass% or less, more preferably 4 mass% or more and 60 mass% or less, with respect to the total solid content of the photosensitive colored resin composition, in terms of dispersibility and dispersion stability. When the content of the coloring material is not less than the above-mentioned lower limit value with respect to the total amount of solid content of the photosensitive coloring resin composition, the colored layer tends to have a sufficient color density when the photosensitive coloring resin composition is applied to a specific film thickness (usually 1.0 μm to 5.0 μm). Further, when the content of the color material is not more than the above-mentioned upper limit value with respect to the total amount of solid content of the photosensitive colored resin composition, a colored layer excellent in storage stability and having sufficient hardness and adhesion to a substrate can be obtained. In particular, when forming a colored layer having a high color material concentration, the total content of the color materials is, for example, preferably 15 mass% or more and 65 mass% or less, and more preferably 25 mass% or more and 60 mass% or less, relative to the total amount of solid components of the photosensitive colored resin composition.
[ alkali-soluble resin ]
The alkali-soluble resin in the present invention has an acidic group, and can be used by appropriately selecting from alkali developer which functions as a binder resin and is soluble in the alkali developer used for patterning.
In the present invention, the alkali-soluble resin may have an acid value of 40mgKOH/g or more.
Preferred alkali-soluble resins in the present invention are resins having an acidic group, usually having a carboxyl group, and specifically, can be exemplified by: acrylic copolymers having a carboxyl group, acrylic resins such as styrene-acrylic copolymers having a carboxyl group, epoxy (meth) acrylate resins having a carboxyl group, and the like. Of these, those having a carboxyl group in a side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain are particularly preferable. The reason for this is that the film strength of the cured film formed by containing the photopolymerizable functional group is improved. In addition, 2 or more types of acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.
Acrylic resins such as acrylic copolymers containing a constituent unit having a carboxyl group and styrene-acrylic copolymers having a carboxyl group are (co) polymers obtained by (co) polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other copolymerizable monomers by a known method.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include: (meth) acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, it is also possible to use: and addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ω -carboxy-polycaprolactone mono (meth) acrylate, and the like. Further, as the precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, or the like may be used. Among them, (meth) acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.
Regarding the alkali-soluble resin, the alkali-soluble resin preferably further has a hydrocarbon ring in terms of excellent adhesion of the colored layer. It is possible to obtain an insight that solvent resistance of the obtained colored layer, particularly swelling of the colored layer, is suppressed by having a hydrocarbon ring as a bulky group in the alkali-soluble resin. Although the effect is not clear, it is presumed that the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the migration of molecules in the colored layer, and as a result, the strength of the coating film increases, and swelling due to the solvent is suppressed.
Examples of such hydrocarbon rings include: the hydrocarbon ring may have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, or an amide group. In the case of containing an aliphatic ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved.
Specific examples of the hydrocarbon ring include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2, 6) ] decane (dicyclopentane), and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene, and the like; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene (stilbene), and the like, cardo structures (9, 9-diaryl fluorene); a group in which a part of these groups is substituted with a substituent, and the like.
Examples of the substituent include: alkyl, cycloalkyl, alkylcycloalkyl, hydroxy, carbonyl, nitro, amino, halogen atoms, and the like.
The alkali-soluble resin preferably has a maleimide structure represented by the following general formula (ii).
[ chemical 12]
General formula (ii)
(in the general formula (ii), R M Is a hydrocarbon ring which may be substituted. )
In the case where the alkali-soluble resin has the maleimide structure represented by the general formula (ii), since the hydrocarbon ring has a nitrogen atom, the compatibility with the alkali dispersant which is a polymer having a constituent unit represented by the general formula (I) is extremely good, and the effect of suppressing development residues is improved.
R as said formula (ii) M In which the hydrocarbon ring may be substitutedSpecific examples thereof include the same as those of the hydrocarbon ring.
When the aliphatic ring is contained as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved, which is preferable.
In addition, in the case of containing Cardo structure, the curability of the colored layer is improved, and the solvent resistance (NMP swelling inhibition) is improved, which is particularly preferable.
In the alkali-soluble resin used in the present invention, it is preferable to use an acrylic copolymer containing a constituent unit having a hydrocarbon ring in addition to a constituent unit having a carboxyl group, in order to easily adjust the amount of each constituent unit and increase the amount of the constituent unit having the hydrocarbon ring to improve the functions of the constituent unit.
The acrylic copolymer containing a constituent unit having a carboxyl group and the hydrocarbon ring can be produced by using an ethylenically unsaturated monomer having a hydrocarbon ring as the "copolymerizable other monomer".
Examples of the ethylenically unsaturated monomer having the hydrocarbon ring include: the cyclohexyl (meth) acrylate, the dicyclopentanyl (meth) acrylate, the adamantyl (meth) acrylate, the isobornyl (meth) acrylate, the benzyl (meth) acrylate, the phenoxyethyl (meth) acrylate, and the styrene are preferable, and the cyclohexyl (meth) acrylate, the dicyclopentanyl (meth) acrylate, the adamantyl (meth) acrylate, the benzyl (meth) acrylate, and the styrene are particularly preferable, since the effect of maintaining the cross-sectional shape of the colored layer after development even in the heat treatment is strong.
In addition, in terms of the effect of suppressing the development residue, the ethylenically unsaturated monomer having the hydrocarbon ring is preferably a monomer having the maleimide structure, and styrene, and particularly preferably styrene.
In addition, the alkali-soluble resin used in the present invention preferably has an olefinic double bond in a side chain. In the case of having an olefinic double bond, the alkali-soluble resins or the alkali-soluble resins and the photopolymerizable compound may form a crosslinking bond with each other in the curing step of the resin composition at the time of manufacturing the color filter. In combination with the specific photoinitiator used in the present invention, the cured film has a higher film strength and a higher development resistance, and the cured film is suppressed in heat shrinkage and is excellent in adhesion to a substrate.
The method for introducing the olefinic double bond into the alkali-soluble resin can be appropriately selected from conventionally known methods. For example, the following methods are exemplified: a compound having an epoxy group and an olefinic double bond in the molecule, for example, glycidyl (meth) acrylate or the like is added to a carboxyl group of an alkali-soluble resin, and an olefinic double bond is introduced into a side chain; introducing a constituent unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an olefinic double bond in the molecule, and introducing an olefinic double bond into a side chain; etc.
The alkali-soluble resin of the present invention may further contain other constituent units such as methyl (meth) acrylate, ethyl (meth) acrylate, and the like, and constituent units having an ester group. The constituent unit having an ester group functions not only as a component that inhibits alkali solubility of the photosensitive colored resin composition for a color filter, but also as a component that improves solubility in a solvent and further improves solvent resolubility.
The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer containing a constituent unit having a carboxyl group and a constituent unit having a hydrocarbon ring, and more preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer containing a constituent unit having a carboxyl group, a constituent unit having a hydrocarbon ring, and a constituent unit having an olefinic double bond.
The alkali-soluble resin can be an alkali-soluble resin having desired properties by appropriately adjusting the amount of each constituent unit added.
Regarding the amount of the carboxyl group-containing ethylenically unsaturated monomer to be added, the amount of the carboxyl group-containing ethylenically unsaturated monomer to be added is preferably 5 mass% or more, more preferably 10 mass% or more, relative to the total amount of the monomers, in terms of obtaining a good pattern. On the other hand, in terms of suppressing film roughening or the like on the pattern surface after development, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50 mass% or less, more preferably 40 mass% or less, relative to the total amount of the monomers.
In addition, in the acrylic resin such as the acrylic copolymer and the styrene-acrylic copolymer containing a constituent unit having an olefinic double bond, which are more preferably used as the alkali-soluble resin, the amount of the compound having an epoxy group and an olefinic double bond added to the carboxyl group-containing ethylenically unsaturated monomer is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.
The weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If the preferable weight average molecular weight (Mw) of the carboxyl group-containing copolymer is less than 1,000, the function of the binder after curing may be significantly reduced, and if the preferable weight average molecular weight (Mw) of the carboxyl group-containing copolymer exceeds 50,000, the pattern formation may be difficult when development is performed with an alkali developer.
The weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by GPC (using THF as an eluent and Shodex GPC System to 21H) using polystyrene as a standard substance.
The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and an epoxy (meth) acrylate compound obtained by reacting an acid anhydride with a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid is preferable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride may be appropriately selected from known ones and used. The epoxy (meth) acrylate resin having a carboxyl group may be used alone in an amount of 1 kind or in an amount of two or more kinds.
Regarding the alkali-soluble resin, in terms of developability (solubility) with respect to an alkaline aqueous solution used for the developer, the alkali-soluble resin is preferably used with an acid value of 50mgKOH/g or more. The acid value of the alkali-soluble resin is preferably 70mgKOH/g or more and 300mgKOH/g or less, and among these, 70mgKOH/g or more and 280mgKOH/g or less, in terms of developability (solubility) with respect to an alkali aqueous solution used for the developer and in terms of adhesion to a substrate.
In the present invention, the acid value may be determined according to JIS K0070: 1992.
In terms of the effect of improving the film strength of the cured film, improving the development resistance, and having excellent adhesion to a substrate, the ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group is preferably in the range of 100 to 2000, particularly preferably in the range of 140 to 1500, by combining with the compound represented by the above general formula (1) used in the present invention. When the equivalent of the ethylenic unsaturated bond is 2000 or less, the development resistance and the adhesion are excellent. Further, when the equivalent of the ethylenic unsaturated bond is 100 or more, the ratio of the constituent unit having the above-mentioned carboxyl group or the other constituent unit having a hydrocarbon ring or the like can be relatively increased, and therefore the developability and heat resistance are excellent. The compound represented by the general formula (1) used in the present invention is preferably used in combination with the content.
Here, the ethylenically unsaturated bond equivalent means a weight average molecular weight per 1 mol of ethylenically unsaturated bonds in the alkali-soluble resin, and is represented by the following formula (1).
Mathematics (1)
Equivalent of ethylenically unsaturated bond (g/mol) =w (g)/M (mol)
(in the formula (1), W represents the mass (g) of the alkali-soluble resin, M represents the number of moles (mol) of the olefinic double bond contained in the alkali-soluble resin W (g))
The ethylenically unsaturated bond equivalent can be calculated, for example, by following the method according to JIS K0070: the iodine value test method described in 1992 measures the number of olefinic double bonds contained in 1g of the alkali-soluble resin.
The alkali-soluble resin used in the photosensitive colored resin composition may be used alone in an amount of 1 or in combination of 2 or more, and the content thereof is not particularly limited. The total content of the alkali-soluble resins is, for example, preferably 5 to 60 mass%, more preferably 10 to 40 mass%, based on the total solid content of the photosensitive colored resin composition. When the content of the alkali-soluble resin is not less than the lower limit, sufficient alkali developability is easily obtained, and when the content of the alkali-soluble resin is not more than the upper limit, film roughness and pattern defects during development can be suppressed.
[ solvent ]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with the components in the photosensitive colored resin composition and can dissolve or disperse them. The solvent may be used alone or in combination of 2 or more.
Specific examples of the solvent include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as gamma-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; organic solvents such as aromatic hydrocarbons including toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in terms of solubility with other components. Among them, the solvent used in the present invention is preferably 1 or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl Carbitol Acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate in terms of solubility with other components and coating suitability.
In the photosensitive colored resin composition of the present invention, the content of the solvent may be appropriately set within a range in which a colored layer can be formed with high accuracy. The content of the solvent is preferably in a range of usually 55 mass% or more and 95 mass% or less, more preferably 65 mass% or more and 88 mass% or less, relative to the total amount of the photosensitive colored resin composition containing the solvent. The solvent content falling within the above range can provide excellent coating properties.
[ dispersant ]
In the photosensitive colored resin composition of the present invention, the color material is preferably dispersed in a solvent by a dispersant. In the present invention, the dispersant may be appropriately selected from conventionally known dispersants. As the dispersant, for example, usable are: cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymeric dispersant is preferable in terms of being uniformly and finely dispersible.
Examples of the polymer dispersant include: (co) polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates, and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reaction of poly (lower alkylene imine) with free carboxyl group-containing polyesters, their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with 1 or more compounds selected from 3 compounds including polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides)), and the like.
When the polymer dispersant is a copolymer, the polymer dispersant may be any of a block copolymer, a graft copolymer and a random copolymer, and from the viewpoint of dispersibility, the block copolymer and the graft copolymer are preferable.
Among them, a polymer dispersant having an amine value and containing a nitrogen atom in the main chain or side chain is preferable in terms of being capable of suitably dispersing the color material and having good dispersion stability, and a polymer dispersant containing a polymer having a repeating unit containing a tertiary amine is preferable in terms of being good in dispersibility, not precipitating foreign matter at the time of forming a coating film, and improving brightness and contrast.
The repeating unit having a tertiary amine is a site having affinity with the color material. Polymeric dispersants comprising polymers containing repeat units having tertiary amines generally contain repeat units that become sites with affinity for solvents. Among these polymers, a block copolymer containing a block containing a repeating unit having a tertiary amine and a block having a solvent affinity is preferable in terms of excellent heat resistance and formation of a coating film having high brightness.
The repeating unit having a tertiary amine may be any unit having a tertiary amine, and the tertiary amine may be contained in a side chain of the block polymer or may constitute a main chain.
Among them, the repeating unit having a tertiary amine in a side chain is preferable, and among them, the structure represented by the following general formula (I) is more preferable in terms of the main chain skeleton being less likely to be thermally decomposed and having high heat resistance.
[ chemical 13]
General formula (I)
(in the general formula (I), R 1 Represents a hydrogen atom or a methyl group, A 1 Represents a divalent linking group, R 2 R is R 3 R is independently a hydrogen atom or a hydrocarbon group which may contain a hetero atom 2 R is R 3 Can also be bonded to form a ring structure. )
The constituent unit represented by the general formula (I) has basicity and functions as an adsorption site to the color material.
In the general formula (I), A 1 Is a divalent linking group. Examples of the divalent linking group include: linear, branched or cyclic alkylene, linear, branched or cyclic alkylene having a hydroxyl group, arylene, -CONH-group, -COO-group, -NHCOO-group, ether group (-O-group), thioether group (-S-group), combinations thereof, and the like. In the present invention, the bonding direction of the divalent linking group is arbitrary. That is, in the case where the divalent linking group comprises-CONH-, the-CO may be on the carbon atom side of the main chain, -NH may be on the nitrogen atom side of the side chain, whereas-NH may be on the carbon atom side of the main chain, -CO may be on the nitrogen atom side of the side chain.
Wherein A in the general formula (I) is as follows in terms of dispersibility 1 Preferably a divalent linking group comprising a-CONH-group or-COO-group, more preferably a divalent linking group comprising a-CONH-or-COO-group and an alkylene group having 1 to 10 carbon atoms.
As R 2 R is R 3 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom include: alkyl, aralkyl, aryl, and the like.
Examples of the "alkyl" may include: methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc., the number of carbon atoms of the alkyl group is preferably 1 to 18, and among them, methyl or ethyl is more preferred.
Examples of the aralkyl group include: benzyl, phenethyl, naphthylmethyl, biphenylmethyl, and the like. The number of carbon atoms of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Further, examples of the aryl group include: phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced with a substituent containing a heteroatom. Examples of the hetero atom which may be contained in the hydrocarbon group include: oxygen atom, nitrogen atom, sulfur atom, silicon atom, etc.
The hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.
R 2 And R is R 3 Bonding to form a ring structure means that R 2 And R is R 3 A ring structure is formed via a nitrogen atom. R is R 2 R is R 3 Heteroatoms may also be included in the ring structure formed. The ring structure is not particularly limited, and examples thereof include: pyrrolidine ring, piperidine ring, morpholine ring, and the like.
In the present invention, R is preferably 2 And R is R 3 Independently of each other, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R 2 And R is R 3 Bonding to form pyrrolidine ring, piperidine ring and morpholine ring.
Examples of the monomers from which the constituent unit represented by the general formula (I) is derived include: and (meth) acrylamides containing an alkyl-substituted amino group such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide are preferably used in terms of improving dispersibility and dispersion stability.
The constituent unit represented by the general formula (I) may include 1 kind or 2 or more kinds.
In the block portion including the repeating unit having the tertiary amine, the constituent unit represented by the general formula (I) preferably includes 3 or more. Among them, 3 or more and 100 or less are preferable, 3 or more and 50 or less are more preferable, and 3 or more and 30 or less are still more preferable in terms of improving dispersibility and dispersion stability.
In a block copolymer containing a block containing a repeating unit having the tertiary amine (hereinafter, sometimes referred to as an a block) and a block having solvent affinity (hereinafter, sometimes referred to as a B block), the solvent affinity is improved in terms of improving the dispersibility by improving the solvent affinity, and the block copolymer contains a solvent affinity block having a constituent unit copolymerizable with the general formula (I) but not having a constituent unit represented by the general formula (I). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, it may be: AB block copolymers, ABA block copolymers, BAB block copolymers, and the like. Among them, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.
The B block may be the same as the B block of International publication No. 2016/104493.
The number of constituent units constituting the block portion of the solvent affinity can be appropriately adjusted within a range where dispersibility of the color material is improved. Among them, the number of constituent units of the block portion constituting the solvent affinity is preferably 10 or more and 200 or less, more preferably 10 or more and 100 or less, still more preferably 10 or more and 70 or less, in terms of effectively functioning the solvent affinity portion and the color material affinity portion and improving dispersibility of the color material.
The solvent affinity block may be selected so as to function as a solvent affinity site, and the repeating units constituting the solvent affinity block may include 1 kind or 2 or more kinds of repeating units.
In the block copolymer used as the dispersant of the present invention, the ratio m/n of the number m of the constituent units represented by the general formula (I) to the number n of the other constituent units constituting the block portion having affinity for the solvent is preferably in the range of 0.01 to 1, more preferably in the range of 0.05 to 0.7 in terms of dispersibility and dispersion stability of the color material.
In the present invention, the dispersant is preferably a polymer having an amine value of 40mgKOH/g or more and 120mgKOH/g or less, which contains the structure represented by the general formula (I), in terms of good dispersibility, no precipitation of foreign matter during formation of a coating film, and improved brightness and contrast.
When the amine number is within the above range, the viscosity is excellent in stability with time and heat resistance, and alkali developability and solvent resolubility are also excellent. If the amine value of the dispersant is high, the dispersibility and dispersion stability are improved, the solvent solubility and solvent resolubility are improved, compatibility with other components is improved, linearity of the thin line pattern of the colored layer is improved, and the smoothness of micropores is easily suppressed. In the present invention, the amine value of the dispersant is preferably 80mgKOH/g or more, more preferably 90mgKOH/g or more. On the other hand, in terms of solvent resolubility, the amine value of the dispersant is preferably 110mgKOH/g or less, more preferably 105mgKOH/g or less.
The amine number is the number of mg of potassium hydroxide equivalent to perchloric acid required for neutralizing the amine component contained in sample 1g, and can be measured by the method defined in JIS K7237. In the case of measurement by this method, even if an amino group forms a salt with an organic acid compound in the dispersant, the organic acid compound is usually dissociated, and thus the amine value of the block copolymer itself used as the dispersant can be measured.
The lower limit of the acid value of the dispersant used in the present invention is preferably 1mgKOH/g or more in terms of the effect of suppressing the development residue. Among these, the acid value of the dispersant is more preferably 2mgKOH/g or more in terms of more excellent suppression effect of the development residue. In addition, the upper limit of the acid value of the dispersant used in the present invention is preferably 18mgKOH/g or less in terms of preventing deterioration of development adhesion and solvent resolubility, improving the linearity of the fine line pattern of the colored layer, and suppressing the smoothness of the micropores. Among them, the acid value of the dispersant is more preferably 16mgKOH/g or less, and still more preferably 14mgKOH/g or less, in terms of improving the development adhesion and solvent resolubility.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1mgKOH/g or more, and more preferably 2mgKOH/g or more. This is because the inhibition effect of the development residues is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18mgKOH/g or less, more preferably 16mgKOH/g or less, and still more preferably 14mgKOH/g or less. This is because the development adhesion and the solvent resolubility are improved.
In the present invention, the glass transition temperature of the dispersant is preferably 30 ℃ or higher in terms of improving the development adhesion. That is, the glass transition temperature of the dispersant is preferably 30℃or higher, regardless of whether the dispersant is a block copolymer before salt formation or a block copolymer before salt formation. If the glass transition temperature of the dispersant is low, the dispersant may be particularly close to the developer temperature (usually about 23 ℃), and the development adhesion may be lowered. It is assumed that this is because, when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, and as a result, the development adhesion becomes poor. By setting the glass transition temperature to 30 ℃ or higher, molecular movement of the dispersant in the development is suppressed, and therefore it is estimated that the decrease in development adhesion is suppressed.
Regarding the glass transition temperature of the dispersant, the glass transition temperature of the dispersant is preferably 32 ℃ or higher, more preferably 35 ℃ or higher, in terms of development adhesion. On the other hand, the temperature is preferably 200℃or lower in view of ease of handling in use such as accurate weighing.
The glass transition temperature of the dispersant of the present invention can be obtained by measuring the glass transition temperature by Differential Scanning Calorimetry (DSC) according to JIS K7121. When 2 or more peaks indicating the glass transition temperature are observed, the peak area, that is, the peak having the largest area of the portion protruding from the base line of the obtained graph is set as a representative value of the glass transition temperature.
The glass transition temperature (Tg) of the block and the block copolymer can be calculated by the following formula.
1/Tg＝∑(Xi/Tgi)
Here, the block is copolymerized from n monomer components of i=1 to n. Xi is the weight percent of the ith monomer (Σxi=1), tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Wherein Σ is set to the sum of i=1 to n. The value of the glass transition temperature (Tgi) of the homopolymer of each monomer may be the value of Polymer Handbook (3 rd Edition) (J.Brandrup, E.H.Immergut (Wiley-Interscience, 1989)).
When the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, and therefore the colored resin layer is easily peeled from the base substrate at the time of development. By providing the dispersant with a B block containing a constituent unit derived from a carboxyl group-containing monomer, the development adhesion is improved by providing the dispersant with the specific acid value and glass transition temperature. It is estimated that when the acid value is too high, the developing property is excellent, but the polarity is too high, and peeling easily occurs during development.
As is clear from the above, in the present invention, the dispersant is preferably a polymer having a structure represented by the general formula (I) and an amine value of 40mgKOH/g or more and 120mgKOH/g or less, an acid value of 1mgKOH/g or more and 18mgKOH/g or less and a glass transition temperature of 30 ℃ or more, because the dispersant is excellent in dispersion stability of a color material and contrast, and is excellent in solvent resolubility, has high development adhesion, and is easy to form micropores excellent in shape, and the development residue is easy to be inhibited, when the dispersant is a colored resin composition containing the compound represented by the general formula (1).
As the carboxyl group-containing monomer, there may be used: a monomer copolymerizable with the monomer having the constituent unit represented by the general formula (I) and containing an unsaturated double bond and a carboxyl group. Examples of such monomers include: (meth) acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω -carboxyl-polycaprolactone mono (meth) acrylate, and the like can be used. In addition, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as a precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.
The content ratio of the constituent unit derived from the carboxyl group-containing monomer in the block copolymer before salt formation is not particularly limited, and is preferably 0.05 mass% or more and 4.5 mass% or less, more preferably 0.07 mass% or more and 3.7 mass% or less, based on the total mass of the total constituent units of the block copolymer, so that the acid value of the block copolymer can be appropriately set within the specific acid value range.
The content ratio of the constituent unit derived from the carboxyl group-containing monomer is set to the lower limit or more, whereby the effect of suppressing the development residue can be exhibited, and the content ratio of the constituent unit derived from the carboxyl group-containing monomer is set to the upper limit or less, whereby deterioration in development adhesion and deterioration in solvent resolubility can be prevented.
The constituent unit derived from the carboxyl group-containing monomer may be 1 or 2 or more constituent units, and may have the specific acid value.
In addition, in terms of improving development adhesion by setting the glass transition temperature of the dispersant used in the present invention to a specific value or more, it is preferable to set the total of monomers having a glass transition temperature value (Tgi) of a homopolymer of the monomers of 10 ℃ or more to 75 mass% or more, and more preferably to 85 mass% or more in the B block.
In the block copolymer, the ratio m/n of the number m of the constituent units of the a block to the number n of the constituent units of the B block is preferably in the range of 0.05 to 1.5, more preferably in the range of 0.1 to 1.0 in terms of dispersibility and dispersion stability of the color material.
The weight average molecular weight Mw of the block copolymer is not particularly limited, and is preferably 1000 to 20000, more preferably 2000 to 15000, even more preferably 3000 to 12000, in terms of improving the dispersibility and dispersion stability of the color material.
The weight average molecular weight (Mw) was obtained by Gel Permeation Chromatography (GPC) in terms of standard polystyrene. The macromer, the salt-type block copolymer, and the graft copolymer, which are raw materials of the block copolymer, are also prepared under the above-mentioned conditions.
Specific examples of such a block copolymer containing a block containing a repeating unit having a tertiary amine and a block having a solvent affinity include, for example, the block copolymers described in Japanese patent No. 4911253.
When the polymer containing the repeating unit having the tertiary amine is used as the dispersant to disperse the color material, the content of the polymer containing the repeating unit having the tertiary amine is preferably 15 parts by mass or more and 300 parts by mass or less, more preferably 20 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of the color material. When the content of the polymer containing the repeating unit having the tertiary amine is within the above range, the dispersibility and dispersion stability are excellent, and the effect of improving the contrast is improved.
In the present invention, it is also preferable to use a dispersant which is obtained by forming a salt with an organic acid compound or a halogenated hydrocarbon in at least a part of amino groups in a polymer containing a repeating unit of the tertiary amine (hereinafter, such a polymer may be referred to as a salt polymer) in terms of dispersibility and dispersion stability of the color material.
Among them, in terms of excellent dispersibility and dispersion stability of the color material, it is preferable that the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. Specific examples of the organic acid compound used for such a dispersant include, for example, those described in japanese patent application laid-open No. 2012-236882.
In addition, the halogenated hydrocarbon is preferably at least 1 kind of allyl halide such as allyl bromide and benzyl chloride and aralkyl halide in terms of excellent dispersibility and dispersion stability of the color material.
The content of the dispersing agent in the case of using the dispersing agent is not particularly limited as long as the color material can be uniformly dispersed, and for example, the dispersing agent may be used in an amount of 1 mass% or more and 40 mass% or less with respect to the total amount of solid components of the photosensitive colored resin composition. The content of the dispersant in the case of using the dispersant is preferably in the range of 2 mass% or more and 30 mass% or less, more preferably 3 mass% or more and 25 mass% or less, relative to the total amount of solid components of the photosensitive colored resin composition. When the content of the dispersant is not less than the above-mentioned lower limit, the dispersibility and dispersion stability of the color material can be easily improved, and the storage stability of the photosensitive colored resin composition can be further improved. In addition, when the content of the dispersant is not more than the above-mentioned upper limit, the development property is easily improved. In particular, when a colored layer having a high color material concentration is formed, the content of the dispersant is preferably in the range of 2 mass% to 25 mass%, more preferably 3 mass% to 20 mass%, relative to the total amount of solid components of the photosensitive colored resin composition.
[ multifunctional thiol Compound ]
In the photosensitive colored resin composition of the present invention, a polyfunctional thiol compound is preferably used in order to improve the adhesion of the substrate.
The polyfunctional thiol compound generates sulfur radicals by radicals generated from the photoinitiator upon exposure. It is presumed that the sulfur radical is crosslinked by thiol-ene reaction through unsaturated bond of a polyfunctional monomer or the like, and the coating film curability is improved, and as a result, the water spot suppression effect is improved.
The polyfunctional thiol compound used in the present invention is a compound having 2 or more thiol groups in 1 molecule.
The polyfunctional thiol compound may be appropriately selected from known compounds having 2 or more thiol groups in 1 molecule. In the photosensitive colored resin composition of the present invention, 1 kind of polyfunctional thiol compound may be used alone, or 2 or more kinds may be used in combination.
Specific examples of the polyfunctional thiol compound include: 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 2-cyclohexanedithiol, decanedithiol, ethylene glycol dimercaptoacetate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol dimercaptoacetate, 1, 4-butanedithioglycolate, 1, 4-butanedithiobis (3-mercaptopropionate), trimethylol propane trimercapto acetate, trimethylol propane tris (3-mercaptopropionate), pentaerythritol tetramercapto acetate, pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetra (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptopropionate), esters of various polyhydric alcohols with thiol-containing carboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, tri (2-hydroxyethyl) isocyanurate of trimercapto-propionic acid, 1, 4-dimethylmercapto benzene, 2,4, 6-trimercapto-s-triazine, 2- (N, N-di-butylamino) -4, 6-dimercapto-triazine, and the like.
The polyfunctional thiol compound may be a polyfunctional thiol compound having a substituent at a carbon atom at an α -position and/or a β -position with respect to a thiol group. As such specific examples, for example, there may be exemplified: 2, 5-hexanedithiol, 2, 9-decanedithiol, 1, 4-bis (1-mercaptoethyl) benzene, bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, bis (3-mercaptoisobutyl) phthalate, and the like.
In addition, it is possible to exemplify: ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tris (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), pentaerythritol tris (3-mercaptovalerate), and the like.
In the present invention, the polyfunctional thiol compound is preferably a polyfunctional secondary thiol compound having a secondary thiol group in which the carbon atom to which the thiol group is bonded is a secondary carbon atom. This is because the reactivity of the secondary thiol is lower than that of the primary thiol, and thus the secondary thiol is less likely to react with each component in the photosensitive colored resin composition, and the photosensitive colored resin composition is excellent in storage stability.
In addition, in terms of improving the substrate adhesion and the water spot suppression effect, the polyfunctional thiol compound is preferably a polyfunctional thiol compound represented by the following general formula (iii).
[ chemical 14]
General formula (iii)
(in the general formula (iii), R 20 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms 21 An alkylene group having 1 to 6 carbon atoms, E represents a residue of a polyhydric alcohol having 2 to 6 hydroxyl groups, and s is an integer of 2 to 6. )
In the general formula (iii), R 20 Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Wherein R is as follows in terms of storage stability of the photosensitive colored resin composition 20 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
The alkyl group having 1 to 6 carbon atoms is a linear, branched or cyclic alkyl group, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl, various hexyl, cyclopentyl, cyclohexyl, and the like. The alkylene group having 1 to 6 carbon atoms is a linear or branched alkylene group, and examples thereof include: methylene, ethylene, trimethylene, propylene, various butylene, various pentylene, various hexylene, and the like.
In addition, E is the residue of a polyol that forms an ester with a particular thiol group-containing carboxylic acid. Here, as the polyol used, there may be exemplified: ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like, but are not limited thereto. s represents the number of esters of a specific thiol group-containing carboxylic acid and a polyol, and is an integer of 2 to 6 corresponding to the hydroxyl number of the residue of the polyol having a hydroxyl number of 2 to 6.
In the polyfunctional thiol compound used in the present invention, the number of thiol groups in 1 molecule is preferably 3 or more, and further, from the viewpoint of curability, it is preferably 3 to 6.
In the general formula (iii), s is more preferably an integer of 3 to 6.
The content of the polyfunctional thiol compound is, for example, preferably in a range of usually 0.01% by mass or more and 15.0% by mass or less, more preferably 0.1% by mass or more and 10.0% by mass or less, and still more preferably 0.5% by mass or more and 5.0% by mass or less, relative to the total amount of solid content of the photosensitive colored resin composition. When the content of the polyfunctional thiol compound is not less than the lower limit, the effect of suppressing the occurrence of water spots is easily enhanced. On the other hand, if the content of the polyfunctional thiol compound is not more than the upper limit value, the pattern can be made finer.
[ optional additional Components ]
Various additives may be optionally contained in the photosensitive colored resin composition. Examples of the additive include: antioxidants, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
Specific examples of the surfactant and the plasticizer include: japanese patent application laid-open No. 2013-029832.
The photosensitive colored resin composition of the present invention preferably further contains an antioxidant in terms of suppressing the line width shift amount. By including an antioxidant in combination with the specific photoinitiator in the photosensitive colored resin composition of the present invention, excessive radical chain reaction can be controlled without impairing curability when forming a cured film, and therefore linearity is improved even more when forming a fine line pattern, or the ability to form a fine line pattern as designed by a mask line width is improved. In addition, heat resistance can be improved, and reduction in brightness after exposure and post baking can be suppressed, so that brightness can be improved.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known antioxidants. Specific examples of the antioxidant include: the hindered phenol-based antioxidant, amine-based antioxidant, phosphorus-based antioxidant, sulfur-based antioxidant, hydrazine-based antioxidant, and the like are preferably used in terms of the ability to form a fine line pattern as designed by the mask line width and in terms of heat resistance. Can be a latent antioxidant as described in International publication No. 2014/021023.
Examples of the hindered phenol-based antioxidant include: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF corporation), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: irganox 3114, manufactured by BASF), 2,4, 6-tris (4-hydroxy-3, 5-di-tert-butylbenzyl) mesitylene (trade name: irganox 1330, manufactured by BASF), 2 '-methylenebis (6-tert-butyl-4-methylphenol) (trade name: sumizer MDP-S, manufactured by Sumitomo chemical corporation), 6' -thiobis (2-tert-butyl-4-methylphenol) (trade name: irganox 1081, manufactured by BASF), diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: irgamod 195, manufactured by BASF), and the like. Among them, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF corporation) is preferable in terms of heat resistance and light resistance.
The content of the antioxidant is, for example, usually preferably 0.1 mass% or more and 10.0 mass% or less, more preferably 0.5 mass% or more and 5.0 mass% or less, relative to the total amount of solid components of the photosensitive colored resin composition. When the antioxidant content is not less than the lower limit, the ability to form a fine line pattern as designed by the mask line width can be easily improved, and heat resistance is excellent. On the other hand, if the content of the antioxidant is not more than the above-mentioned upper limit, the photosensitive colored resin composition of the present invention can be easily made into a photosensitive colored resin composition having high sensitivity.
< method for producing photosensitive colored resin composition >
The method for producing the photosensitive colored resin composition of the present invention is preferably a method comprising the steps of containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, a polyfunctional thiol compound, and various optional additives, and dispersing the coloring material uniformly in the solvent with the dispersant, in order to improve the contrast; can be prepared by mixing using a known mixing method.
Examples of the method for producing the resin composition include the following methods: (1) First, a method of preparing a color material dispersion by adding a color material and a dispersant to a solvent, and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and, if necessary, various additional components into the dispersion; (2) A method of simultaneously adding a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives to a solvent and mixing them; (3) A method in which a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally various additional components are added to a solvent, and the mixture is mixed and then a color material is added to disperse the mixture; (4) A method of preparing a color material dispersion by adding a color material, a dispersant, and an alkali-soluble resin to a solvent, and mixing the dispersion with the alkali-soluble resin, the solvent, the photopolymerizable compound, the photoinitiator, and, if necessary, various additional components; etc.
Among these methods, the methods (1) and (4) are preferable in that the coloring material is effectively prevented from agglomerating and uniformly dispersed.
As a dispersing machine for carrying out the dispersing treatment, there can be mentioned: roller mills such as a two-roller mill and a three-roller mill, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill and a continuous ring type bead mill. The bead diameter used as a preferable dispersing condition of the bead mill is preferably 0.03mm or more and 2.00mm or less, more preferably 0.10mm or more and 1.0mm or less.
II. cured product
The cured product of the present invention is a cured product of the photosensitive colored resin composition of the present invention.
The cured product of the present invention can be obtained, for example, by forming a coating film of the photosensitive colored resin composition of the present invention, drying the coating film, and then exposing the coating film to light and optionally developing the coating film. The method for forming, exposing, and developing the coating film may be, for example, the same method as that used for forming the colored layer provided in the color filter of the present invention described below.
The cured product of the present invention can suppress the generation of sublimates during drying, is formed by excellent developability, and can suppress the generation of water spots, and is therefore preferably used as a colored layer of a color filter.
III color filter
The color filter of the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a cured product of the photosensitive colored resin composition of the present invention.
The color filter according to the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention. Referring to fig. 1, a color filter 10 of the present invention includes a substrate 1, a light shielding portion 2, and a colored layer 3.
(colored layer)
At least 1 of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition of the present invention.
The colored layer is usually formed in an opening of a light shielding portion on a substrate described below, and usually includes a colored pattern of 3 colors or more.
The arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic (mosaic) type, a delta type, or a 4-pixel arrangement type. The width, area, etc. of the colored layer can be arbitrarily set.
The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the concentration of the solid content component of the photosensitive colored resin composition, the viscosity, and the like, and is generally preferably in the range of 1 μm to 5 μm.
The colored layer can be formed, for example, by the following method.
First, the photosensitive colored resin composition of the present invention is applied to a substrate described below by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die-nozzle coating method, to form a wet coating film. Among them, the spin coating method and the die-nozzle coating method can be preferably used.
Next, the wet coating film is dried by heating using a heating plate, an oven, or the like, and then exposed to light through a specific pattern mask to cause photopolymerization of an alkali-soluble resin, a photopolymerizable compound, or the like, thereby forming a cured coating film. Examples of the light source used for exposure include: ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and electron beams. The exposure amount can be appropriately adjusted according to the light source used, the thickness of the coating film, and the like.
In addition, a heat treatment may be performed to promote polymerization after exposure. The heating conditions may be appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.
Next, development treatment is performed using a developer to dissolve and remove the unexposed portions, whereby a coating film can be formed in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is generally used. A surfactant or the like may be added to the alkaline solution in an appropriate amount.
In addition, the development method may employ a general method.
After the development treatment, the colored layer is usually formed by washing the developer and drying the cured coating film of the photosensitive colored resin composition. The heat treatment may be performed after the development treatment to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.
In addition, according to the use of the color filter of the present invention, minute holes may be formed in the colored layer at the time of the development treatment. In the present invention, the photosensitive colored resin composition is used, so that the desired minute holes can be easily formed in the colored layer. The shape of the micropores is not particularly limited, and may be appropriately selected according to the application, and in the present invention, for example, micropores having a size of about 10 μm×10 μm to 30 μm×30 μm may be formed. The shape of the minute hole is not particularly limited, and examples thereof include: circular, oval, polygonal, etc.
As a method for forming the micro holes in the colored layer, for example, a method in which a pattern photomask in which a micro mask for forming the micro holes is arranged in an opening pattern of a pattern photomask capable of forming a fine line pattern is used as a photomask used for forming the colored layer can be exemplified.
(light shielding section)
The light shielding portion in the color filter of the present invention may be formed in a pattern on a substrate described below, and may be the same as that used as a light shielding portion in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include: stripe, matrix, etc. The light shielding portion may be a metal thin film of chromium or the like obtained by sputtering, vacuum deposition, or the like. Alternatively, the light shielding portion may be a resin layer containing light shielding particles such as carbon particles, metal oxides, inorganic pigments, or organic pigments in the resin binder. In the case of a resin layer containing light-shielding particles, there are the following methods: patterning by development using a photosensitive resist; patterning using an inkjet ink containing light-blocking particles; performing thermal transfer printing on the photosensitive resist; etc.
The film thickness of the light shielding portion is set to be about 0.2 μm or more and about 0.4 μm or less in the case of a metal thin film, and is set to be about 0.5 μm or more and about 2 μm or less in the case of dispersing or dissolving the black pigment in the binder resin.
(substrate)
As the substrate, a transparent substrate, a silicon substrate, a transparent substrate or a silicon substrate on which aluminum, silver/copper/palladium alloy thin films, or the like are formed is used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, examples thereof include: transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, which are not flexible, and transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass, which are flexible.
The thickness of the transparent substrate is not particularly limited, and for example, a thickness of 100 μm or more and 1mm or less may be used according to the application of the color filter of the present invention.
In the color filter of the present invention, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like may be formed in addition to the substrate, the light shielding portion, and the colored layer.
IV display device
The display device of the present invention is characterized by having the color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from conventionally known display devices, for example: liquid crystal display devices, organic light emitting display devices, and the like.
[ liquid Crystal display device ]
The liquid crystal display device of the present invention comprises: the color filter, the opposite substrate and the liquid crystal layer formed between the color filter and the opposite substrate are provided.
The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in fig. 2, the liquid crystal display device 40 of the present invention includes: a color filter 10, an opposite substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the color filter 10 and the opposite substrate 20.
The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and may be a known configuration as a liquid crystal display device using a color filter.
The driving method of the liquid crystal display device of the present invention is not particularly limited, and in general, a driving method used for the liquid crystal display device can be employed. Examples of such a driving method include: TN system, IPS system, OCB system, MVA system, and the like. In the present invention, any of these modes can be suitably used.
The counter substrate may be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies, and mixtures thereof can be used according to the driving method or the like of the liquid crystal display device of the present invention.
As a method for forming the liquid crystal layer, a method used as a method for manufacturing a liquid crystal cell can be generally used, and examples thereof include: vacuum injection, liquid crystal dropping, and the like. After the liquid crystal layer is formed by the above method, the liquid crystal cell is allowed to cool down to room temperature, whereby the enclosed liquid crystal can be aligned.
[ organic light-emitting display device ]
The organic light-emitting display device of the present invention includes the color filter of the present invention and an organic light-emitting body.
The organic light emitting display device according to the present invention will be described with reference to the accompanying drawings. Fig. 3 is a schematic view showing an example of the organic light emitting display device of the present invention. As illustrated in fig. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. The organic protective layer 50 and the inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.
Examples of the method for stacking the organic light-emitting body 80 include: a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter; and a method of bonding the organic light-emitting body 80 formed on the other substrate to the inorganic oxide film 60. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light-emitting body 80 can be appropriately used. The organic light emitting display device 100 manufactured in this way can be applied to, for example, a passive driving type organic EL display, and also to an active driving type organic EL display.
The organic light-emitting display device of the present invention is not limited to the configuration shown in fig. 3, and may be a known configuration as an organic light-emitting display device using a color filter.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these descriptions.
The structure of the obtained compound was confirmed by mass spectrometry using a liquid chromatography mass spectrometry device (LC-MS) (company of shimadzu, LC-30A,Bruker Daltonics, microotofq 2).
The content (mass%) of the compound having a molecular weight of less than 500 contained in the photopolymerizable compound was determined by LC-MS.
The number of main functional groups in the photopolymerizable compound having an acidic group represents the number of functional groups in 1 molecule of the compound having the highest content, and the number of main functional groups is determined by LC-MS.
The acid value and the hydroxyl value were obtained by the measurement method described in the specification of the present invention.
The weight average molecular weight was obtained by GPC (gel permeation chromatography) according to the measurement method of the present invention described above, based on standard polystyrene conversion values.
( Production example 1: production of photopolymerizable Compound 1 containing acidic group )
Into a separable round-bottomed flask were placed 100 parts by mass of propylene glycol monomethyl ether acetate, 86.4 parts by mass of a hydroxyl group-containing polyfunctional (meth) acrylate (trade name ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 90mgKOH/g, manufactured by Tokyo synthesis), 13.6 parts by mass of pyromellitic dianhydride (manufactured by Tokyo chemical industry), and 0.3 part by mass of dimethylbenzylamine as a catalyst, and the mixture was heated and stirred at 100℃for 3 hours to obtain an acidic group-containing photopolymerizable compound 1.
As the ratio (B/a) of the carboxyl equivalent of the polycarboxylic acid (B) to the hydroxyl equivalent of the hydroxyl-containing polyfunctional (meth) acrylate (a), assuming that 2 carboxyl groups of the acid dianhydride react with hydroxyl groups, the molecular weight (carboxyl equivalent) of each 1 carboxyl group of pyromellitic acid is 218.12/2= 109.06, the result was 0.90 as calculated from the hydroxyl equivalent (=56.1×1000/hydroxyl value 90= 623.4) of the hydroxyl-containing polyfunctional (meth) acrylate by (13.6/109.06)/(86.4/623.4).
The photopolymerizable compound 1 having an acidic group had a weight average molecular weight of 2000, an acid value of 74mgKOH/g, a main functional group number of 10 functions, and a content of a compound having a molecular weight of less than 500 was 0 mass%.
( Production examples 2 to 5: production of photopolymerizable Compounds 2 to 5 containing an acidic group )
In production example 1, acid group-containing photopolymerizable compounds 2 to 5 were obtained in the same manner as in production example 1, except that the content ratio of the hydroxyl group-containing polyfunctional (meth) acrylate and pyromellitic dianhydride in the total 100 parts by mass was changed so that the ratio (B/a) of the carboxyl group equivalent of pyromellitic dianhydride to the hydroxyl group equivalent of the hydroxyl group-containing polyfunctional (meth) acrylate became the values shown in table 1.
The weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of the photopolymerizable compounds 2 to 5 containing an acidic group are shown in table 1.
( Production examples 6 to 7: production of photopolymerizable Compounds 6 and 7 containing acidic group )
Photopolymerizable compounds 6 and 7 having an acidic group were obtained in the same manner as in production example 1, except that the acid dianhydride shown in table 1 was used instead of pyromellitic dianhydride in production example 1.
The weight average molecular weight, acid value, number of main functional groups, and content of the compounds having a molecular weight of less than 500 of the photopolymerizable compounds 6 and 7 containing acidic groups are shown in Table 1.
( Production examples 8 to 9: production of photopolymerizable Compounds 8 and 9 containing acidic group )
In production example 1, as shown in Table 1, instead of the hydroxyl group-containing polyfunctional (meth) acrylate, the hydroxyl group-containing polyfunctional (meth) acrylate and pyromellitic dianhydride were obtained in the same manner as in production example 1 except that the hydroxyl group equivalent ratio (B/A) of pyromellitic dianhydride to the hydroxyl group equivalent ratio of the hydroxyl group-containing polyfunctional (meth) acrylate was changed to the value shown in Table 1 by using the trade names ARONIX MT3545 (dipentaerythritol tetraacrylate and dipentaerythritol pentaacrylate, hydroxyl value 129mgKOH/g, manufactured by east Asia synthesis) or the trade names ARONIX M-402 (dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 29mgKOH/g, manufactured by east Asia synthesis) in place of the trade names ARONIX M-403.
The weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of the photopolymerizable compounds 8 and 9 containing an acidic group are shown in table 1.
( Production example 10: production of photopolymerizable Compound 10 containing acidic group )
99.4 parts by mass of a hydroxyl group-containing polyfunctional (meth) acrylate (trade name: viscoat # -802, tripentaerythritol heptaacrylate and tripentaerythritol octaacrylate, manufactured by the organic chemical industry of osaka, having a hydroxyl value of 32 mgKOH/g), 0.6 parts by mass of thioglycolic acid, 0.5 parts by mass of N, N-dimethylbenzylamine, and 0.6 parts by mass of 4-methoxyphenol were charged into a four-necked flask having a capacity of 1L, and the reaction was carried out at a temperature of 50 to 60 ℃ for 6 hours to obtain an acidic group-containing photopolymerizable compound 10.
Table 1 shows the weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of the acidic group-containing photopolymerizable compound 10.
( Comparative production examples 1 to 2: comparative production of photopolymerizable Compounds 1 and 2 )
In production example 1, as a hydroxyl group-containing polyfunctional (meth) acrylate, as shown in table 1, trade names aromix M-305 (pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value 118mgKOH/g, manufactured by east asia synthesis) or trade names aromix MT3548 (dipentaerythritol diacrylate and dipentaerythritol triacrylate, manufactured by east asia synthesis) were used instead of trade names aromix M-403, and the content ratio of hydroxyl groups equivalent of pyromellitic dianhydride to hydroxyl groups equivalent of the hydroxyl group-containing polyfunctional (meth) acrylate (B/a) was changed to the value shown in table 1 in 100 parts by mass in total, to obtain comparative photopolymerizable compounds 1 and 2 in the same manner as production example 1.
Table 1 shows the weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of the comparative photopolymerizable compounds 1 and 2.
Comparative production example 3 production of comparative photopolymerizable Compound 3
In production example 1, as shown in Table 1, a comparative photopolymerizable compound 3 was obtained in the same manner as in production example 1 except that the hydroxyl group-containing multifunctional (meth) acrylate and succinic anhydride were changed in the total content ratio of 100 parts by mass in such a manner that the hydroxyl group-containing multifunctional (meth) acrylate and succinic anhydride were changed, as shown in Table 1, by using the trade names ARONIX M-402 (dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, having hydroxyl numbers of 29mgKOH/g, manufactured by east Asia synthesis) instead of the trade names ARONIX M-403 and succinic anhydride instead of pyromellitic dianhydride. It was assumed that 1 carboxyl group of succinic anhydride was reacted with a hydroxyl group, and the molecular weight (carboxyl equivalent) per 1 carboxyl group was calculated.
Table 1 shows the weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of comparative photopolymerizable compound 3.
Comparative production example 4 production of comparative photopolymerizable Compound 4
In 80% of the solid content, 85.5 parts by mass of a hydroxyl group-containing polyfunctional (meth) acrylate (trade name ARONIX M-403, manufactured by Toyama Synthesis) and 14.5 parts by mass of isophorone diisocyanate (IPDI, manufactured by Mitsui chemical Co., ltd.) were dissolved in propylene glycol monomethyl ether, and 1 part by mass of a catalyst (Neostann U-830, manufactured by Nissin chemical Co., ltd.) was placed therein, and the mixture was heated and stirred at 100℃for 2 hours. The disappearance of the peak of isocyanate group was confirmed by IR, and the end point of the reaction was set.
Table 1 shows the weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of comparative photopolymerizable compound 4.
Comparative production example 5 production of comparative photopolymerizable Compound 5
Comparative photopolymerizable compound 5 was obtained in the same manner as in production example 1 except that 1,2, 3-propanetricarboxylic acid was used instead of pyromellitic dianhydride in production example 1, and the content ratio of the hydroxyl group-containing polyfunctional (meth) acrylate and 1,2, 3-propanetricarboxylic acid in total 100 parts by mass was changed so that the ratio (B/a) of the carboxyl group equivalent of 1,2, 3-propanetricarboxylic acid to the hydroxyl group equivalent of the hydroxyl group-containing polyfunctional (meth) acrylate became the value shown in table 1. It was assumed that 3 carboxyl groups of 1,2, 3-propanetricarboxylic acid were reacted with hydroxyl groups, and the molecular weight (carboxyl equivalent) per 1 carboxyl group was calculated.
Table 1 shows the weight average molecular weight, acid value, number of main functional groups, and content of the compound having a molecular weight of less than 500 of comparative photopolymerizable compound 5.
TABLE 1
Table 1.
Synthesis example 1 Synthesis of Compound A-1
(1) Synthesis of intermediate A1
0.2mol of diphenyl sulfide and crushed AlCl are put into a 500ml four-necked flask 3 0.22mol of ethylene dichloride (150 ml) was stirred, argon was introduced, the mixture was cooled in an ice bath, and when the temperature was lowered to 0 ℃, a solution containing 0.22mol of cyclohexylpropionyl chloride and 42g of ethylene dichloride was started to be added dropwise, and the mixture was added over about 1.5 hours while the temperature was adjusted to 10 ℃. The temperature was raised to 15℃and the reaction mixture was stirred for 2 hours, followed by discharging the reaction mixture.
The reaction solution was slowly poured into dilute hydrochloric acid containing 400g of ice and 65ml of concentrated hydrochloric acid under stirring, the lower layer was separated by a separating funnel, the upper layer was extracted with 50ml of dichloroethane, and the extracts and the lower layer were combined. Thereafter, by compounding with NaHCO 3 10g and 200g NaHCO water 3 The solution was washed, then 3 times with 200ml of water until the pH was neutral, over 60g of anhydrous MgSO 4 Drying is carried out to remove moisture, after which the dichloroethane is evaporated by rotary evaporation. The solid powder remaining in the rotary evaporation bottle was put into 200ml of petroleum ether, suction-filtered, and then put into 150ml of absolute ethanol, heated, and refluxed. Thereafter, it was cooled to room temperature, then cooled by ice for 2 hours, suction-filtered, and dried in an oven at 50 ℃ for 2 hours, thereby obtaining the following intermediate A1.
[ 15]
Intermediate A1
(2) Synthesis of intermediate A2
142g of the intermediate A, 400g of tetrahydrofuran, 200g of concentrated hydrochloric acid and 24.2g of isoamyl nitrite were put into a 500ml four-necked flask, and the mixture was stirred at room temperature for 5 hours, followed by discharging the reaction solution.
The reaction solution was put into a beaker, 1000ml of water was added thereto and stirred, and then the mixture was allowed to stand overnight, whereby a yellow viscous liquid was obtained by delamination. The viscous liquid was extracted with dichloroethane, and 50g of anhydrous MgS was chargedO 4 After drying, suction filtration was performed to remove the solvent by rotary evaporation of the filtrate, and an oily viscous material was obtained. Then, the viscous material was put into 150ml of petroleum ether, stirred and precipitated, and suction filtration was performed to obtain a white powdery solid. Thereafter, it was dried at 60℃for 5 hours to obtain the following intermediate A2.
[ 16]
Intermediate A2
(3) Synthesis of Compound A-1
234g of the intermediate A, 350ml of dichloroethane and 12.7g of triethylamine were put into a 1000ml four-necked flask and stirred, and then cooled in an ice bath, and when the temperature was lowered to 0 ℃, the dropwise addition of a solution containing 15.7g of acetyl chloride and 15g of dichloroethane was started, and the addition took about 1.5 hours. Then, after stirring for 1 hour, 500ml of cold water was added dropwise, and the mixture was separated into layers by a separating funnel. By 5% NaHCO 3 The solution was washed 1 time with 200m1, 2 times with 200ml of water until the pH was neutral, 1 time with diluted hydrochloric acid containing 20g of concentrated hydrochloric acid and 400ml of water, 3 times with 200ml of water, and 100g of anhydrous MgSO 4 Drying is performed, and the solvent is removed by rotary evaporation, thereby obtaining a viscous liquid. An appropriate amount of methanol was added to the viscous liquid, and the white solid thus precipitated was filtered and dried to obtain a compound A-1 represented by the following chemical formula (A-1). The molecular weight of the following compound A-1 was 395.51.
[ chemical 17]
Chemical formula (A-1)
Synthesis example 2 Synthesis of Compound B-1
35.5g of fluorene, 120g of methylene chloride and 30.1g of isobutyryl chloride were mixed, cooled until the temperature became-5 ℃ or higher and 0 ℃ or lower, and then 10 times of aluminum trichloride was added thereto and reacted at 10 ℃ for 6 hours. The obtained reaction solution was poured into a mixture of 50g of hydrochloric acid and 150g of ice, and 150g of methylene chloride was added thereto and stirred for 3 hours. Thereafter, the organic phase obtained by the separation was concentrated, 150g of methanol was added to give a solid phase, and then the solid phase was cooled to crystallize the organic phase, and the organic phase was filtered and dried to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone.
27g of the obtained 2-methyl-1-fluorenyl-2-chloro-1-propanone was charged into a 250mL three-necked flask, and 1.76g of calcium oxide and 7.0g of sodium methoxide were further added thereto, followed by epoxidation at 68℃for 6 hours. After cooling to 50℃68g of morpholine were added and the reaction was continued for 14 hours. Then, the mixture was refluxed with a mixed solvent of toluene and methanol to obtain 2-methyl-1-fluorenyl-2-morpholinyl-1-propanone.
The obtained 2-methyl-1-fluorenyl-2-morpholinyl-1-propanone (20 g), tetrabutylammonium bromide (TBAB) (0.6 g) and chlorobutane (34 g) were mixed, the temperature was raised to 78 ℃, and a 50% aqueous NaOH solution (72 g) was added dropwise thereto to maintain the reaction at 82℃for 4 hours. Thereafter, the temperature was lowered, 50g of water and 58g of toluene were added thereto, and the mixture was stirred for 0.5 hour. The obtained organic phase was decolorized with activated carbon, filtered, crystallized using a mixed solvent of toluene and methanol, and the precipitate was filtered and dried to obtain a compound B-1 represented by the following chemical formula (B-1). The molecular weight of the following compound B-1 was 433.63.
[ chemical 18]
Chemical formula (B-1)
Synthesis example 3 preparation of dispersant (Block copolymer A)
A500 mL round-bottom four-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 250 parts by mass of THF and 0.6 part by mass of lithium chloride, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to-60 ℃, 4.9 parts by mass of butyllithium (15% by mass of hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. The addition funnel was used to drop 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-Butyl Methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of Methyl Methacrylate (MMA) as monomers for the B block. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) as a monomer for the A block was added dropwise over a period of 20 minutes. After the reaction was performed for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was re-precipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to give a 30 mass% solution of solid content. 32.5 parts by mass of water was added thereto, and the temperature was raised to 100℃and the reaction was carried out for 7 hours, whereby the constituent units derived from EEMA were deprotected to prepare constituent units derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was further precipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer A (acid value: 8mgKOH/g, tg: 38 ℃ C.) comprising an A block comprising constituent units represented by the general formula (I) and a B block comprising constituent units derived from a carboxyl group-containing monomer and having solphilicity. The block copolymer a obtained in this way was confirmed by GPC (gel permeation chromatography), and as a result, the weight average molecular weight Mw was 7730. The amine value was 95mgKOH/g.
Synthesis example 4 Synthesis of alkali-soluble resin A solution
A mixture of 40 parts by mass of styrene, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of Azobisisobutyronitrile (AIBN) was dropwise added to a polymerization tank charged with 150 parts by mass of PGMEA under a nitrogen flow at 100℃for 3 hours. After the completion of the dropwise addition, the mixture was heated at 100℃for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000.
Next, 20 parts by mass of Glycidyl Methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the polymer solution obtained, and the mixture was heated at 110 ℃ for 10 hours, and air was introduced into the reaction solution. The alkali-soluble resin A obtained was a resin in which a side chain having an olefinic double bond was introduced into a main chain formed by copolymerization of styrene with MMA and MAA using GMA, and the solid content was 42.6% by mass, the acid value was 74mgKOH/g, and the weight-average molecular weight was 12000. The weight average molecular weight was measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. The method for measuring the acid value was carried out based on JIS K0070.
Example 1
(1) Production of color Material Dispersion 1
5.1 parts by mass of the block copolymer a of synthesis example 3 as a dispersant, 15 parts by mass of c.i. pigment red 291 (trade name: manufactured by MT-CF CINIC) as a color material, 5.1 parts by mass of the alkali-soluble resin a solution obtained in synthesis example 4 in terms of solid content, 76.8 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, and were oscillated for 1 hour by a paint shaker (manufactured by shallow iron works company limited) as a pre-crushing, then the zirconia beads having a particle diameter of 2.0mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly, as a main crushing, dispersed for 4 hours by a paint shaker, to obtain a color material dispersion 1.
(2) Production of photosensitive colored resin composition 1
1286.1 parts by mass of the color material dispersion liquid obtained in the above (1), 8.6 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 4 in terms of solid content, 118.2 parts by mass of the acid group-containing photopolymerizable compound obtained in Synthesis example 1 as a photopolymerizable compound, 15.1 parts by mass of the compound A-15.2 parts by mass obtained in Synthesis example 1 as a photoinitiator, and 42.2 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 1.
Examples 2 to 9
In the procedure of preparing the photosensitive colored resin composition of example 1, photosensitive colored resin compositions 2 to 9 were obtained in the same manner as in example 1, except that the acidic group-containing photopolymerizable compounds 2 to 9 of production examples 2 to 9 were used instead of the acidic group-containing photopolymerizable compound 1 of production example 1 as shown in table 2.
Example 10
In the procedure of preparing the photosensitive colored resin composition of example 1, the photosensitive colored resin composition 10 was obtained in the same manner as in example 1, except that the acidic group-containing photopolymerizable compound 1 of production example 1 was replaced with the acidic group-containing photopolymerizable compound 10 of production example 10, 2.55 parts by mass of the compound a-1 and 2.55 parts by mass of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (trade name Irgacure 369, manufactured by basf, irg 369) were replaced with 5.1 parts by mass of the compound a-1, and further that a polyfunctional thiol compound (pentaerythritol tetrakis (3-mercaptobutyrate), trade name Karenz PE1, manufactured by sho electrician, polyfunctional thiol a) was added to the photosensitive colored resin composition as a photoinitiator.
Example 11
A photosensitive colored resin composition 11 was obtained in the same manner as in example 1, except that 1.0 part by mass of a polyfunctional thiol compound (trade name: karenz MT PE1, manufactured by sho and electrician) was added to the photosensitive colored resin composition in example 1.
Example 12
In example 1, a photosensitive colored resin composition 12 was obtained in the same manner as in example 1, except that 2.55 parts by mass of compound a-1 and 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (manufactured by basf) were used as photoinitiators in place of 5.1 parts by mass of compound a-1, and 1.0 parts by mass of a polyfunctional thiol compound (manufactured by Karenz MT PE1, manufactured by sho. Electrician) was added to the photosensitive colored resin composition.
Example 13
In example 1, a photosensitive colored resin composition 13 was obtained in the same manner as in example 1, except that the compound B-15.1 parts by mass obtained in synthesis example 2 was used as a photoinitiator instead of using 5.1 parts by mass of the compound a-1.
Example 14
A photosensitive colored resin composition 14 was obtained in the same manner as in example 13, except that 1.0 part by mass of a polyfunctional thiol compound (trade name: karenz MT PE1, manufactured by sho and electrician) was further added to the photosensitive colored resin composition in example 13.
Example 15
In example 12, a photosensitive colored resin composition 15 was obtained in the same manner as in example 12, except that 5.1 parts by mass of the compound B-1 was used as a photoinitiator instead of using 5.1 parts by mass of the compound a-1.
Example 16
(1) Production of color Material Dispersion 2
As the color material, c.i. pigment blue 15:6 (trade name fastagen BLUE a510, manufactured by DIC corporation) 11.6 parts by mass and 1.4 parts by mass of c.i. pigment violet 23 (trade name Hostaperm Violet RL-NF, manufactured by Clariant) were used instead of using 15 parts by mass of c.i. pigment red 291 (trade name MT-CF, manufactured by CINIC), a color material dispersion 2 was obtained in the same manner as in the color material dispersion 1.
(2) Production of photosensitive colored resin composition 16
A photosensitive colored resin composition 16 was obtained in the same manner as in example 12, except that the color material dispersion liquid 2 was used instead of the color material dispersion liquid 1 in example 12.
Example 17
(1) Production of color Material Dispersion 3
A color material dispersion 3 was obtained in the same manner as in the color material dispersion 1, except that 10.5 parts by mass of c.i. pigment GREEN 58 (trade name fastagen GREEN a350, manufactured by DIC corporation) and 4.5 parts by mass of c.i. pigment yellow 138 (trade name Chromofine Yellow 6206EC, manufactured by the geneva refinement industry) were used instead of using 15 parts by mass of c.i. pigment red 291 (trade name MT-CF, manufactured by CINIC) as the color material.
(2) Production of photosensitive colored resin composition 17
A photosensitive colored resin composition 17 was obtained in the same manner as in example 12, except that the color material dispersion 3 was used instead of the color material dispersion 1 in example 12.
Comparative examples 1 to 5
In the procedure of preparing the photosensitive colored resin composition of example 1, comparative photosensitive colored resin compositions 1 to 5 were obtained in the same manner as in example 1 except that comparative photopolymerizable compounds 1 to 5 of comparative production examples 1 to 5 were used instead of the acidic group-containing photopolymerizable compound 1 of production example 1 as shown in table 2.
Comparative example 6
In example 1, a comparative photosensitive colored resin composition 6 was obtained in the same manner as in example 1, except that 2.55 parts by mass of an α -aminoketone photoinitiator Irg907 (trade name Irgacure 907, manufactured by basf) and 2.55 parts by mass of an oxime ester photoinitiator OXE02 (trade name Irgacure OXE-02, manufactured by basf) were used as photoinitiators in place of 5.1 parts by mass of the compound B-1 obtained in synthesis example 1.
[ evaluation ]
When the evaluation result is "o", the evaluation is relatively good, and the order of "excellent", "very excellent", and "very excellent" is more good.
< sublimation >
The photosensitive colored resin compositions obtained in each example and each comparative example were applied to the entire surface of a 5cm square GLASS substrate (manufactured by NH techon gloss corporation, NA 35) using a spin coater so that the film thickness after heat drying became 2.5 μm, and dried under reduced pressure at a limiting pressure of 40Pa, whereby a coating film was formed. The glass substrate having the coating film formed on one surface thereof was placed on the heating plate so that the glass substrate side was in contact with the heating plate, and the glass substrate (10 cm square) on the upper surface was placed at a position 0.7mm from the surface of the coating film so as to cover the entire coating film. The coated film of the photosensitive colored resin composition was heated to 100 ℃ and held for 10 minutes in a state where the heated plate, the glass substrate, the coated film of the photosensitive colored resin composition, and the glass substrate on the upper surface were arranged in this order, whereby the coated film was heated and dried. After the heat drying, the surface of the glass substrate on the upper surface was observed by visual inspection and an optical microscope (magnification 100 times), and evaluated by the following evaluation criteria. In each example and each comparative example, 10 samples were evaluated. Table 2 shows the evaluation results of the most sublimates adhering to the upper surface of the glass substrate.
(sublimation evaluation reference)
And (3) the following materials: the sublimate was not observed to adhere to the glass substrate on the upper surface by either visual observation or microscopic observation.
O: the sublimates were observed to adhere to the glass substrate on the upper surface, with an adhesion area of less than 10% of the glass substrate.
Delta: the sublimates were observed to adhere to the glass substrate on the upper surface, and the adhering area was 10% or more and less than 50% of the glass substrate.
X: the sublimates were observed to adhere to the glass substrate on the upper surface, and the adhering area was 50% or more of the glass substrate.
< developability >
The photosensitive colored resin compositions obtained in each example and each comparative example were applied to a GLASS substrate (manufactured by NH techeno GLASS group, inc. On "NA 35") using a spin coater so that the thickness of the cured coating film became 2.5 μm, and dried under reduced pressure at a limiting pressure of 40Pa, and then dried at 100 ℃ for 10 minutes using a hot plate to form a coating film on the GLASS substrate. A20 μm by 20 μm chromium mask was placed in the center of each of the individual thin lines having an opening size of 90 μm by 300 μm, and passed through a 40mJ/cm ultra-high pressure mercury lamp 2 The coating film is exposed to ultraviolet rays, thereby forming a post-exposure coating film on the glass substrate. Then, a developing treatment was performed by spin developing with a 0.05 mass% aqueous potassium hydroxide solution as a developing solution, followed by 60 seconds of liquid-contacting with the developing solution and washing with pure water, whereby an independent fine line pattern-like coating film having minute holes was obtained. The speed of the time of patterning was measured.
(developability evaluation criterion)
Very good: and less than 10 seconds.
Very good: more than 10 seconds and 20 seconds or less.
And (3) the following materials: more than 20 seconds and 40 seconds or less.
O: more than 40 seconds and 60 seconds or less.
X: over 60 seconds.
< inhibition of Water Spot >
The photosensitive colored resin compositions obtained in each example and each comparative example were applied onto a GLASS substrate (manufactured by NH TECHNO GLASS Co., ltd., "NA35", thickness 0.7mm,100 mm. Times.100 mm) using a spin coater so that the thickness of the cured coating film became 2.5 μm, and dried at 100℃for 3 minutes using a heating plate, and the entire surface was irradiated with an ultra-high pressure mercury lamp with 40mJ/cm without sandwiching a photomask therebetween 2 Thereby forming a colored layer on the glass substrate. Next, 0.05wt% potassium (KOH) was set as a developer, and after spray development was performed for 60 seconds, the substrate was subjected to development treatment by washing with pure water, and after spin-washing, the substrate was subjected to spin-washing for 10 seconds, and immediately after water was removed by centrifugation, the contact angle of pure water was measured to evaluate water spots as described below.
For measurement of the contact angle of pure water, 1.0. Mu.L of a droplet of pure water was dropped onto the surface of the colored layer immediately after the water was removed by centrifugation, and the static contact angle after 10 seconds of dropping was measured according to the θ/2 method. The measuring device uses a contact angle meter DM 500 manufactured by the interfacial science for measurement.
(Water spot evaluation criterion)
Very good: the contact angle is 70 degrees or more.
And (3) the following materials: the contact angle is 50 degrees or more and less than 70 degrees.
O: the contact angle is 30 degrees or more and less than 50 degrees.
Delta: the contact angle is less than 30 degrees.
< substrate adhesion >
The photosensitive colored resin compositions obtained in each of examples and comparative examples were used to form colored layers in the same manner as in the evaluation of water spot inhibition, and the cross-cut test according to JIS K5600-5-6 was performed, and after repeating the peeling operation with an adhesive tape 5 times, the presence or absence of peeling of the colored layers was observed, and evaluated based on the following evaluation criteria.
(substrate adhesion evaluation criterion)
Very good: any lattice was not peeled off.
And (3) the following materials: there are portions where the coloring layer is peeled off along the dicing lines, but there are no portions where the entire lattice is peeled off.
O: the whole lattice peeling part exists, and the peeling occupied area is less than 25%.
Delta: the entire lattice is peeled, and the area occupied by peeling is 25% or more.
< defect resistance >
The photosensitive colored resin compositions of examples and comparative examples were applied to a GLASS substrate (manufactured by NH techon GLASS group, inc., NA 35) using a spin coater so that the thickness of the cured coating film became 2.5 μm, and dried at 100 ℃ for 3 minutes using a hot plate, thereby forming a colored layer. Irradiating the colored layer with 40mJ/cm using an extra-high pressure mercury lamp with a photomask having a mask opening width of 80 μm and a mask light shielding width of 160 μm therebetween 2 Is a ultraviolet ray of (a). The glass plate on which the colored layer was formed was subjected to spray development using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer for 100 seconds. The substrate after development was observed with an optical microscope at a magnification of 10 times, and the number of defects at the edge of the colored layer was measured in the range of 50mm×50 mm. In the desired linear coloring pattern having a width of 80 μm, a portion of 5 μm or more was removed as a defect in the edge portion.
(evaluation criterion for defective resistance)
Very good: no defect.
And (3) the following materials: less than 20.
O: more than 20 and less than 50.
Delta: more than 50.
< line width offset of thin line >
The photosensitive colored resin compositions of examples and comparative examples were applied to GLASS substrates (NH TECHNO GLASS Co., ltd.) having a thickness of 0.7mm using a spin coater so that the thickness of the cured coating film became 2.5. Mu.mManufactured by limited corporation, "NA 35"). Thereafter, the film was heated and dried on a heating plate at 100℃for 3 minutes, and thereafter, a photomask pattern having a fine line pattern (pattern for evaluating line width deviation) with an opening width of 20 μm was sandwiched therebetween, and irradiated with an extra-high pressure mercury lamp at 40mJ/cm 2 Is a ultraviolet ray of (a). Thereafter, the glass plate on which the colored layer was formed was subjected to spray development using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer, and post-baking was performed for 30 minutes by passing through a clean oven at 230 ℃. The line width of the individual thin lines of the thin line pattern of the colored layer formed on the glass substrate, which was actually measured when the opening width of the photomask was 20 μm and the design line width was 25 μm), was measured and evaluated by the following criteria.
(line width offset evaluation reference)
The line width offset value (μm) from the designed line width was calculated by the following equation.
Linewidth offset value (μm) =measured linewidth (μm) -25 (μm)
And (3) the following materials: the line width offset value is-2 μm or more and 2 μm or less.
O: the line width offset value is-4 μm or more and less than-2 μm.
X: the line width offset value is less than-4 μm or exceeds 2 μm.
The smaller the deviation from the designed line width, the more it can be evaluated that a pattern is formed with a desired line width.
TABLE 2
Table 2.
< summary of results >
In the comparative photosensitive colored resin compositions of comparative examples 1 to 3, although the specific initiator was used as the photoinitiator, the photopolymerizable compound containing the photopolymerizable compound having a molecular weight of less than 500 and the photopolymerizable compound having an acidic group having a main functional group of less than 7 was used as the photopolymerizable compound, and sublimates were generated upon drying, and the water spot suppressing effect was also inferior to that of examples.
In the comparative photosensitive colored resin compositions of comparative examples 4 to 5, although the specific initiator was used as the photoinitiator, the photopolymerizable compound having no acid value was used as the photopolymerizable compound, the developability was poor, the water spot suppressing effect was also inferior to that of examples, and the deviation of the fine line pattern from the design line width was also large.
In the comparative photosensitive colored resin composition of comparative example 6, the same photopolymerizable compound as in example was used, but the combination of Irgacure 907 and Irgacure OXE-02 used in patent document 2 was used as a photoinitiator, and sublimates were generated during drying, and the water spot suppression effect was also poor, and the chipping resistance was also poor.
In contrast, the photosensitive colored resin compositions of examples 1 to 17, which used a photopolymerizable compound containing an acidic group having 7 or more unsaturated double bond groups and an acidic group in 1 molecule and having a molecular weight of 500 or more in combination with a photoinitiator containing 1 or more selected from the group consisting of the compound represented by the general formula (a) and the compound represented by the general formula (B) specified in the present application, were represented by the following photosensitive colored resin compositions: can inhibit the generation of sublimates during drying, has excellent developability, and can inhibit the generation of water spots.
Description of the reference numerals
1: substrate board
2: light shielding part
3: coloring layer
10: color filter
20: opposite substrate
30: liquid crystal layer
40: liquid crystal display device having a light shielding layer
50: organic protective layer
60: inorganic oxide film
71: transparent anode
72: hole injection layer
73: hole transport layer
74: light-emitting layer
75: electron injection layer
76: cathode electrode
80: organic light-emitting body
100: organic light emitting display device

Claims (7)

1. A photosensitive coloring resin composition comprising: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
the photopolymerizable compound contains 1 acid group-containing photopolymerizable compound having 7 or more unsaturated double bond groups and acid groups in the molecule and has a molecular weight of 500 or more,
the photoinitiator contains 1 or more selected from compounds represented by the following general formula (A) and compounds represented by the following general formula (B):
general formula (A)
In the general formula (A), Z 1 、Z 3 、Z 4 Z is as follows 5 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, the alkyl group, cycloalkyl group, and phenyl group being optionally substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and phenyl group; z is Z 2 Represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group,
general formula (B)
In the general formula (B), R a R is R b Each independently represents an alkyl group having 2 to 8 carbon atoms.
2. The photosensitive colored resin composition according to claim 1, wherein the acidic group-containing photopolymerizable compound comprises a compound represented by the following general formula (1):
General formula (1)
In the general formula (1), Q represents a tetracarboxylic acid residue or a tetracarboxylic dianhydride residue, R independently represents a hydrogen atom or a (meth) acryloyl group, n represents an integer of 1 to 4, m represents an integer of 0 to 4, j represents an integer of 1 or more, n×j+m is an integer of 3 or more, R of each repeating unit is optionally the same or different when n, m and j are 2 or more, and 7 or more R in 1 molecule are (meth) acryloyl groups.
3. The photosensitive colored resin composition according to claim 1 or 2, wherein the photoinitiator further comprises at least 1 selected from the group consisting of an α -aminoketone photoinitiator, an oxime ester photoinitiator having a carbazole skeleton, and a bisimidazole photoinitiator having a molecular weight of 300 or more.
4. The photosensitive colored resin composition according to any one of claims 1 to 3, further comprising a polyfunctional thiol compound.
5. A cured product of the photosensitive colored resin composition according to any one of claims 1 to 4.
6. A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a cured product of the photosensitive colored resin composition according to claim 5.
7. A display device having the color filter of claim 6.
CN202280014044.2A 2021-02-24 2022-02-16 Photosensitive colored resin composition, cured product, color filter and display device Pending CN116917807A (en)

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