CN111771163A

CN111771163A - Negative photosensitive coloring composition, cured film, and touch panel using same

Info

Publication number: CN111771163A
Application number: CN201980015528.7A
Authority: CN
Inventors: 小林秀行; 诹访充史; 饭冢英祐; 东后行伦
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2018-03-14
Filing date: 2019-03-08
Publication date: 2020-10-13
Anticipated expiration: 2039-03-08
Also published as: WO2019176785A1; CN111771163B; KR20200132843A; TW201939164A; JPWO2019176785A1; TWI808137B; JP7306264B2; KR102617582B1

Abstract

A negative photosensitive coloring composition comprising (A) a white pigment, (B) a silicone resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, wherein the silicone resin (B) contains at least: a repeating unit represented by the following general formula (1) and/or a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3), wherein the total of 40 to 80 mol% of the repeating unit represented by the following general formula (1) and the repeating unit represented by the following general formula (2) is contained in the total repeating units of the silicone resin (B); in the above general formulae (1) to (3), R¹An alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 10 carbon atoms, wherein all or a part of the hydrogen atoms are substituted with fluorine atoms; r²Represents a single bond, -O-, -CH₂-CO-, -CO-or-O-CO-; r³A 1-valent organic group having 1 to 20 carbon atoms; r⁴The organic groups may be the same or different and each represents a 1-valent organic group having 1 to 20 carbon atoms. Provided is a negative photosensitive coloring composition which can form a cured film having high resolution, high reflectance and excellent heat resistance even when the film is thick.

Description

Negative photosensitive coloring composition, cured film, and touch panel using same

Technical Field

The present invention relates to a negative photosensitive coloring composition, a cured film, a method for producing the same, and a touch panel using the same.

Background

In recent years, mobile devices using a projection type capacitance touch panel, such as smartphones and tablet PCs, have rapidly become widespread. In general, a projection type capacitance touch panel has a pattern of an ITO (Indium tin oxide) film in a screen region, and further has a metal wiring portion such as molybdenum in a peripheral portion thereof. In order to hide such metal wiring portions from the viewpoint of design, a light-shielding pattern of black, white, or the like is often provided on the inner side of the cover glass of the projection-type capacitance touch panel. As touch panel-mounted terminals have diversified, higher-definition light-shielding patterns have been required, and instead of the conventional printing method, a photolithography method capable of performing processing with higher resolution has become the mainstream as a method for forming such light-shielding patterns (for example, see patent document 1). In addition, since white light-shielding patterns generally have low light-shielding properties of white pigments, thick film processing is required.

The touch panel is roughly classified into an Out-cell type In which a touch panel layer is formed between a cover Glass and a liquid crystal panel, an On-cell type In which a touch panel layer is formed On a liquid crystal panel, an In-cell type In which a touch panel layer is formed inside a liquid crystal panel, and an ogs (one Glass solution) type In which a touch panel layer is directly formed On a cover Glass. In recent years, OGS type touch panels have been actively developed because they can be made thinner and lighter than conventional ones.

In the method for manufacturing the OGS type touch panel, high-temperature processing such as ITO film formation is required, and therefore, as a material of the light shielding pattern, a material having high heat resistance with less cracks and color change in the high-temperature processing is required. Therefore, it is proposed that: a negative photosensitive coloring composition containing a white pigment, a polysiloxane having a specific structure, a polyfunctional acrylic monomer, a photo radical polymerization initiator, and an organic solvent (for example, see patent document 2); a negative photosensitive white composition for a touch panel, which contains a white pigment, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator (see, for example, patent document 3).

Further, since a highly fine and highly reflective partition wall pattern can be easily formed on a substrate by photolithography, application of a luminance improvement technique to a display device has been studied as a method for improving light extraction efficiency of a light-emitting body.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2012 and 242928

Patent document 2: international publication No. 2014/126013

Patent document 3: international publication No. 2015/12228

Disclosure of Invention

Problems to be solved by the invention

However, in the composition described in patent document 2, since the refractive index of the polysiloxane is high and the difference in refractive index with the white pigment is small, the reflection at the interface between the polysiloxane and the white pigment is insufficient, and the reflectance of the white light-shielding pattern is insufficient. On the other hand, although the composition described in patent document 3 improves the reflectance of the white light-shielding pattern, further improvement is required. Further, when the film thickness is large, there is a problem that cracks are likely to occur by high-temperature treatment, and the heat resistance is insufficient.

Accordingly, an object of the present invention is to provide a negative photosensitive coloring composition capable of forming a cured film having high resolution, high reflectance and excellent heat resistance even when the film is thick.

Means for solving the problems

In order to solve the above problems, the present inventors have made intensive studies with attention paid to the structure of a silicone resin in a negative photosensitive coloring composition containing a white pigment. As a result, they have found that the above problems can be solved by a silicone resin containing a combination of a structural unit derived from a fluorine-containing alkoxysilane compound and a structural unit derived from a 2-functional alkoxysilane compound. That is, the present invention has the following configuration.

A negative photosensitive coloring composition comprising (A) a white pigment, (B) a silicone resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, wherein the silicone resin (B) contains at least: the silicone resin composition comprises a repeating unit represented by the following general formula (1) and/or a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3), wherein the total of 40 to 80 mol% of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2) are contained in the total repeating units of the silicone resin (B).

In the above general formulae (1) to (3), R¹Represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms wherein all or a part of the hydrogen atoms are replaced by fluorine. R²Represents a single bond, -O-, -CH₂-CO-, -CO-or-O-CO-. R³Represents a 1-valent organic group having 1 to 20 carbon atoms. R⁴The organic groups may be the same or different and each represents a 1-valent organic group having 1 to 20 carbon atoms.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the negative photosensitive coloring composition of the present invention, a thick cured film having high reflectance, high resolution and excellent heat resistance can be formed.

Drawings

Fig. 1 is a sectional view showing an embodiment of a substrate with a partition wall of the present invention having a patterned partition wall.

Fig. 2 is a sectional view showing an embodiment of the substrate with a partition wall of the present invention having a patterned partition wall and a layer containing a color-converting luminescent material.

Fig. 3 is a sectional view showing an aspect of the substrate with partition walls of the present invention having a low refractive index layer.

Fig. 4 is a sectional view showing an aspect of the substrate with partition walls of the present invention having a low refractive index layer and an inorganic protective layer I.

Fig. 5 is a sectional view showing an aspect of the substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer II.

Fig. 6 is a sectional view showing an aspect of the substrate with partition walls of the present invention having a color filter.

Fig. 7 is a sectional view showing an aspect of the substrate with partition walls of the present invention having a color filter and an inorganic protective layer III.

Fig. 8 is a sectional view showing an aspect of the substrate with partition walls of the present invention having an inorganic protective layer IV.

Fig. 9 is a sectional view showing an aspect of the substrate with a partition wall of the present invention having a light-shielding partition wall.

Fig. 10 is a schematic diagram showing an example of a cross section of the touch panel of the present invention.

Fig. 11 is a schematic view showing an example of a method for manufacturing a touch panel according to the present invention.

Detailed Description

The negative photosensitive coloring composition of the present invention contains (a) a white pigment, (B) a silicone resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent.

(A) White pigment

The inclusion of the white pigment (a) can improve the reflectance of the resulting cured film.

Examples of the white pigment (a) include compounds selected from titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof. May contain 2 or more of them. Among them, titanium dioxide having a high reflectance and easy industrial utilization is preferable.

The crystal structure of titanium dioxide is classified into anatase type, rutile type, brookite type. Among them, rutile type titanium oxide is preferable in view of low photocatalytic activity.

The white pigment (a) may be subjected to surface treatment. Preferably, surface treatment with Al, Si and/or Zr can improve the dispersibility of the white pigment (a) in the negative photosensitive coloring composition and further improve the light resistance and heat resistance of the cured film.

The median particle diameter of the white pigment (A) is preferably 100 to 500nm, more preferably 170 to 310nm, from the viewpoint of further improving the reflectance. Here, the median particle diameter refers to an average primary particle diameter of the white pigment (a) calculated from a particle size distribution measured by a laser diffraction method.

As titanium dioxide pigments preferably used as (a) white pigments, there may be mentioned, for example, R960; デュポン (rutile type, SiO)₂/Al₂O₃Treatment, the median diameter is 210nm), CR-97; rutile type Al produced by Shishao industries Ltd₂O₃/ZrO₂Treatment, the median diameter is 250nm), JR-301; テイカ (rutile type, Al)₂O₃Treatment, the median diameter is 300nm), JR-405; テイカ (rutile type, Al)₂O₃Treatment, the median diameter is 210nm), JR-600A; テイカ strain (rutile type, Al)₂O₃Treatment, the median diameter is 250nm), JR-603; テイカ strain (rutile type, Al)₂O₃/ZrO₂Treatment, median particle size 280nm), etc. May contain 2 or more of them.

(A) The refractive index of the white pigment at a wavelength of 587.5nm is preferably 2.00-2.70. By setting the refractive index of the white pigment (a) to 2.00 or more, the interface reflection between the white pigment (a) and the silicone resin (B) can be increased, and the reflectance can be further improved. (A) The refractive index of the white pigment is more preferably 2.40 or more. On the other hand, when the refractive index of the white pigment (a) is 2.70 or less, excessive interface reflection between the white pigment (a) and the silicone resin (B) can be suppressed, and the resolution can be further improved. The refractive index of the white pigment (A) can be measured by the Beck method defined in JIS K7142-2014 (established year, month, day: 2014/04/20). The measurement wavelength was set to 587.5nm as standard. When 2 or more kinds of (a) white pigments are contained, it is preferable that at least 1 kind of the white pigments have a refractive index in the above range.

From the viewpoint of further improving the reflectance, the content of the white pigment (a) in the negative photosensitive coloring composition of the present invention is preferably 20% by weight or more, more preferably 40% by weight or more, and further preferably 45% by weight or more, in the solid content. On the other hand, the content of the white pigment (a) in the solid content is preferably 65% by weight or less, and more preferably 60% by weight or less, from the viewpoint of suppressing development residue and forming a pattern with higher resolution. The solid component herein refers to all components except volatile components such as a solvent among the components contained in the negative photosensitive coloring composition. The amount of the solid component can be determined by measuring the residual component after heating the negative photosensitive coloring composition at 170 ℃ for 30 minutes to evaporate the volatile component.

The negative photosensitive coloring composition of the present invention may contain a pigment dispersant together with the white pigment (a), and the dispersibility of the white pigment (a) in the negative photosensitive coloring composition may be improved. The pigment dispersant may be appropriately selected depending on the kind and surface state of the white pigment used. The pigment dispersant preferably contains an acidic group and/or a basic group. Examples of commercially available pigment dispersants include "Disperbyk" (registered trademark) 106, 108, 110, 180, 190, 2001, 2155, 140, and 145 (trade name, manufactured by ビックケミー, ltd.). May contain 2 or more of them.

(B) Siloxane resins

By containing the silicone resin (B) having the above-mentioned specific structure, the difference in refractive index between the white pigment (a) and the silicone resin (B) can be increased, and the reflectance of the resulting cured film can be further improved. The silicone resin (B) having the above-mentioned specific structure is excellent in heat resistance, and can suppress color change and cracks of a cured film. Further, a high-resolution pattern can be formed.

(B) The siloxane resin is a hydrolysis/dehydration condensate of an organosilane. The negative photosensitive coloring composition of the present invention comprises at least: a repeating unit represented by the following general formula (1) and/or a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3). Other repeating units may be further included.

The repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are characterized by containing fluorine. By including these repeating units, the refractive index of the silicone resin (B) decreases, and therefore the refractive index difference with the white pigment (a) increases, and the reflectance of the cured film can be improved by light reflection at the interface between the white pigment (a) and the silicone resin (B).

Further, by including a repeating unit derived from the 2-functional alkoxysilane compound represented by the general formula (3), excessive thermal polymerization (condensation) of the silicone resin (B) during heat treatment can be suppressed, and the heat resistance can be improved. This can suppress cracking and color change of the cured film during heat treatment.

In the present invention, the siloxane resin (B) is characterized by containing 40 to 80 mol% in total of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). If the total content of the repeating unit represented by the general formula (1) and the general formula (2) is less than 40 mol%, the interface reflection between the white pigment (a) and the silicone resin (B) becomes insufficient, and the reflectance decreases. The total content of the repeating unit represented by the general formula (1) and the general formula (2) is preferably 50 mol% or more. On the other hand, if the total content of the repeating unit represented by the general formula (1) and the general formula (2) exceeds 80 mol%, the hydrophobic property of the silicone resin (B) decreases the compatibility with other components in the composition, and thus the resolution decreases. The total content of the repeating unit represented by the general formula (1) and the general formula (2) is preferably 70 mol% or less. The content of the repeating unit represented by the general formula (3) is preferably 50 mol% or less. When the content of the repeating unit represented by the general formula (3) is excessive, crosslinking of the cured film becomes insufficient, and the film characteristics are degraded. On the other hand, the content of the repeating unit represented by the general formula (3) is preferably 10 mol% or more. If the content of the repeating unit represented by the general formula (3) is less than 10 mol%, the crosslinking of the cured film is excessively formed, and thus the crack resistance is lowered. When the polymer contains a repeating unit other than the repeating units represented by the general formulae (1) to (3), the content thereof is preferably 10 to 50 mol%.

In the above general formulae (1) to (3), R¹Represents that all or part of the hydrogen is replaced by fluorineAnd an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms. R²Represents a single bond, -O-, -CH₂-CO-, -CO-or-O-CO-. R³Represents a 1-valent organic group having 1 to 20 carbon atoms. R⁴The organic groups may be the same or different and each represents a 1-valent organic group having 1 to 20 carbon atoms. As R¹From the viewpoint of further lowering the refractive index of the silicone resin, an alkyl group in which all or a part of hydrogen is substituted with fluorine is preferable. In this case, the number of carbon atoms in the alkyl group is preferably 1 to 6. As R³And R⁴From the viewpoint of further reducing the refractive index of the silicone resin, the silicone resin is preferably a group selected from an alkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 10 carbon atoms.

The repeating units represented by the general formulae (1) to (3) are derived from alkoxysilane compounds represented by the general formulae (4) to (6). That is, the siloxane resin containing the repeating unit represented by the above general formula (1) and/or the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3) can be obtained by hydrolyzing and polycondensing a plurality of alkoxysilane compounds containing the alkoxysilane compound represented by the following general formula (4) and/or the alkoxysilane compound represented by the following general formula (5), and the alkoxysilane compound represented by the following general formula (6). Other alkoxysilane compounds may be further used.

In the above general formulae (4) to (6), R⁵、R⁶、R⁸And R⁹Respectively represent R in general formulas (1) to (3)¹、R²、R³And R⁴The same groups. R⁷The same or different, and represents a 1-valent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxysilane compound represented by the general formula (4) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctytripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane. More than 2 of them may be used.

Examples of the alkoxysilane compound represented by the general formula (5) include bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and the like. More than 2 of them may be used.

Examples of the alkoxysilane compound represented by the general formula (6) include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-acryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, and mixtures thereof, Gamma-acryloylpropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylethyldimethoxysilane and the like. More than 2 of them may be used.

Examples of the other alkoxysilane compounds include 3-functional alkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; 4-functional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetraethoxysilane oligomer); monofunctional alkoxysilane compounds such as trimethylmethoxysilane and triphenylmethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, alkoxysilane compounds containing an epoxy group and/or an oxetanyl group, such as 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyldimethoxysilane, 3-ethyl-3- { [3- (trimethoxysilyl) propoxy ] methyl } oxetane, and 3-ethyl-3- { [3- (triethoxysilyl) propoxy ] methyl } oxetane: phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, tolyltrimethoxysilane, an alkoxysilane compound having an aromatic ring such as tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethylethoxysilylpropylphthalic anhydride or the like; alkoxysilane compounds containing a radical polymerizable group such as styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, gamma-acryloylpropyltrimethoxysilane, gamma-acryloylpropyltriethoxysilane, gamma-methacryloylpropyltrimethoxysilane, and gamma-methacryloylpropyltriethoxysilane; 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutanoic acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutanoic acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylpentanoic acid, 5-dimethylmethoxysilylpentanoic acid, 5-dimethylethoxysilylpentanoic acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxybutylmethoxybutylmethoxybutylpropionic acid, 4-dimethylmethoxybutylbutyric acid, and carboxyl group-containing alkoxysilane compounds such as 3-trimethoxysilylpropylcyclohexylanhydride, 3-triethoxysilylpropylcyclohexylanhydride, 3-dimethylmethoxysilylpropylcyclohexylanhydride, 3-dimethylethoxysilylpropylcyclohexylanhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, and 3-dimethylethoxysilylpropylphthalic anhydride.

From the viewpoint of setting the content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) in all the repeating units of the silicone resin (B) to the above range, the total content of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) in the mixture of alkoxysilane compounds serving as the raw material of the silicone resin (B) is preferably 40 mol% or more, and more preferably 50 mol% or more. On the other hand, from the same viewpoint, the total content of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) is preferably 80 mol% or less, and more preferably 70 mol% or less. In addition, when only one of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) is contained, the alkoxysilane compound may be contained in the above range, and when both the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) are contained, the total amount of these may be contained in the above range.

The weight average molecular weight (Mw) of the silicone resin (B) is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of coating characteristics. On the other hand, from the viewpoint of developability, the Mw of the silicone resin (B) is preferably 50,000 or less, and more preferably 20,000 or less. Herein, the Mw of the silicone resin (B) in the present invention means a polystyrene equivalent value measured by Gel Permeation Chromatography (GPC).

(B) The refractive index of the siloxane resin at a wavelength of 587.5nm is preferably 1.35-1.55. By setting the refractive index of the silicone resin (B) to 1.35 or more, excessive interface reflection between the white pigment (a) and the silicone resin (B) can be suppressed, and the resolution can be further improved. (B) The refractive index of the silicone resin is more preferably 1.40 or more. On the other hand, by setting the refractive index of the silicone resin (B) to 1.55 or less, the interface reflection between the white pigment (a) and the silicone resin (B) can be increased, and the reflectance can be further improved. (B) The refractive index of the silicone resin is more preferably 1.50 or less. Here, as for the refractive index of the silicone resin (B), the cured film of the silicone resin formed on a silicon wafer was irradiated with light having a wavelength of 587.5nm from the perpendicular direction to the cured film surface under the atmospheric pressure at 20 ℃. However, the third digit after the decimal point is rounded off. The cured film of the silicone resin was prepared by spin-coating a silicone resin solution in which the silicone resin was dissolved in an organic solvent so that the solid content concentration became 40 wt% on a silicon wafer, drying the silicon wafer for 2 minutes on a 90 ℃ hot plate, and then curing the silicon wafer for 30 minutes at 230 ℃ in air using an oven. When the negative photosensitive coloring composition contains 2 or more types of (B) siloxane resins, it is preferable that at least 1 type of the siloxane resin has a refractive index in the above range.

(A) The difference in refractive index between the white pigment and the silicone resin (B) at a wavelength of 587.5nm is preferably 1.16 to 1.26. By setting the refractive index difference to 1.16 or more, the interface reflection between (a) the white pigment and (B) the silicone resin can be increased, and the reflectance can be further improved. The refractive index difference is more preferably 1.18 or more. On the other hand, when the refractive index difference is 1.26 or less, excessive interfacial reflection between (a) the white pigment and (B) the silicone resin can be suppressed, and the resolution can be further improved. The difference in refractive index is more preferably 1.24 or less.

The content of the silicone resin (B) in the negative photosensitive coloring composition of the present invention can be arbitrarily set according to the desired film thickness and application, but is preferably 10 to 60% by weight in the negative photosensitive coloring composition. The content of the silicone resin (B) is preferably 10% by weight or more, and more preferably 20% by weight or more, in the solid content of the negative photosensitive coloring composition. On the other hand, the content of the (B) silicone resin is preferably 60% by weight or less, and more preferably 50% by weight or less, in the solid content of the negative photosensitive coloring composition.

(B) The silicone resin can be obtained by hydrolyzing the above-mentioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence or absence of a solvent.

The conditions for hydrolysis may be set in consideration of the scale of the reaction, the size and shape of the reaction vessel, and the like, and may be set according to physical properties suitable for the intended use. Examples of the various conditions include acid concentration, reaction temperature, reaction time, and the like.

In the hydrolysis reaction, an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid, an acid anhydride thereof, and an ion exchange resin can be used. Among them, an acidic aqueous solution containing formic acid, acetic acid and/or phosphoric acid is preferable.

In the case where an acid catalyst is used for the hydrolysis reaction, the amount of the acid catalyst to be added is preferably 0.05 parts by weight or more, and more preferably 0.1 parts by weight or more, based on 100 parts by weight of the total alkoxysilane compound used for the hydrolysis reaction, from the viewpoint of more rapidly progressing the hydrolysis. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the amount of the acid catalyst to be added is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the entire alkoxysilane compound. The total amount of the alkoxysilane compound is an amount containing all of the alkoxysilane compound, the hydrolysate thereof, and the condensate thereof.

The hydrolysis reaction may be carried out in an organic solvent. The organic solvent may be appropriately selected in consideration of stability, wettability, volatility, and the like of the negative photosensitive coloring composition. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; gamma-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. More than 2 of them may be used.

Among them, diacetone alcohol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ -butyrolactone, and the like are preferably used from the viewpoint of crack resistance of the cured film.

In the case where an organic solvent is produced by the hydrolysis reaction, the hydrolysis can be carried out in the absence of a solvent. It is also preferable to adjust the concentration to an appropriate level for use in the preparation of a negative photosensitive coloring composition by further adding an organic solvent to the obtained composition after the completion of the hydrolysis reaction. After hydrolysis, the whole or a part of the produced alcohol and the like may be distilled off and removed under heating and/or reduced pressure, and then a suitable organic solvent may be added.

In the case where an organic solvent is used for the hydrolysis reaction, the amount of the organic solvent to be added is preferably 50 parts by weight or more, and more preferably 80 parts by weight or more, per 100 parts by weight of the entire alkoxysilane compound, from the viewpoint of suppressing the formation of gel. On the other hand, the amount of the organic solvent to be added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the total alkoxysilane compound, from the viewpoint of more rapidly proceeding the hydrolysis.

The water used for the hydrolysis reaction is preferably ion-exchanged water. The amount of water may be arbitrarily set, but is preferably 1.0 to 4.0 moles per 1 mole of the entire alkoxysilane compound.

Examples of the dehydration condensation reaction include a method in which a silanol compound solution obtained by hydrolysis of an organic silane compound is directly heated. The heating temperature is preferably 50 ℃ or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Further, reheating or addition of an alkali catalyst may be performed in order to increase the polymerization degree of the silicone resin. After the hydrolysis, an appropriate amount of the formed alcohol or the like may be distilled off under heating and/or reduced pressure, removed, and then an appropriate solvent may be added, depending on the purpose.

From the viewpoint of storage stability of the negative photosensitive coloring composition, it is preferable that the siloxane resin solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. The catalyst removal method is preferably water washing, treatment with an ion exchange resin, or the like, from the viewpoint of ease of operation and removability. The washing with water is a method in which a silicone resin solution is diluted with an appropriate hydrophobic solvent, washed several times with water, and the resulting organic layer is concentrated with an evaporator or the like. The treatment with an ion exchange resin is a method of bringing a silicone resin solution into contact with an appropriate ion exchange resin.

(C) Photopolymerization initiator

By containing the (C) photopolymerization initiator and the (D) photopolymerizable compound, the polymerization of the (D) photopolymerizable compound proceeds by radicals generated from the (C) photopolymerization initiator by light irradiation, and the exposed portion of the negative photosensitive coloring composition is insoluble to an alkaline aqueous solution, so that a negative pattern can be formed.

(C) The photopolymerization initiator may be any initiator as long as it generates radicals by decomposition and/or reaction with light (including ultraviolet rays and electron beams). Examples thereof include α -aminoalkylphenone compounds such as 2-methyl- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxide compounds such as 2,4, 6-trimethylbenzoylphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) -phosphine oxide, and the like; oxime ester compounds such as 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1, 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl oxime) ], 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime); benzil ketal compounds such as benzil dimethyl ketal; α -hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, and 1-hydroxycyclohexyl-phenylketone; benzophenone compounds such as benzophenone, 4, 4-bis (dimethylamino) benzophenone, 4, 4-bis (diethylamino) benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4, 4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenyl sulfide, alkylated benzophenone, and 3,3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone; acetophenone compounds such as 2, 2-diethoxyacetophenone, 2, 3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzylideneacetophenone and 4-azidobenzylideneacetophenone; aromatic ketone ester compounds such as methyl 2-phenyl-2-oxoacetate; and benzoate compounds such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. May contain 2 or more of them.

In the case where the negative photosensitive coloring composition of the present invention does not contain a colorant other than (a) the white pigment, in order to suppress coloring by (C) the photopolymerization initiator, acylphosphine oxide-based photopolymerization initiators such as 2,4, 6-trimethylbenzoyl phenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) -phosphine oxide and the like are preferable.

The content of the photopolymerization initiator (C) in the negative photosensitive coloring composition of the present invention is preferably 0.01% by weight or more, and more preferably 1% by weight or more, in terms of solid content, from the viewpoint of efficiently performing radical curing. On the other hand, the content of the (C) photopolymerization initiator in the solid content is preferably 20% by weight or less, more preferably 10% by weight or less, from the viewpoint of suppressing elution of the residual (C) photopolymerization initiator and the like and further improving yellowing.

(D) Photopolymerizable compound

The photopolymerizable compound in the present invention means a compound having an ethylenically unsaturated double bond in the molecule. The photopolymerizable compound preferably has 2 or more ethylenically unsaturated double bonds in the molecule. In view of the ease of proceeding of radical polymerizability, the photopolymerizable compound (D) preferably has a (meth) acryloyl group. In addition, the double bond equivalent of the photopolymerizable compound (D) is preferably 400g/mol or less from the viewpoint of further improving the sensitivity in pattern processing. On the other hand, the double bond equivalent of the photopolymerizable compound (D) is preferably 80g/mol or more from the viewpoint of further improving the resolution in pattern processing.

Examples of the photopolymerizable compound (D) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1, 3-butanediol diacrylate, 1, 3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, and mixtures thereof, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, "メガファック" (registered trade mark) RS-76-E, RS-56, pentaerythritol tetraacrylate, pentaacrylate, pentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-76, RS-90 (trade name, manufactured by DIC corporation), and the like. May contain 2 or more of them.

Among them, a compound having a fluorine atom is preferable from the viewpoint of further improving the reflectance. The photopolymerizable compound having a fluorine atom and the other photopolymerizable compound may be contained.

The content of the photopolymerizable compound (D) in the negative photosensitive coloring composition of the present invention is preferably 1 wt% or more in the solid content from the viewpoint of efficiently performing radical curing. On the other hand, from the viewpoint of suppressing the excessive reaction of the radicals to further improve the resolution, the content of the (D) photopolymerizable compound in the solid content is preferably 40% by weight or less.

(E) Organic solvent

By containing the organic solvent (E), the negative photosensitive coloring composition can be easily adjusted to a viscosity suitable for coating, and the uniformity of the coating film can be improved.

The organic solvent is preferably an organic solvent having a boiling point of more than 150 ℃ and 250 ℃ or lower under atmospheric pressure, and is preferably combined with an organic solvent having a boiling point of 150 ℃ or lower. The negative photosensitive coloring composition contains the organic solvent having a boiling point of more than 150 ℃ and 250 ℃ or less, so that the organic solvent is appropriately volatilized during coating to dry the coating film, thereby suppressing coating unevenness and improving the film thickness uniformity. Further, by containing an organic solvent having a boiling point of 150 ℃ or lower under atmospheric pressure, the residual organic solvent in the cured film of the present invention described later can be suppressed. From the viewpoint of suppressing the residual of the organic solvent in the cured film and further improving the chemical resistance and adhesion for a long period of time, it is preferable to contain an organic solvent having a boiling point of 150 ℃ or lower at atmospheric pressure of 50 wt% or more of the entire organic solvent.

Examples of the organic solvent having a boiling point of 150 ℃ or lower under atmospheric pressure include ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, isoamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, n-heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-hydroxy-3-methyl-2-butanone, methyl ethyl acetate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-hydroxy-3-methyl-2, 4-hydroxy-3-methyl-2-butanone and 5-hydroxy-2-pentanone. More than 2 of them may be used.

Examples of the organic solvent having a boiling point of more than 150 ℃ and 250 ℃ or lower under atmospheric pressure include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ -butyrolactone, γ -valerolactone, propylene carbonate, and mixtures thereof, N-methyl pyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether and ethylene glycol dibutyl ether. More than 2 of them may be used.

The content of the organic solvent may be arbitrarily set according to the coating method and the like. For example, when the film is formed by spin coating, the content of the organic solvent in the negative photosensitive coloring composition is preferably 50% by weight or more and 95% by weight or less.

The negative photosensitive coloring composition of the present invention may further contain an adhesion improver, an ultraviolet absorber, a polymerization inhibitor, a surfactant, and the like, as necessary.

By adding the adhesion improver to the negative photosensitive coloring composition, the adhesion to the substrate is improved, and a cured film with high reliability can be obtained. Examples of the adhesion improver include alicyclic epoxy compounds and silane coupling agents. Among them, the alicyclic epoxy compound has high heat resistance, and therefore can further suppress the color change of the cured film after heating.

Examples of the alicyclic epoxy compound include 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, caprolactone-modified 3 ', 4' -epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, 1, 2-epoxy-4-vinylcyclohexane, butane tetracarboxylic acid tetrakis (3, 4-epoxycyclohexylmethyl) -modified caprolactone, 3, 4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, and mixtures thereof, Hydrogenated bisphenol a bis (propylene glycol glycidyl ether) ether, hydrogenated bisphenol a bis (ethylene glycol glycidyl ether) ether, 1, 4-cyclohexanedicarboxylic acid diglycidyl ester, 1, 4-cyclohexanedimethanol diglycidyl ether, and the like. May contain 2 or more of them.

The silane coupling agent is preferably a compound represented by the following general formula (7).

In the above general formula (7), each R¹⁰Each independently represents an alkyl group having 1 to 6 carbon atoms. From the viewpoint of lowering the refractive index, R is¹⁰Preferably, the alkyl group has 1 to 3 carbon atoms. p represents 0 or 1. From the viewpoint of further improving the adhesion to the substrate, p is preferably 0. R¹¹The organic group has a valence of 3 to 30 carbon atoms, preferably a 3-valent hydrocarbon group having 3 to 10 carbon atoms. R¹²Each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. From the viewpoint of lowering the refractive index, R is¹²Preferably, the alkyl group has 1 to 3 carbon atoms or 1 to 3 carbon atoms.

Examples of the silane coupling agent represented by the above general formula (7) include 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (isopropylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (isobutylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 3- (tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, and 2- (2- (tert-pentylamino) -2-oxoethyl) -5- (trimethoxysilyl) hexanoic acid - (trimethoxysilyl) pentanoic acid, 6- (dimethoxymethylsilyl) -3- (tert-butylcarbamoyl) hexanoic acid, 5- (dimethoxy (methyl) silyl-2- (2- (tert-butylamino) -2-oxoethyl) pentanoic acid, 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) pentanoic acid, 2- (2- (tert-butylamino) -2-oxoethyl) -5- (trimethoxysilyl) butanoic acid, 2- (tert-butylcarbamoyl) -4- (2- (trimethoxysilyl) ethyl) cyclohexanecarboxylic acid, 2- (tert-butylcarbamoyl) -5- (2- (trimethoxysilyl) ethyl) cyclohexanecarboxylic acid, etc. 2 or more of these may be contained.

From the viewpoint of further improving the adhesion to the substrate, the content of the adhesion improver in the negative photosensitive coloring composition is preferably 0.1% by weight or more, more preferably 1% by weight or more, in terms of solid content. On the other hand, the content of the adhesion improver is preferably 20% by weight or less, more preferably 10% by weight or less, in the solid content, from the viewpoint of further suppressing the color change due to heating.

By including an ultraviolet absorber in the negative photosensitive coloring composition, the light resistance of the cured film can be improved, and the resolution can be further improved. As the ultraviolet absorber, from the viewpoint of further suppressing the color change caused by heating, benzotriazole-based compounds such as 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4, 6-tert-amylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, and 2- (2 '-hydroxy-5' -methacryloyloxyethylphenyl) -2H-benzotriazole are preferably used; benzophenone-based compounds such as 2-hydroxy-4-methoxybenzophenone; triazine compounds such as 2- (4, 6-diphenyl-1, 3,5 triazin-2-yl) -5- [ (hexyl) oxy ] -phenol. May contain 2 or more of them.

By including a polymerization inhibitor in the negative photosensitive coloring composition, the resolution of the resulting cured film can be improved. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1, 4-benzoquinone, and t-butylcatechol. Examples of commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (trade name, manufactured by BASF ジャパン, ltd.). May contain 2 or more of them.

By adding a surfactant to the negative photosensitive coloring composition, the fluidity at the time of coating can be improved. Examples of the surfactant include fluorine-based surfactants such as "メガファック" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (trade name, manufactured by DIC corporation); silicone surfactants such as "BYK" (registered trademark) -333, 301, 331, 345, and 307 (trade name, manufactured by ビックケミー & ジャパン corporation); a polyoxyalkylene-based surfactant; poly (meth) acrylate surfactants, and the like. May contain 2 or more of them.

The solid content concentration of the negative photosensitive coloring composition can be arbitrarily set according to the coating method and the like. For example, when the film is formed by spin coating as described later, the solid content concentration is preferably 5% by weight or more and 50% by weight or less.

Next, a method for producing the negative photosensitive coloring composition of the present invention will be described below. The negative photosensitive coloring composition of the present invention can be obtained by mixing the above-mentioned components (a) to (E) with other components as necessary. More specifically, for example, first, a mixed liquid of (a) a white pigment, (B) a silicone resin, and (E) an organic solvent is preferably dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a pigment dispersion liquid. On the other hand, it is preferable to obtain a diluted solution by stirring and dissolving (B) a silicone resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, (E) an organic solvent, and if necessary, other components. Further, it is preferable to mix and stir the pigment dispersion liquid and the diluent, and then filter the mixture.

Next, the cured film of the present invention will be explained. The cured film of the present invention is a cured product of the negative photosensitive coloring composition of the present invention. The cured film of the present invention can be suitably used as a light-shielding pattern in an OGS-type touch panel or a partition pattern of an image display device. The thickness of the cured film is preferably 10 μm or more.

The method for producing the cured film of the present invention will be described by way of example. The method for producing a cured film of the present invention preferably comprises the steps of: (I) a step of coating the negative photosensitive coloring composition of the present invention on a substrate to form a coating film; (II) exposing and developing the coating film; and (III) heating the developed coating film. The respective steps will be explained below.

(I) The step of applying the negative photosensitive coloring composition of the present invention to a substrate to form a coating film includes, for example, a glass substrate such as soda lime glass or alkali-free glass.

The negative photosensitive coloring composition of the present invention is applied to these substrates to form a coating film. Examples of the coating method include spin coating, slit coating, screen printing, inkjet coating, and bar coater coating.

After the coating film is formed, the substrate coated with the negative photosensitive coloring composition is preferably dried (prebaked). Examples of the drying method include drying under reduced pressure and drying by heating. Examples of the heating device include an electric hot plate and an oven. The heating temperature is preferably 60-150 ℃, and the heating time is preferably 30 seconds-3 minutes. The film thickness of the pre-baked coating film is preferably 5 to 20 μm.

(II) exposing and developing the coating film

The coating film obtained in this way is exposed and developed to obtain a substrate having a patterned coating film.

The exposure may be performed through a desired mask or may not be performed through a mask. Examples of the exposure machine include a stepper, a mirror projection mask exposure Machine (MPA), and a parallel photo mask exposure machine (hereinafter, "PLA"). The exposure intensity is preferably 10 to 4000J/m²Left and right (conversion of 365nm wavelength exposure). Examples of the exposure light source include ultraviolet rays such as i-ray, g-ray, and h-ray, KrF (wavelength 248nm) laser, ArF (wavelength 193nm) laser, and the like.

Examples of the developing method include a method such as shower, dipping, and paddle. The time for immersing in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include inorganic bases such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals; amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; and aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and choline. Rinsing with water after development is preferred. Then, the drying and baking can be performed at 50-140 ℃.

(III) heating the developed coating film

The substrate having the coating film with the pattern formed thereon obtained in this way is heated to cure the coating film, thereby obtaining a processed substrate with a pattern. Here, the processing substrate with a pattern is a substrate having a cured film on which a pattern is formed.

Examples of the heating device include an electric hot plate and an oven. The heating temperature is preferably 120-250 ℃, and the heating time is preferably 15 minutes-2 hours.

Next, a patterned processed substrate of the present invention will be described. The processing substrate with a pattern of the present invention has a pattern formed by the cured film of the present invention on a substrate. Such a pattern has high resolution and high reflectance, and thus can be suitably used as a white light-shielding pattern of a touch panel.

Examples of the substrate include those exemplified in the method for producing a cured film of the present invention.

In the case of using the cured film pattern as a light-shielding pattern of, for example, a touch panel, the total reflection (incident angle 8 DEG, light source: D-65(2 DEG field of view)) of the light-shielding pattern is preferably 82. ltoreq. L.ltoreq.99, -5. ltoreq. b.ltoreq.5, -5. ltoreq. a.ltoreq.5, and more preferably 82.5. ltoreq. L.ltoreq.97, -2. ltoreq. b.ltoreq.2, -2. ltoreq. a.ltoreq.2, respectively, in the CIE1976(L, a.ltoreq.5) color space. The cured film pattern having the color characteristics can be obtained, for example, by performing pattern processing by the preferred production method using the negative photosensitive coloring composition of the present invention.

Next, a substrate with a partition wall of the present invention will be described. The partition-equipped substrate of the present invention has patterned partition walls (hereinafter, sometimes referred to as "partition walls (F-1)") formed of the cured film on a substrate.

The partition wall in the present invention is a material having a repetitive pattern corresponding to the number of pixels of the image display device. The number of pixels of the image display device is, for example, 4000 pixels in the vertical direction and 2000 pixels in the horizontal direction. The number of pixels affects the resolution (accuracy) of the image being displayed. Therefore, it is necessary to form pixels of a number corresponding to the required resolution of the image and the screen size of the image display device, and it is preferable to determine the partition wall pattern formation size at the same time.

The substrate has a function as a support in the substrate with the partition walls. When a pixel including a color-converting light-emitting material is configured by forming a layer including a color-converting light-emitting material, which will be described later, between adjacent partitions, the partitions have a function of preventing color mixing of light between adjacent pixels. In the present invention, the partition wall (F-1) preferably has a reflectance of 60 to 90% per 10 μm of thickness at a wavelength of 550 nm. By setting the reflectance to 60% or more, the luminance of the display device can be improved by the reflection from the side surfaces of the (F-1) partition walls. On the other hand, the reflectance is preferably 90% or less from the viewpoint of improving the pattern forming accuracy.

Fig. 1 is a cross-sectional view showing an embodiment of a substrate with partition walls of the present invention having partition walls on which a pattern is formed. The substrate 1 has partition walls 2 on which a pattern is formed.

< substrate >

Examples of the substrate include a glass plate, a resin plate, and a resin film. The glass plate is preferably made of alkali-free glass. As materials of the resin plate and the resin film, polyester, (meth) acrylic polymer, transparent polyimide, polyether sulfone, and the like are preferable. The thickness of the glass plate and the resin plate is preferably 1mm or less, and preferably 0.8mm or less. The thickness of the resin film is preferably 100 μm or less.

< bulkhead (F-1) >

The barrier ribs (F-1) preferably have a reflectance of 60 to 90% per 10 μm of thickness at a wavelength of 550 nm. Here, the thickness of the partition wall (F-1) means the length of the partition wall (F-1) in the direction perpendicular to the substrate (height direction). In the case of the substrate with partition walls shown in fig. 1, the thickness of the partition walls 2 is represented by symbol X. The length of the partition wall (F-1) in the horizontal direction of the substrate is the width of the partition wall (F-1). In the case of the substrate with partition walls shown in fig. 1, the width of the partition walls 2 is denoted by symbol L. In the present invention, it is considered that the reflection at the side surfaces of the partition walls contributes to the improvement of the luminance of the display device. On the other hand, since the reflectance per thickness is considered to be the same regardless of the thickness direction and the width direction, in the present invention, attention is paid to the reflectance per thickness of the partition wall. As described later, the partition wall (F-1) preferably has a thickness of 0.5 to 50 μm and a width of 5 to 40 μm. Therefore, in the present invention, 10 μm is selected as a representative value of the thickness of the partition wall (F-1), and the reflectance per 10 μm is focused. If the reflectance per 10 μm thickness is less than 60%, the reflection at the side surfaces of the partition walls becomes small, and the luminance of the display device becomes insufficient. The higher the reflectance, the greater the reflection from the side surfaces of the partition walls, and hence the luminance of the display device can be improved, and therefore the reflectance is preferably 70% or more. On the other hand, the reflectance is preferably 90% or less from the viewpoint of improving the pattern forming accuracy. The reflectance of the partition wall (F-1) at a wavelength of 550nm at 10 μm per thickness can be measured from above by using a spectrophotometer (for example, CM-2600d manufactured by コニカミノルタ, Inc.) for the partition wall (F-1) having a thickness of 10 μm in the height direction in SCI mode. However, when a sufficient area for measurement cannot be secured, or when a measurement sample having a thickness of 10 μm cannot be collected, if the composition of the partition wall (F-1) is known, a full film having a thickness of 10 μm and having the same composition as that of the partition wall (F-1) may be prepared, and the reflectance may be measured on the full film instead of the partition wall (F-1). For example, a full-size film may be prepared under the same processing conditions as those for the formation of the partition walls (F-1) except that the material for forming the partition walls (F-1) is used and the thickness is set to 10 μm without forming a pattern, and the reflectance of the obtained full-size film may be measured from the top surface in the same manner. In addition, as a method for making the reflectance within the above range, for example, the negative photosensitive coloring composition of the present invention can be used to pattern the partition wall by the above preferred production method.

When the substrate with a partition has a layer (G) containing a color-converting luminescent material (hereinafter, sometimes referred to as "layer (G) containing a color-converting luminescent material"), which will be described later, the thickness of the partition (F-1) is preferably larger than the thickness of the layer (G) containing a color-converting luminescent material. Specifically, the thickness of the partition wall (F-1) is preferably 0.5 μm or more, more preferably 10 μm or more. On the other hand, the thickness of the partition wall (F-1) is preferably 50 μm or less, more preferably 20 μm or less, from the viewpoint of more efficiently extracting light emission from the bottom of the layer (G) containing the color conversion light-emitting material. The width of the partition wall (F-1) may be sufficient for suppressing color mixing of the adjacent layers (G) containing the color conversion light-emitting material due to light leakage, as long as the luminance is improved by light reflection at the side surfaces of the partition wall. Specifically, the width of the partition wall is preferably 5 μm or more, and more preferably 15 μm or more. On the other hand, the width of the partition wall (F-1) is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of securing a light-emitting region of the layer (G) containing a color conversion light-emitting material more reliably to improve the luminance.

From the viewpoint of improving the ink-jet coatability and facilitating the separate application of the color conversion light-emitting material, the surface contact angle of the partition wall (F-1) to propylene glycol monomethyl ether acetate is preferably 10 ° or more, more preferably 20 ° or more, and still more preferably 40 ° or more. On the other hand, from the viewpoint of improving the adhesion between the partition wall and the substrate, the surface contact angle of the partition wall (F-1) is preferably 70 DEG or less, and more preferably 60 DEG or less. Here, the contact angle of the surface of the partition wall (A-1) can be measured by the wettability test method of the surface of the substrate glass defined in JIS R3257 (established year, month, day: 1999/04/20). In addition, as a method for making the surface contact angle of the partition wall (F-1) within the above range, for example, the partition wall can be obtained by patterning the negative photosensitive coloring composition containing the photopolymerizable compound having a fluorine atom in the negative photosensitive coloring composition of the present invention by the above preferred production method.

< light-shielding partition (F-2) >

The substrate with a partition wall of the present invention preferably further comprises (F-2) a patterned light-shielding partition wall (hereinafter, sometimes referred to as "light-shielding partition wall (F-2)") having an optical density of 0.1 to 4.0 per 1.0 μm thickness between the substrate and the partition wall (F-1). By providing the light-shielding partition (F-2), light-shielding properties are improved, light leakage from the backlight in the display device is suppressed, and a clear image with high contrast can be obtained. Here, the light-shielding partition (F-2) is preferably formed in the same pattern as the partition (F-1).

Fig. 9 is a sectional view showing an aspect of the substrate with a partition wall of the present invention having a light shielding partition wall. The substrate 1 has a patterned partition wall 2 and a patterned light-shielding partition wall 10, and a layer 3 containing a color conversion luminescent material is arranged in a region partitioned by the partition wall 2 and the light-shielding partition wall 10.

The light-shielding partition (F-2) has an optical density of 0.1 to 4.0 per 1.0 μm of thickness. Here, the thickness of the light-shielding partition wall (F-2) is preferably 0.5 to 10 μm as described later. Therefore, in the present invention, 1.0 μm was selected as a representative value of the thickness of the partition wall (F-2), and attention was paid to the optical density per 1.0 μm thickness. By setting the optical density per 1.0 μm thickness to 0.1 or more, the light-shielding property can be further improved, and a sharp image with higher contrast can be obtained. The optical density per 1.0 μm thickness is more preferably 0.5 or more. On the other hand, the pattern processability can be improved by setting the optical density per 1.0 μm thickness to 4.0 or less. The optical density per 1.0 μm thickness is more preferably 3.0 or less. The optical density (OD value) of the light-shielding partition (F-2) can be calculated from the following formula (11) by measuring the intensity of incident light and transmitted light with a densitometer (361T (visual); manufactured by X-ray).

OD value log10 (I)₀I. formula (11)

I₀: intensity of incident light

I: the intensity of the transmitted light.

Further, as a method for adjusting the optical density to the above range, for example, a light-shielding partition wall (F-2) having a preferable composition described later can be given.

The thickness of the light-shielding partition (F-2) is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of improving the light-shielding property. On the other hand, the thickness of the light-shielding partition wall (F-2) is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint of improving flatness. The width of the light-shielding partition (F-2) is preferably about the same as that of the partition (F-1).

The light-shielding partition (F-2) preferably contains a resin and a black pigment. The resin has a function of improving the crack resistance and light resistance of the partition wall. The black pigment has a function of absorbing incident light and reducing emitted light.

Examples of the resin include epoxy resins, (meth) acrylic polymers, polyurethanes, polyesters, polyimides, polyolefins, and polysiloxanes. May contain 2 or more of them. Among them, polyimide is preferable from the viewpoint of excellent heat resistance and solvent resistance.

Examples of the black pigment include a black organic pigment, a mixed color organic pigment, and an inorganic pigment. Examples of the black organic pigment include carbon black, perylene black aniline black, and benzofuranone pigments. They may be coated with resin. Examples of the mixed color organic pigment include those in which 2 or more kinds of pigments such as red, blue, green, violet, yellow, magenta, and/or cyan are mixed to form a pseudo black color. Examples of the black inorganic pigment include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; a metal oxide; a metal composite oxide; a metal sulfide; a metal nitride; a metal oxynitride; metal carbides, and the like.

As a method for patterning the light-shielding partition wall (F-2) on the substrate, for example, a method for patterning the partition wall (F-1) by a photosensitive paste method is preferable, using a photosensitive material described in Japanese patent laid-open publication No. 2015-1654.

In the substrate with a partition wall of the present invention, a layer (G) containing a color conversion luminescent material is preferably formed between adjacent partition walls (F-1). The layer containing a color conversion light-emitting material has a function of converting at least a part of a wavelength region of incident light to emit emitted light in a wavelength region different from the wavelength region of the incident light, thereby performing color display. In the case where the substrate with a partition wall of the present invention is used for an image display device, the layer (G) containing a color conversion light-emitting material is generally referred to as a pixel.

Fig. 2 is a cross-sectional view showing an embodiment of the substrate with a partition wall of the present invention having a patterned partition wall and a layer (G) containing a color-converting luminescent material. The substrate 1 has patterned partition walls 2, and layers 3 containing color conversion luminescent materials are arranged in regions partitioned by the partition walls 2.

The color-converting luminescent material preferably contains an inorganic phosphor and/or an organic phosphor. For example, in the case of a display device in which a backlight for emitting blue light, a liquid crystal cell driven by a TFT, and a color filter having a layer (G) containing a color conversion light-emitting material are combined, it is preferable that a red phosphor for emitting red fluorescence by being excited by blue excitation light is contained in a region corresponding to a red pixel, a green phosphor for emitting green fluorescence by being excited by blue excitation light is contained in a region corresponding to a green pixel, and it is preferable that no phosphor is contained in a region corresponding to a blue pixel. On the other hand, the partition-wall-attached substrate of the present invention can be used for a display device of a type using blue micro LEDs corresponding to respective pixels separated by white partition walls as a backlight. ON/OFF of each pixel can be realized by ON/OFF of the blue micro LED, and liquid crystal is not required. In this case, it is preferable to have 2 kinds of partitions, that is, partitions for separating pixels on a substrate and partitions for separating blue micro LEDs in a backlight.

The inorganic phosphor emits light of various colors such as green and red depending on the peak wavelength of the emission spectrum. Examples of the inorganic phosphor include: a substance which is excited by excitation light having a wavelength of 400 to 500nm and has a peak in a region having an emission spectrum of 500 to 700 nm; inorganic semiconductor fine particles called quantum dots, and the like. Examples of the former inorganic phosphor include spherical and columnar shapes. Examples of such inorganic phosphors include YAG phosphors, TAG phosphors, and sialon phosphors、Mn⁴⁺Activated fluoride complex phosphors, and the like. More than 2 of them may be used.

Among them, quantum dots are preferable. Since the quantum dots have a smaller average particle size than other phosphors, the surface of the layer (G) containing the color conversion light-emitting material can be smoothed to suppress light scattering on the surface, and thus the light extraction efficiency can be further improved and the luminance can be further improved.

Examples of the material of the quantum dot include group II-IV, group III-V, group IV-VI, group IV semiconductors, and the like. Examples of such inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si₃N₄、Ge₃N₄、Al₂O₃And the like. More than 2 of them may be used.

The quantum dots may contain a p-type dopant or an n-type dopant. In addition, the quantum dot may have a core-shell structure. In the core-shell structure, any suitable functional layer (single layer or multiple layers) may be formed around the shell according to the purpose, and the surface of the shell may be subjected to surface treatment and/or chemical modification.

Examples of the shape of the quantum dot include a spherical shape, a columnar shape, a phosphor flake shape, a plate shape, and an amorphous shape. The average particle diameter of the quantum dot can be selected according to a desired emission wavelength, and is preferably 1 to 30 nm. When the average particle diameter of the quantum dot is 1 to 10nm, a peak in an emission spectrum can be made sharper in any of blue, green, and red. For example, the quantum dots emit blue light when the average particle diameter is about 2nm, green light when the average particle diameter is about 3nm, and red light when the average particle diameter is about 6 nm. The average particle diameter of the quantum dots is preferably 2nm or more, and preferably 8nm or less. The average particle size of the quantum dots can be measured by a dynamic light scattering method. Examples of a device for measuring the average particle diameter include a dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Denshi Co., Ltd.).

Examples of the organic phosphor include a methylene pyrrole derivative having a basic skeleton represented by the following structural formula (8) as a phosphor that emits red fluorescence when excited by blue excitation light, and a methylene pyrrole derivative having a basic skeleton represented by the following structural formula (9) as a phosphor that emits green fluorescence when excited by blue excitation light. Further, perylene derivatives, porphyrin derivatives, perylene derivatives which emit red or green fluorescence by selection of substituents, porphyrin derivatives, perylene derivatives, porphyrin derivatives,

oxazine derivatives, pyrazine derivatives, and the like. May contain 2 or more of them. Among them, a methylene pyrrole derivative is preferable from the viewpoint of high quantum yield. The methylene pyrrole derivative can be obtained by, for example, the method described in Japanese patent application laid-open No. 2011-241160.

The organic phosphor is soluble in a solvent, and thus can easily form a layer (G) containing a color-converting light-emitting material in a desired thickness.

The thickness of the layer (G) containing a color-converting light-emitting material is preferably 0.5 μm or more, and more preferably 1 μm or more, from the viewpoint of improving color characteristics. On the other hand, the thickness of the layer (G) containing the color-converting light-emitting material is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of thinning and curved surface workability of the display device.

In the image display device, the size of the layer containing the color conversion luminescent material is generally about 20 to 200 μm.

The layers (G) containing the color-converting luminescent material are preferably arranged with a partition (F-1) therebetween. By providing the partition wall between the adjacent layers (G) containing the color conversion light-emitting material, diffusion and color mixing of light emitted can be further suppressed.

As a method for forming the layer (G) containing a color-converting luminescent material, for example, a method of filling a color-converting luminescent material coating liquid containing a color-converting luminescent material in a space partitioned by the partition wall (F-1) can be cited. The color conversion luminescent material coating liquid may further contain a resin and a solvent.

The method of filling the color conversion luminescent material coating liquid is preferably an inkjet coating method or the like from the viewpoint of easily applying different kinds of color conversion luminescent materials separately to each pixel.

The resulting coating film may be dried under reduced pressure and/or dried by heating. In the case of reduced-pressure drying, the reduced-pressure drying temperature is preferably 80 ℃ or lower in order to prevent recondensation of the drying solvent on the inner wall of the reduced-pressure chamber. The pressure for drying under reduced pressure is preferably not more than the vapor pressure of the solvent contained in the coating film, and is preferably 1 to 1000 Pa. The drying time under reduced pressure is preferably 10 to 600 seconds. In the case of heat drying, examples of the heat drying device include an oven and an electric hot plate. The heating and drying temperature is preferably 60-200 ℃. The heating and drying time is preferably 1 to 60 minutes.

The substrate with a partition wall of the present invention preferably further has a low refractive index layer (hereinafter, sometimes referred to as "low refractive index layer (H)") having a refractive index of 1.20 to 1.35 at a wavelength of 550nm, on the layer (G) containing a color conversion light-emitting material. By having the low refractive index layer (H), the light extraction efficiency can be further improved, and the luminance of the display device can be further improved.

Fig. 3 shows a cross-sectional view of an aspect of the substrate with partition walls of the present invention having a low refractive index layer. The substrate 1 has patterned partition walls 2 and a layer 3 containing a color conversion light-emitting material, and further has a low refractive index layer 4 thereon.

In the display device, the refractive index of the low refractive index layer (H) is preferably 1.20 or more, and more preferably 1.23 or more, from the viewpoint of appropriately suppressing reflection of light from the backlight and making light incident on the layer (G) containing the color conversion light-emitting material with good efficiency. On the other hand, the refractive index of the low refractive index layer (H) is preferably 1.35 or less, more preferably 1.30 or less, from the viewpoint of improving the luminance. Here, the refractive index of the low refractive index layer (H) can be measured by irradiating a cured film surface with light having a wavelength of 550nm from a direction perpendicular thereto under atmospheric pressure and at 20 ℃.

The low refractive index layer (H) preferably contains polysiloxane and silica particles having no hollow structure. Polysiloxane has high compatibility with inorganic particles such as silica particles, and functions as a binder capable of forming a transparent layer. Further, by containing the silica particles, fine voids can be efficiently formed in the low refractive index layer (H) to lower the refractive index, and the refractive index can be easily adjusted to the above range. Further, by using silica particles having no hollow structure as the silica particles, since there is no hollow structure in which cracks are likely to occur at the time of curing shrinkage, cracks can be suppressed. In the low refractive index layer (H), the polysiloxane and the silica particles having no hollow structure may be contained independently of each other, or the polysiloxane and the silica particles having no hollow structure may be contained in a combined state. From the viewpoint of uniformity of the low refractive index layer (H), it is preferable that the polysiloxane and the silica particles having no hollow structure are contained in a combined state.

The polysiloxane contained in the low refractive index layer (H) preferably contains fluorine. The polysiloxane contains fluorine, so that the refractive index of the low refractive index layer (H) can be easily adjusted to 1.20-1.35. The fluorine-containing polysiloxane can be obtained by hydrolyzing and polycondensing an alkoxysilane compound containing a fluorine-containing alkoxysilane compound represented by the following general formula (10). Other alkoxysilane compounds may be further used.

R¹³ _mSi(OR⁷)_4-m(10)

In the above general formula (10), R¹³Represents a fluoroalkyl group having a fluorine number of 3 to 17. R⁷Represents R in general formulae (4) to (6)⁷The same groups. m represents 1 or 2. 4-m R⁷And m R¹³May be the same as or different from each other.

Examples of the fluorine-containing alkoxysilane compound represented by the general formula (10) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltriisopropoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriisopropoxysilane, trifluoroethylmethyldimethoxysilane, trifluoroethylmethyldiethoxysilane, trifluoroethylmethyldiisopropoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldiisopropyloxysilane, heptadecafluorodecylmethyldimethoxysilane, and the like, Heptadecafluorodecylmethyldiethoxysilane, heptadecafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane, tridecafluorooctylmethyldiisopropoxysilane, trifluoroethylethyldimethoxysilane, trifluoroethylethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiisopropoxysilane, heptadecafluorodecylethyldiethoxysilane, heptadecafluorodecylethyldiisopropoxysilane, tridecafluorooctylethyldiethoxysilane, tridecafluorooctylethyldimethoxysilane, tridecafluorooctylethyldiethoxysilane, etc. More than 2 of them may be used.

The content of the polysiloxane in the low refractive index layer (H) is preferably 4% by weight or more from the viewpoint of suppressing cracks. On the other hand, from the viewpoint of ensuring thixotropy due to the network between silica particles, appropriately maintaining an air layer in the low refractive index layer (H), and further lowering the refractive index, the content of the polysiloxane is preferably 32% by weight or less.

Examples of the silica particles having no hollow structure in the low refractive index layer (H) include, for example, "スノーテックス" (registered trademark), "オルガノシリカゾル" (registered trademark) series (isopropyl alcohol dispersion, ethylene glycol dispersion, methyl ethyl ketone dispersion, dimethylacetamide dispersion, methyl isobutyl ketone dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n-butanol dispersion, toluene dispersion, and the like, manufactured by nippon chemical industry, inc., PGM-ST, PMA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, and the like). May contain 2 or more of them.

From the viewpoint of ensuring thixotropy due to the network between silica particles, appropriately maintaining an air layer in the low refractive index layer (H), and further lowering the refractive index, the content of silica particles having no hollow structure in the low refractive index layer (H) is preferably 68% by weight or more. On the other hand, the content of the silica particles having no hollow structure is preferably 96% by weight or less from the viewpoint of suppressing cracks.

The thickness of the low refractive index layer (H) is preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of suppressing the generation of defects by covering the level difference of the layer (G) containing the color conversion light emitting material. On the other hand, the thickness of the low refractive index layer (H) is preferably 20 μm or less, and more preferably 10 μm or less, from the viewpoint of reducing the pressure that causes cracks in the low refractive index layer (H).

The method for forming the low refractive index layer (H) is preferably a coating method in view of ease of the formation method. For example, the low refractive index layer (H) can be formed by applying a low refractive index resin composition containing polysiloxane and silica particles to the layer (G) containing the color conversion light emitting material, drying the composition, and then heating the composition.

The substrate with a partition wall of the present invention preferably further comprises (I-1) an inorganic protective layer I having a thickness of 50 to 1,000nm on the low refractive index layer (H). By providing the inorganic protective layer I, moisture in the atmosphere hardly reaches the low refractive index layer (H), and therefore, variation in the refractive index of the low refractive index layer (H) can be suppressed, and luminance degradation can be suppressed.

Fig. 4 shows a cross-sectional view of an embodiment of the substrate with partition walls of the present invention having a low refractive index layer and an inorganic protective layer I. The substrate 1 has patterned partition walls 2 and a layer 3 containing a color conversion light-emitting material thereon, and further has a low refractive index layer 4 and an inorganic protective layer I (5) thereon in this order.

The substrate with a partition wall of the present invention preferably further comprises (I-2) an inorganic protective layer II having a thickness of 50 to 1,000nm, under the low refractive index layer (H). By having the inorganic protective layer II, the raw material for forming the color conversion luminescent material-containing layer (G) is less likely to move from the color conversion luminescent material-containing layer (G) to the low refractive index layer, and therefore, the refractive index variation of the low refractive index layer (H) can be suppressed, and the luminance degradation can be suppressed.

Fig. 5 shows a cross-sectional view of an embodiment of the substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer II. The substrate 1 has patterned partition walls 2 and a layer 3 containing a color conversion light-emitting material thereon, and further has an inorganic protective layer II (6) and a low refractive index layer 4 thereon in this order.

The partition-wall-provided substrate of the present invention preferably further has a color filter (hereinafter, sometimes referred to as "color filter (J)") having a thickness of 1 to 5 μm between the substrate and the layer (G) containing a color conversion luminescent material. The color filter (J) has a function of transmitting visible light in a specific wavelength range and making the transmitted light have a desired hue. By providing the color filter (J), the color purity can be improved. The color purity can be further improved by making the thickness of the color filter (J) 1 μm or more. On the other hand, the brightness of the display device can be further improved by making the thickness of the color filter (J) 5 μm or less.

Fig. 6 shows a cross-sectional view of an aspect of the substrate with partition walls of the present invention having a color filter. The substrate 1 has patterned partition walls 2 and a color filter 7, and the color filter 7 has a layer 3 containing a color conversion light-emitting material thereon.

As the color filter, for example, a color filter used for a flat panel display such as a liquid crystal display, which uses a pigment dispersion type material in which a pigment is dispersed in a photoresist, or the like can be used. More specifically, there may be mentioned a blue color filter which selectively transmits wavelengths of 400nm to 550nm, a green color filter which selectively transmits wavelengths of 500nm to 600nm, a yellow color filter which selectively transmits wavelengths of 500nm or more, a red color filter which selectively transmits wavelengths of 600nm or more, and the like. The color filter may be separately stacked from the layer (G) containing the color conversion light-emitting material, or may be integrally stacked.

The substrate with a partition wall of the present invention preferably further comprises (I-3) an inorganic protective layer III having a thickness of 50 to 1,000nm between the color filter (J) and the layer (G) containing a color conversion luminescent material. By having the inorganic protective layer III, the raw material for forming the color filter (J) does not easily reach the layer (G) containing the color-converting luminescent material from the color filter (J), and thus the luminance variation of the layer (G) containing the color-converting luminescent material can be suppressed.

Fig. 7 shows a cross-sectional view of an aspect of the substrate with partition walls of the present invention having a color filter and an inorganic protective layer III. The substrate 1 has patterned partition walls 2 and color filters 7, an inorganic protective layer III (8) thereon, and a layer 3 containing a color conversion light-emitting material arranged to be partitioned by the partition walls 2 covered with the inorganic protective layer III (8).

The substrate with a partition wall of the present invention preferably further comprises (I-4) an inorganic protective layer IV having a thickness of 50 to 1,000nm on the substrate. The inorganic protective layer IV functions as a refractive index adjusting layer, and can extract light emitted from the layer (G) containing a color conversion light emitting material more efficiently, thereby improving the luminance of the display device. More preferably, an inorganic protective layer IV is provided between the substrate and the partition wall (F) and the layer (G) containing the color-converting luminescent material.

Fig. 8 shows a cross-sectional view of an aspect of the substrate with partition walls of the present invention having an inorganic protective layer IV. An inorganic protective layer IV (9) is provided on the substrate 1, and on these, patterned partition walls 2 and color filters 7 are provided, and on these, patterned partition walls 2 and a layer 3 containing a color conversion luminescent material are provided.

Examples of the material constituting the inorganic protective layers I to IV include metal oxides such as silicon oxide, indium tin oxide, and gallium zinc oxide; metal nitrides such as silicon nitride; and fluorides such as magnesium fluoride. May contain 2 or more of them. Among them, from the viewpoint of low water vapor permeability and high permeability, more preferably 1 or more selected from silicon nitride and silicon oxide.

The thickness of the inorganic protective layers I to IV is preferably 50nm or more, and more preferably 100nm or more, from the viewpoint of sufficiently suppressing the permeation of substances such as water vapor. On the other hand, the thickness of the inorganic protective layers I to IV is preferably 800nm or less, and more preferably 500nm or less, from the viewpoint of suppressing the decrease in transmittance.

The thickness of the inorganic protective layers I to IV can be measured by exposing a cross section perpendicular to the substrate using a polishing apparatus such as a cross section polisher, and observing the cross section under magnification using a scanning electron microscope or a transmission electron microscope.

Examples of the method for forming the inorganic protective layers I to IV include a sputtering method.

Next, a display device of the present invention will be explained. The display device of the present invention includes the substrate with a partition wall and a light-emitting source. As the light-emitting light source, a light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell is preferable. From the viewpoint of excellent light emission characteristics, an organic EL unit is more preferable.

The method for manufacturing a display device of the present invention will be described by taking an example of a display device including a substrate with a partition wall and an organic EL unit of the present invention. Photosensitive polyimide resin was applied on a glass substrate, and an insulating film was formed by photolithography. After aluminum was sputtered as the back electrode layer, the back electrode layer was patterned by photolithography, and the back electrode layer was formed in the opening portion without the insulating film. Next, tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq3) was formed as an electron transport layer by a vacuum vapor deposition method, and then a white light-emitting layer in which dicyanomethylenepyran, quinacridone, or 4, 4' -bis (2, 2-diphenylvinyl) biphenyl was doped in Alq3 was formed as a light-emitting layer. Next, as a hole transport layer, N '-diphenyl-N, N' -bis (α -naphthyl) -1,1 '-biphenyl-4, 4' -diamine was formed into a film by a vacuum evaporation method. Finally, ITO was formed as a transparent electrode by sputtering, and an organic EL cell having a white light-emitting layer was produced. The organic EL unit obtained in this manner was opposed to the substrate with the partition wall and bonded with a sealant, thereby producing a display device.

Next, a touch panel of the present invention will be explained. The touch panel of the present invention includes the substrate with a pattern of the present invention, a transparent electrode, a metal wiring, and a transparent film.

Fig. 10 shows an example of a cross section of a touch panel of the present invention. A glass substrate 11 has a white light-shielding cured film 12 made of the cured film of the present invention, a transparent electrode 13, and a transparent insulating film 14 and metal wiring 15 on the transparent electrode 13.

The transparent electrode is preferably an ITO electrode or the like, because it is not easily visible.

Examples of the material constituting the metal wiring include materials having a low resistance value, such as copper, MAM (molybdenum/aluminum/molybdenum laminated film), and silver.

The transparent film is preferably a transparent insulating film that prevents conduction due to contact between metal wirings, and examples thereof include inorganic films such as silicon oxide and silicon nitride; and a cured film of a negative photosensitive transparent resin composition containing an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator.

Examples of the method for manufacturing a touch panel of the present invention include a method for forming a transparent electrode, a transparent insulating film, and a metal wiring on the patterned processing substrate of the present invention. Hereinafter, a typical production method will be described.

Fig. 11 shows an example of a method for manufacturing a touch panel according to the present invention. Fig. 11 a is a plan view of a patterned processed substrate of the present invention having a white light-shielding cured film 12 on a glass substrate 1. A transparent electrode 13 is formed on the glass substrate 11. Examples of a method for forming the transparent electrode 13 include a method in which ITO is formed by a sputtering method, a photoresist is formed, a pattern is formed by etching, and the photoresist is peeled off. Fig. 11 b shows a top view after the transparent electrode is formed. Next, the transparent insulating film 14 is formed at a predetermined position. As a method for manufacturing the transparent insulating film, when the transparent insulating film is an inorganic film, for example, a CVD (Chemical Vapor Deposition) method is given. When the transparent insulating film is a cured film of a negative photosensitive transparent resin composition, for example, a method using photolithography is exemplified. Fig. 11 c shows a plan view of the transparent insulating film after it is formed. Then, the metal wiring 15 is formed. Examples of the method of forming the metal wiring include: a method of forming a metal film for forming wiring by an evaporation method or a sputtering method, forming a photoresist, forming a pattern by etching, and peeling the photoresist; a printing method of a silver paste; photolithography, and the like. Fig. 11 d shows a top view after the metal wiring is formed.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The following shows compounds using abbreviations among the compounds used in the synthesis examples and examples.

PGMEA: propylene glycol monomethyl ether acetate

DAA: diacetone alcohol

BHT: dibutylhydroxytoluene.

The solid content concentrations of the silicone resin solutions of synthesis examples 1 to 9 and the acrylic resin of synthesis example 10 were determined by the following method. 1.5g of a silicone resin solution or an acrylic resin solution was weighed in an aluminum cup, and heated at 250 ℃ for 30 minutes using a hot plate to evaporate the liquid components. The weight of the solid content remaining in the heated aluminum cup was measured, and the solid content concentration of the silicone resin solution or acrylic resin solution was determined from the ratio to the weight before heating.

The weight average molecular weights of the silicone resins of synthesis examples 1 to 9 and the acrylic resin of synthesis example 10 were determined by the following methods. GPC analysis was performed using a GPC analyzer (HLC-8220; manufactured by DONG ソー, Inc.) and tetrahydrofuran as a mobile phase in accordance with JIS K7252-3 (established year, month, and day: 2008/03/20), and the weight average molecular weight in terms of polystyrene was measured.

The content ratio of each repeating unit in the silicone resins of synthesis examples 1 to 9 was determined by the following method. The silicone resin solution was injected into a10 mm diameter NMR sample tube made of "テフロン" (registered trade name)²⁹In the Si-NMR measurement, the content ratio of each repeating unit is calculated from the ratio of the integrated value of Si derived from a specific organosilane to the integrated value of the entire Si derived from the organosilane. The following shows²⁹Si-NMR measurement conditions.

The device comprises the following steps: nuclear magnetic resonance apparatus (JNM-GX 270; manufactured by Nippon electronics Co., Ltd.)

The determination method comprises the following steps: gated decoupling method

Measurement of nuclear frequency: 53.6693MHz (²⁹Si nucleus)

Spectral width: 20000Hz

Pulse width: 12 mu s (45 degree pulse)

Pulse repetition time: 30.0 seconds

Solvent: acetone-d 6

Reference substance: tetramethylsilane

Measuring temperature: 23 deg.C

Sample rotation speed: 0.0 Hz.

Synthesis example 1 Silicone resin (B-1) solution

A1000 ml three-necked flask was charged with 147.32g (0.675mol) of trifluoropropyltrimethoxysilane, 40.66g (0.175mol) of 3-methacryloxypropylmethyldimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.808g of BHT, and 171.62g of PGMEA, and an aqueous solution of phosphoric acid prepared by dissolving 2.265g (1.0% by weight based on the charged monomer) of phosphoric acid in 52.65g of water was added thereto at room temperature with stirring for 30 minutes. Then, the flask was immersed in an oil bath at 70 ℃ and stirred for 90 minutes, and then the temperature of the oil bath was raised to 115 ℃ over 30 minutes. 1 hour after the start of the temperature rise, the solution temperature (internal temperature) reached 100 ℃ and from this was heated and stirred for 2 hours (internal temperature 100 to 110 ℃ C.), thereby obtaining a silicone resin solution. In addition, during heating and stirringA mixed gas of 95 vol% nitrogen and 5 vol% oxygen was circulated at 0.05 liter/min. 131.35g of methanol and water were distilled off as by-products during the reaction. PGMEA was added to the obtained silicone resin solution so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-1) solution. The weight average molecular weight of the obtained silicone resin (B-1) was 4,000 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the silicone resin (B-1) were 67.5 mol%, 17.5 mol%, 10 mol% and 5 mol%, respectively.

Synthesis example 2 Silicone resin (B-2) solution

A1000 ml three-necked flask was charged with 81.84g (0.375mol) of trifluoropropyltrimethoxysilane, 60.66g (0.3mol) of trifluoropropylmethyldimethoxysilane, 40.66g (0.175mol) of 3-methacryloxypropylmethyldimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.78g of BHT, and 174.95g of PGMEA, and an aqueous solution of phosphoric acid in which 2.217g (1.0% by weight based on the charged monomer) of phosphoric acid was dissolved in 44.55g of water was added thereto at room temperature with stirring for 30 minutes. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 128.40g of methanol and water were distilled off as by-products during the reaction. PGMEA was added to the obtained silicone resin solution so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-2) solution. The weight average molecular weight of the obtained silicone resin (B-2) was 3,200 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of repeating units derived from trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the silicone resin (B-2) were respectively determinedThe amounts were 37.5 mol%, 30 mol%, 17.5 mol%, 10 mol%, and 5 mol%.

Synthesis example 3 Silicone resin (B-3) solution

A1000 ml three-necked flask was charged with 103.67g (0.475mol) of trifluoropropyltrimethoxysilane, 40.66g (0.175mol) of 3-methacryloxypropylmethyldimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 27.24g (0.2mol) of methyltrimethoxysilane, 0.808g of BHT, and 155.37g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 2.101g (1.0% by weight based on the charged monomer) of phosphoric acid in 52.65g of water was added thereto at room temperature with stirring for 30 minutes. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 131.35g of methanol and water were distilled off as by-products during the reaction. PGMEA was added to the obtained silicone resin solution so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-3) solution. The weight average molecular weight of the obtained silicone resin (B-3) was 3,500 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane and methyltrimethoxysilane in the silicone resin (B-3) were 47.5 mol%, 17.5 mol%, 10 mol%, 5 mol% and 20 mol%, respectively.

Synthesis example 4 Silicone resin (B-4) solution

A1000 ml three-necked flask was charged with 103.67g (0.475mol) of trifluoropropyltrimethoxysilane, 24.04g (0.20mol) of dimethyldimethoxysilane, 43.46g (0.175mol) of 3-methacryloxypropyltrimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.736g of BHT, and 161.28g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 2.097g (1.0% by weight based on the charged monomer) of phosphoric acid in 50.85g of water was added thereto with stirring at room temperature over 30 minutes. Then, the same as in Synthesis example 1The same operation was carried out to obtain a silicone resin solution. 130.05g of methanol and water were distilled off as by-products during the reaction. PGMEA was added to the obtained silicone resin solution so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-4) solution. The weight average molecular weight of the obtained silicone resin (B-4) was 3,800 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the silicone resin (B-4) were 47.5 mol%, 20 mol%, 17.5 mol%, 10 mol% and 5 mol%, respectively.

Synthesis example 5 Silicone resin (B-5) solution

A1000 ml three-necked flask was charged with 147.32g (0.675mol) of trifluoropropyltrimethoxysilane, 43.46g (0.175mol) of 3-methacryloxypropyltrimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.810g of BHT, and 172.59g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 2.293g (1.0% by weight based on the charged monomer) of phosphoric acid in 54.45g of water was added thereto at room temperature with stirring for 30 minutes. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 140.05g of methanol and water were distilled off as by-products during the reaction. To the obtained silicone resin solution, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-5) solution. The weight average molecular weight of the obtained silicone resin (B-5) was 4,100 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the silicone resin (B-5) were 67.5 mol%, 17.5 mol%, 10 mol% and 5 mol%, respectively.

Synthesis example 6 Silicone resin (B-6) solution

Into a 1000ml three-necked flask, 76.93g (0.35mol) of trifluoropropyltrimethoxysilane, 41.00g (0.175mol) of 3-acryloxypropyltrimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 51.08g (0.375mol) of methyltrimethoxysilane, 0.375g of BHT, and 136.95g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 2.070g (1.0% by weight based on the charged monomer) of phosphoric acid in 58.50g of water was added over 30 minutes while stirring at room temperature. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 139.50g of methanol and water were distilled off as by-products during the reaction. To the obtained silicone resin solution, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-6) solution. The weight average molecular weight of the obtained silicone resin (B-6) was 5,000 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from trifluoropropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and methyltrimethoxysilane in the silicone resin (B-6) were 35 mol%, 17.5 mol%, 10 mol% and 37.5 mol%, respectively.

Synthesis example 7 Silicone resin (B-7) solution

A1000 ml three-necked flask was charged with 76.39g (0.35mol) of trifluoropropyltrimethoxysilane, 40.66g (0.175mol) of 3-methacryloxypropylmethyldimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 44.27g (0.325mol) of methyltrimethoxysilane, 0.673g of BHT, and 145.22g of PGMEA, and an aqueous solution of phosphoric acid prepared by dissolving 1.999g (1.0% by weight based on the charged monomer) of phosphoric acid in 52.65g of water was added thereto at room temperature with stirring for 30 minutes. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 130.25g of methanol and water were distilled off as by-products during the reaction. To the obtained silicone resin solution, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-7) solution. In addition, what is moreThe weight-average molecular weight of the obtained silicone resin (B-7) was 3,900 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane and methyltrimethoxysilane in the silicone resin (B-7) were 35 mol%, 17.5 mol%, 10 mol%, 5 mol% and 32.5 mol%, respectively.

Synthesis example 8 Silicone resin (B-8) solution

A1000 ml three-necked flask was charged with 185.51g (0.85mol) of trifluoropropyltrimethoxysilane, 17.43g (0.075mol) of 3-methacryloxypropylmethyldimethoxysilane, 19.67g (0.075mol) of 3-trimethoxysilylpropylsuccinic anhydride, 0.779g of BHT, and 166.39g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 2.226g (1.0% by weight based on the charged monomer) of phosphoric acid in 54.00g of water was added thereto at room temperature with stirring over 30 minutes. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 136.90g of methanol and water were distilled off as by-products during the reaction. PGMEA was added to the obtained silicone resin solution so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-8) solution. The weight average molecular weight of the obtained silicone resin (B-8) was 4,600 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride in the silicone resin (B-8) were 85 mol%, 7.5 mol% and 7.5 mol%, respectively.

Synthesis example 9 Silicone resin (B-9) solution

In a 1000ml three-necked flask were placed 164.94g (0.675mol) of diphenyldimethoxysilane, 40.66g (0.175mol) of 3-methacryloxypropylmethyldimethoxysilane, 26.23g (0.1mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.974g of BHT and 201.22g of PGMEA, and the mixture was heated at room temperatureAn aqueous phosphoric acid solution prepared by dissolving 2.442g (1.0 wt% relative to the amount of the monomers added) of phosphoric acid in 40.50g of water was added thereto over 30 minutes while stirring. Then, a silicone resin solution was obtained in the same manner as in synthesis example 1. 136.90g of methanol and water were distilled off as by-products during the reaction. To the obtained silicone resin solution, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a silicone resin (B-9) solution. The weight average molecular weight of the obtained silicone resin (B-9) was 2,800 (in terms of polystyrene). Further, according to²⁹As a result of Si-NMR measurement, the molar ratios of the repeating units derived from diphenyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the silicone resin (B-9) were 67.5 mol%, 17.5 mol%, 10 mol% and 5 mol%, respectively.

The raw material compositions of the silicone resins of synthesis examples 1 to 9 are shown in tables 1 to 2.

Synthesis example 10 acrylic resin (b) solution

In a 500ml three-necked flask, 3g of 2, 2' -azobis (isobutyronitrile) and 50g of PGME were charged. Then, 30g of methacrylic acid, 35g of benzyl methacrylate, and tricyclo [5.2.1.0 ] were added^2,6]Decane-8-yl methacrylate (35 g) was stirred at room temperature for a while, and after replacing the nitrogen in the flask, the mixture was heated and stirred at 70 ℃ for 5 hours. Then, 15g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ℃ for 4 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration became 40% by weight, to obtain an acrylic resin (b) solutionAnd (4) liquid. The weight average molecular weight of the acrylic resin (b) was 10,000 (in terms of polystyrene).

Synthesis example 11 silane coupling agent (G-1) solution

41.97g (0.16mol) of 3-trimethoxysilylpropylsuccinic anhydride and 11.70g (0.16mol) of t-butylamine were added to PGMEA200g, and the mixture was stirred at room temperature for a while and then stirred at 40 ℃ for 2 hours. Then, the temperature was increased to 80 ℃ and the mixture was stirred with heating for 6 hours. PGMEA was added to the obtained solution so that the solid content concentration became 20% by weight, to obtain a silane coupling agent (G-1) which was a mixed solution of 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid and 2- (2- (tert-butylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid.

Synthesis example 12 Green organic phosphor

3, 5-dibromobenzaldehyde (3.0g), 4-tert-butylphenyl boronic acid (5.3g), tetrakis (triphenylphosphine) palladium (0) (0.4g) and potassium carbonate (2.0g) were charged into a flask, and nitrogen substitution was performed. Degassed toluene (30mL) and degassed water (10mL) were added thereto, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3, 5-bis (4-tert-butylphenyl) benzaldehyde (3.5g) as a white solid. Next, 3, 5-bis (4-tert-butylphenyl) benzaldehyde (1.5g) and 2, 4-dimethylpyrrole (0.7g) were added to the flask, dehydrated dichloromethane (200mL) and trifluoroacetic acid (1 drop) were added, and stirring was carried out under a nitrogen atmosphere for 4 hours. A solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (0.85g) in dehydrated dichloromethane was added thereto, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0mL) and diisopropylethylamine (7.0mL) were added and stirred for 4 hours, and then water (100mL) was further added and stirred to separate the organic layer. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 0.4g of a green powder (yield: 17%). Of the resulting green powder¹H-NMR analysisAs a result, it was confirmed that the green powder obtained as described above was [ G-1 ] represented by the following structural formula]。

¹H-NMR(CDCl₃(d＝ppm))：7.95(s，1H)，7.63-7.48(m，10H)，6.00(s，2H)，2.58(s，6H)，1.50(s，6H)，1.37(s，18H)。

Synthesis example 13 polysiloxane solution containing silica particles (LS-1)

In a 500ml three-necked flask, 224.37g of an isopropyl alcohol dispersion (IPA-ST-UP: manufactured by Nissan chemical industries, Ltd.) of methyltrimethoxysilane 0.05g (0.4mmol), trifluoropropyltrimethoxysilane 0.66g (3.0mmol), trimethoxysilylpropylsuccinic anhydride 0.10g (0.4mmol), gamma-acryloyloxypropyltrimethoxysilane 7.97g (34mmol) and 15.6 wt% silica particles were mixed, and 163.93g of ethylene glycol mono-t-butyl ether was added. An aqueous phosphoric acid solution prepared by dissolving 0.088g of phosphoric acid in 4.09g of water was added thereto over 3 minutes while stirring at room temperature. Then, after the flask was immersed in an oil bath at 40 ℃ and stirred for 60 minutes, the oil bath was warmed up to 115 ℃ over 30 minutes. 1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and the solution was stirred by heating for 2 hours (internal temperature 100 to 110 ℃) to obtain a polysiloxane solution (LS-1) containing silica particles. Further, while the temperature was increased and the stirring was performed, nitrogen gas was passed through the mixture at a flow rate of 0.05l (liter) per minute. 194.01g of methanol and water were distilled off as by-products during the reaction. The obtained polysiloxane solution containing silica particles (LS-1) had a solid content concentration of 24.3 wt%, and the contents of polysiloxane and silica particles in the solid content were 15 wt% and 85 wt%, respectively. The molar ratios of the repeating units derived from methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and γ -acryloyloxypropyltrimethoxysilane in the polysiloxane containing silica particles (LS-1) obtained were 1.0 mol%, 8.0 mol%, 1.0 mol%, and 90.0 mol%, respectively.

Preparation example 1 negative photosensitive coloring composition (P-1)

5.00g of a silicone resin (B-1) solution obtained in Synthesis example 1 as (B) a white pigment (A), titanium dioxide pigment (R-960; manufactured by BASF ジャパン Co., Ltd.) was mixed with 5.00g of the silicone resin (B-1). Dispersion was carried out using a mill type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1).

Next, 10.00g of a pigment dispersion (MW-1), 1.15g of a silicone resin (B-1) solution, 0.100g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("イルガキュア" (registered trade name) -907 (product name), manufactured by BASF ジャパン (Co.) as a photopolymerization initiator (C)), 0.200g of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide ("イルガキュア" -819 (product name), manufactured by BASF ジャパン (Co.) Co., Ltd.), 1.50g of pentaerythritol acrylate ("ライトアクリレート" (registered trade name) PE-3A (product name), manufactured by Kyoeisha chemical Co., Ltd.), and 1.38 g of a photopolymerizable fluorine-containing compound ("メガファック" (registered trade name) RS-76-E (product name) ) DIC (manufactured by Ltd.) 1.00G of a 40 wt% PGMEA diluted solution, 0.500G of a20 wt% PGMEA diluted solution of a silane coupling agent (G1), 0.200G of 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate ("セロキサイド" (registered trademark) -2021P (trade name), ダイセル (manufactured by Ltd.), 0.200G of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ] ("イルガノックス" (registered trademark) -1010 (trade name), manufactured by BASF ジャパン (manufactured by Ltd.), 0.300G of a PGMEA10 wt% diluted solution of an acrylic surfactant (trade name, "BYK" (registered trademark) -352, ビックケミー, ジャパン (manufactured by Ltd.) (corresponding to a concentration of 500ppm) dissolved in a mixed solvent of DAA1.000g and PGMEA4.200g, stirring was performed. Then, filtration was performed using a 5.0 μm filter to obtain a negative photosensitive coloring composition (P-1).

Preparation examples 2 to 4 negative photosensitive coloring compositions (P-2) to (P-4)

Negative photosensitive coloring compositions (P-2) to (P-4) were obtained in the same manner as in preparation example 1, except that the solutions of the siloxane resins (B-2) to (B-4) were used instead of the solution of the siloxane resin (B-1).

Preparation example 5 negative photosensitive coloring composition (P-5)

A negative photosensitive coloring composition (P-5) was obtained in the same manner as in preparation example 1, except that 1.00g of a 40 wt% PGMEA dilution solution of pentaerythritol acrylate ("ライトアクリレート" (registered trademark) PE-3A) was used in place of 1.00g of the 40 wt% PGMEA dilution solution of the photopolymerizable fluorine-containing compound ("メガファック" (registered trademark) RS-76-E).

Preparation example 6 negative photosensitive coloring composition (P-6)

A negative photosensitive coloring composition (P-6) was obtained in the same manner as in preparation example 1, except that 1.00g of a 40 wt% PGMEA diluted solution of 2,2, 2-trifluoroethyl acrylate ("ビスコート" (registered trademark) -3F (trade name), manufactured by Osaka organic chemistry, was used instead of 1.00g of the 40 wt% PGMEA diluted solution of the photoreactive fluorine-containing compound ("メガファック" (registered trademark) RS-76-E (trade name) DIC (manufactured by Ltd.).

Preparation example 7 negative-type photosensitive coloring composition (P-7)

A negative photosensitive coloring composition (P-7) was obtained in the same manner as in preparation example 1, except that a titanium dioxide pigment (CR-97; manufactured by BASF ジャパン Co., Ltd.) was used in place of the titanium dioxide pigment (R-960; manufactured by BASF ジャパン Co., Ltd.).

Preparation example 8 negative photosensitive coloring composition (P-8)

A negative photosensitive coloring composition (P-8) was obtained in the same manner as in preparation example 1, except that 0.100g of "イルガキュア" (registered trademark) -MBF (trade name), manufactured by BASF ジャパン (trade name) was used in place of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("イルガキュア' -127).

Preparation examples 9 to 13 negative photosensitive coloring compositions (P-9) to (P-13)

Negative photosensitive coloring compositions (P-9) to (P-13) were obtained in the same manner as in preparation example 1, except that the solutions of the siloxane resins (B-5) to (B-9) were used instead of the solution of the siloxane resin (B-1).

Preparation example 14 negative-type photosensitive coloring composition (P-14)

A negative photosensitive coloring composition (P-14) was obtained in the same manner as in preparation example 1, except that an acrylic resin (B) solution was used instead of the resin (B-1) solution.

Preparation example 15 negative-type photosensitive coloring composition (P-15)

8.00g of a pigment dispersion (MW-1), 1.615g of a polysiloxane (B-1) solution obtained in Synthesis example 1, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetoxy oxime) (1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetoxy) was used as a photopolymerization initiator (hereinafter, "OXE-02" manufactured by "イルガキュア" (registered trademark) BASF ジャパン (trade name)) 0.160g of bis (2,4, 6-trimethylbenzoyl) -phenyl phosphine oxide ("イルガキュア" 819 (trade name)), 0.160g (hereinafter, "IC-819")) prepared by BASF ジャパン (trade name), 1.20g (trade name) of dipentaerythritol hexaacrylate ("KAYARAD" (registered trade name) DPHA (hereinafter, "DPHA")) as a photopolymerizable compound, 1.100 g (trade name) of a 40 wt% PGMEA diluted solution of a photopolymerizable fluorine-containing compound ("メガファック" (registered trade name) RS-76-E (trade name ") DIC (hereinafter," RS-76-E ")) as a lyophobic compound, 0.160g of 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate (" セロキサイド "(registered trade name) 2021P (trade name) prepared by ダイセル (hereinafter," セロキサイド 2021P ")), and 0.160g of ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] (" 5 " イルガノックス "(registered trademark) 1010 (trade name), manufactured by BASF ジャパン (hereinafter," IRGANOX1010 ")) 0.024g, and 0.100g (corresponding to a concentration of 500ppm) of a PGMEA10 wt% diluted solution of an acrylic surfactant (" BYK "(registered trademark) 352 (trade name), manufactured by ビックケミージャパン (manufactured by LTD)) were dissolved in a mixed solvent of DAA1.200g and PGMEA7.281g, and stirred. Then, filtration was performed using a 5.0 μm filter to obtain a negative photosensitive coloring composition (P-15).

Preparation example 16 negative photosensitive coloring composition (P-16)

A negative photosensitive coloring composition (P-16) was obtained in the same manner as in preparation example 15, except that a polysiloxane (B-5) solution was used instead of the polysiloxane (B-1) solution.

Preparation example 17 negative-type photosensitive coloring composition (P-17)

A negative photosensitive coloring composition (P-17) was obtained in the same manner as in preparation example 15, except that the amount of the diluted 40 wt% PGMEA solution of RS-76-E added was changed to 0.01g and the amount of the polysiloxane (B-1) solution was changed to 1.705 g.

Preparation example 18 negative-type photosensitive coloring composition (P-18)

A negative photosensitive coloring composition (P-18) was obtained in the same manner as in preparation example 15, except that 0.100g of a 40% by weight PGMEA diluted solution without adding RS-76-E and the amount of the polysiloxane (B-1) solution was changed to 1.715 g.

Preparation example 19 negative photosensitive coloring composition (P-19)

A negative photosensitive colored composition (P-19) was obtained in the same manner as in preparation example 15, except that the amount of the pigment dispersion (MW-1) added was changed to 4.00g, the amount of the polysiloxane (B-1) solution added was changed to 8.615g, and a mixed solvent of DAA1.200g and PGMEA1.881g was used.

Preparation example 20 negative photosensitive coloring composition (P-20)

A negative photosensitive coloring composition (P-20) was obtained in the same manner as in preparation example 15, except that the amount of the pigment dispersion (MW-1) added was changed to 3.20g, the amount of the polysiloxane (B-1) solution added was changed to 10.015g, and a mixed solvent of DAA1.200g and PGMEA3.681g was used.

Preparation example 21 negative-type photosensitive coloring composition (P-21)

A negative photosensitive coloring composition (P-21) was obtained in the same manner as in preparation example 15, except that the amount of the pigment dispersion (MW-1) added was changed to 1.60g, the amount of the polysiloxane (B-1) solution added was changed to 12.815g, and a mixed solvent of DAA1.200g and PGMEA2.481g was used.

The compositions of preparation examples 1 to 21 are shown in tables 3,4 and 5.

PREPARATION EXAMPLE 22 color-conversion luminescent Material composition (CL-1)

20 parts by weight of a 0.5 wt% toluene solution of a green quantum dot material (Lumidot 640 CdSe/ZnS, average particle diameter 6.3 nm: アルドリッチ Co., Ltd.), 45 parts by weight of DPHA, 5 parts by weight of "イルガキュア" (registered trademark) 907 (manufactured by BASF ジャパン Co., Ltd.), 166 parts by weight of a 30 wt% PGMEA solution of an acrylic resin (SPCR-18 (trade name), manufactured by Showa Denko K.K.) and 97 parts by weight of toluene were mixed and stirred to be uniformly dissolved. The mixture was filtered through a 0.45 μm syringe filter to prepare a color-converted luminescent material composition (CL-1)

PREPARATION EXAMPLE 23 color-conversion luminescent Material composition (CL-2)

A color-converted luminescent material composition (CL-2) was prepared in the same manner as in preparation example 22, except that 10.4 parts by weight of the green phosphor G obtained in Synthesis example 12 was used in place of the green quantum dot material and the amount of toluene added was changed to 117 parts by weight.

Preparation example 24 color Filter Forming Material (CF-1)

A slurry was prepared by mixing 90g of c.i. pigment green 59, 60g of c.i. pigment yellow 150, 75g of a polymeric dispersant (BYK (registered trademark) -6919 (trade name) ビックケミー), 100g of a binder resin (アデカアークルズ (registered trademark) WR301 (trade name) (manufactured by ADEKA corporation), and PGMEA675 g. A beaker containing the slurry was connected to a Diyno-Mill (DYNO-MILL) tube, and dispersion treatment was carried out for 8 hours at a peripheral speed of 14m/s using zirconia beads having a diameter of 0.5mm as a medium to prepare a pigment Green 59 dispersion (GD-1).

56.54g of pigment green 59 dispersion (GD-1), 3.14g of acrylic resin ("サイクロマー" (registered trademark) P (ACA) Z250 (trade name) ダイセル. オルネクス (manufactured by KAPPA Z250) (hereinafter "P (ACA) Z250")), DPHA2.64g, 0.330g of photopolymerization initiator ("オプトマー" (registered trademark) NCI-831 (trade name) (manufactured by KAPPA) (hereinafter "NCI-831")), 0.04g of surfactant (BYK "(registered trademark) -333 (trade name) ビックケミー), 0.01g of BHT as a polymerization inhibitor, and 37.30g of PGMEA as a solvent were added to prepare a color filter forming material (CF-1).

Preparation example 25 resin composition for light-shielding partition wall

150g of carbon black (MA100 (trade name) manufactured by Mitsubishi chemical corporation), 75g of a polymer dispersant BYK (registered trademark) -6919, 100g of P (ACA) Z250, and 675g of PGMEA were mixed to prepare a slurry. The beaker containing the slurry was connected to a tube for a Danuo mill, and dispersion treatment was carried out for 8 hours at a peripheral speed of 14m/s using zirconia beads having a diameter of 0.5mm as a medium to prepare a pigment dispersion (MB-1).

56.54g of the pigment dispersion (MB-1), 3.14g of P (ACA) Z250, 2.64g of DPHA, 0.330g of NCI-831, 0.04g of BYK (registered trademark) -333, 0.01g of t-butylcatechol as a polymerization inhibitor, and 37.30g of PGMEA were added to prepare a resin composition for a light-shielding partition wall.

Preparation example 26 Material for Forming Low refractive index layer

5.350g of the silica particle-containing polysiloxane solution (LS-1) obtained in Synthesis example 13, 1.170g of ethylene glycol mono-t-butyl ether, and 3.48g of DAA were mixed, and then filtered through a 0.45 μm syringe filter to prepare a low refractive index layer forming material.

The evaluation methods in the examples and comparative examples are shown below.

Refractive index of white pigment

The refractive index of the white pigment (A) used in each of the examples and comparative examples was measured by the B method (liquid immersion method using a microscope (Beckline method)) among the refractive index measurement methods of plastics specified in JIS K7142-2014 (established year, month, day: 2014/04/20). The measurement wavelength was 587.5 nm. However, instead of the immersion liquid used in JIS K7142-2014, the (plant) shimadzu デバイス is used to manufacture the "contact liquid", and in the immersion liquid temperature: measured at 20 ℃. As the microscope, a polarization microscope "オプチフォト" (manufactured by Kyowa Kagaku K.K.; ニコン) was used. Each of 30 samples of the white pigment (a) was prepared, and the refractive index thereof was measured, and the average value thereof was defined as the refractive index.

< refractive index of Silicone resin or acrylic resin >

The refractive index of the silicone resin or acrylic resin used in each of the examples and comparative examples was determined by the following method. The silicone resin solutions of Synthesis examples 1 to 9 or the acrylic resin solution of Synthesis example 10 were applied to a silicon wafer by means of a spin coater, and dried for 2 minutes on a hot plate at 90 ℃. Then, the resultant was cured in an oven (IHPS-222; エスペック, Inc.) at 230 ℃ for 30 minutes in air to prepare a cured film. The refractive index of the cured film surface was measured by irradiating the surface with light having a wavelength of 587.5nm from the perpendicular direction at 20 ℃ under atmospheric pressure using a prism coupler (PC-2000, manufactured by Metricon corporation), and the decimal point and the third position are rounded.

< resolution >

The negative photosensitive coloring compositions obtained in examples and comparative examples were spin-coated on an alkali-free glass substrate of 10cm square by using a spin coater (trade name 1H-360S, manufactured by ミカサ corporation) so that the cured film thickness became 10 μm, and were pre-baked at 90 ℃ for 2 minutes by using an electric hot plate (trade name SCW-636, manufactured by スクリーン corporation) to prepare a pre-baked film having a film thickness of 10 μm.

The prebaked film thus prepared was exposed to a Mask Aligner (Mask Aligner) (product name: PLA-501F, キヤノン, manufactured by Ltd.) using an ultrahigh pressure mercury lamp as a light source, with lines having widths of 100 μm, 80 μm, 60 μm, 50 μm, 40 μm and 30 μm being interposed therebetween&A mask of a gap pattern with an exposure amount of 150mJ/cm²(i-ray) exposure was performed at intervals of 100 μm. Then, an automatic developing apparatus (waterfall swamp made by K) was used "AD-2000 (trade name) "), spray development was performed for 100 seconds using a 0.045 wt% potassium hydroxide aqueous solution, followed by rinsing with water for 30 seconds.

The developed pattern was observed under magnification using a microscope adjusted to a magnification of 100, and the narrowest line width among the patterns in which no residue was observed in the unexposed area was defined as the resolution. However, the case where the unexposed portion near the 100 μm wide pattern also had residue was assumed to be "> 100 μm".

< visual reflectance >

The negative photosensitive coloring compositions obtained in the examples and comparative examples were spin-coated on a10 cm-square alkali-free glass substrate using a spin coater (trade name: 1H-360S, manufactured by ミカサ (ltd)) so that the cured film thickness became 10 μm, and were prebaked at 90 ℃ for 2 minutes using a hot plate (SCW-636), thereby forming a prebaked film. The produced prebaked film was exposed, developed and developed in the same manner as in the above evaluation method of < resolution > except that the film was not masked. Further, the resultant was cured in an oven (trade name: IHPS-222, エスペック, Inc.) at 230 ℃ for 30 minutes in air to prepare a cured film.

The alkali-free glass substrate having a cured film was evaluated by measuring the reflectance of the cured film from the glass substrate side using a spectrophotometer (trade name CM-2600d, manufactured by コニカミノルタ corporation) and determining the CIE Y value (visual reflectance). However, when a crack occurs in the cured film, an accurate value cannot be obtained due to a crack or the like, and thus the measurement of the visual reflectance is not performed.

< reflectance >

The negative photosensitive coloring compositions obtained in the examples and comparative examples were spin-coated on a10 cm-square alkali-free glass substrate using a spin coater (trade name: 1H-360S, manufactured by ミカサ (ltd)) so that the cured film thickness became 10 μm, and were prebaked at 90 ℃ for 2 minutes using a hot plate (SCW-636) to form a prebaked film. The produced prebaked film was exposed, developed and developed in the same manner as in the above evaluation method of < resolution > except that the film was not masked. Further, the resultant was cured in an oven (trade name: IHPS-222, エスペック, Inc.) at 230 ℃ for 30 minutes in air to prepare a cured film.

The alkali-free glass substrate having a cured film was measured for reflectance at a wavelength of 550nm from the full-size film side in SCI mode using a spectrocolorimeter (trade name CM-2600d, manufactured by コニカミノルタ Co., Ltd.). However, when a crack occurs in the full-thickness film, an accurate value cannot be obtained due to a crack or the like, and thus the reflectance is not measured.

< Heat resistance-1 crack resistance >

The negative photosensitive coloring compositions obtained in examples and comparative examples were coated on a10 cm-square alkali-free glass substrate using a spin coater (1H-360S; manufactured by ミカサ K.) so that the cured film thicknesses thereof became 5 μm, 10 μm, 15 μm and 20 μm, respectively, and were prebaked at 90 ℃ for 2 minutes using a hot plate (SCW-636), thereby forming prebaked films. The produced prebaked film was exposed, developed and developed in the same manner as in the above evaluation method of < resolution > except that the film was not masked. Further, the resultant was cured in an oven (trade name: IHPS-222, エスペック, Inc.) at 230 ℃ for 30 minutes in air to prepare a cured film.

The cured film thus produced was visually observed to evaluate the presence or absence of cracks. Even if 1 crack was observed, the film thickness was judged to have no crack resistance. For example, when the film thickness was 15 μm and no cracks were present, and when the film thickness was 20 μm and cracks were present, the crack-resistant film thickness was judged to be "≦ 15 μm". The cracking resistance was determined to be ≧ 20 μm when no crack was present even at 20 μm, and "< 5 μm" when cracks were present even at 5 μm, and the crack resistance before curing was added.

The cured film having no cracks was subjected to additional curing in an oven (IHPS-222) at 240 ℃ for 2 hours in air, and then similarly evaluated for the presence or absence of cracks, and the crack resistance after additional curing was determined.

< Heat resistance-2 color Change >

The negative photosensitive coloring compositions obtained in the examples and comparative examples were coated on a10 cm-square alkali-free glass substrate using a spin coater (1H-360S; manufactured by ミカサ K.) so that the cured film thickness became 10 μm, and cured films were produced in the same manner as in the evaluation method of < Heat resistance-1 crack resistance >. However, when cracks were generated in the cured film, the remaining evaluation was not performed.

The obtained alkali-free glass substrate having a cured film was subjected to measurement of the reflection chromaticity of the cured film from the glass substrate side by using a spectrophotometer (trade name CM-2600d, manufactured by コニカミノルタ Co., Ltd.), and the hue of yellow was evaluated by the value of b in the case of using CIE1976(L, a, b) color space to evaluate the hue of yellow to provide color characteristics before additional curing. As the light source, a C light source was used.

The cured film whose color characteristics were evaluated was subjected to additional curing in air at 240 ℃ for 2 hours using an oven (IHPS-222), and then the reflectance was measured in the same manner, and the value expressed by CIE1976(L, a, b) color space was compared with the color characteristics before additional curing, and the color difference (hereinafter, "Δ Eab") was calculated by the following formula (I). The smaller Δ Eab, the better heat resistance. Δ Eab is preferably 1.0 or less, and more preferably 0.7 or less.

ΔEab＝(X1²+X2²+X3²)^0.5The formula (I)

Here, X1, X2, and X3 are as follows.

X1：{L＊(0)}-{L＊(1)}

X2：{a＊(0)}-{a＊(1)}

X3：{b＊(0)}-{b＊(1)}

Wherein L (0), a (0) and b (0) represent the values of L (a), a and b before additional curing, and L (1), a (1) and b (1) represent the values of L (a), b after additional curing.

< OD value >

As a model of the partition wall of the substrate with the partition wall obtained in each of examples and comparative examples, a full-thickness film was formed on the glass substrate in the same manner as the evaluation method of < reflectance >. The intensity of incident light and transmitted light was measured with a densitometer (361T (visual); manufactured by X-ray Co., Ltd.) on the obtained glass substrate having a full thickness film, and the optical density (OD value) was calculated from the following formula (10).

OD value log10 (I)₀I. formula (10)

I₀: intensity of incident light

I: the intensity of the transmitted light.

< surface contact Angle >

As a model of the partition wall of the substrate with the partition wall obtained in each of examples and comparative examples, a full-thickness film was formed on the glass substrate in the same manner as the evaluation method of < reflectance >. For the obtained full size film, DM-700 manufactured by Kyowa interface science (Ltd.) was used, and a microinjector: a contact angle meter manufactured by Kyowa interface science (Co., Ltd.) was coated with テフロン (registered trademark) using a needle 22G, and the surface contact angle to propylene glycol monomethyl ether acetate was measured at 25 ℃ in the air according to the wettability test method of the substrate glass surface defined in JIS R3257 (established year, month, day: 1999/04/20).

< ink-jet coatability >

In the partition-provided substrate before the formation of the layer (G) containing the color conversion luminescent material, which was obtained in each of examples and comparative examples, the pixel portion surrounded by the lattice-shaped partition was subjected to inkjet coating using an inkjet coating apparatus (manufactured by InkjetLabo, クラスターテクノロジー, inc.) with PGMEA as an ink. The PGMEA of 160pL was applied in a grid pattern for every 1 cell, and the presence or absence of a crack (a phenomenon in which ink crosses a partition wall and is mixed into an adjacent pixel portion) was observed, and the inkjet coatability was evaluated by the following criteria. The less cracking indicates higher lyophobic performance and more excellent ink-jet coatability.

A: the ink does not overflow from within the pixel.

B: in some of the ink flows over the partition walls from inside the pixels.

C: the ink overflows from the inside of the pixel to the upper surface of the partition wall over the entire surface.

< thickness >

The thickness of the structure before and after the formation of the color-conversion luminescent material-containing layer (G) was measured using an サーフコム stylus film thickness measuring apparatus, and the difference between the thicknesses was calculated, thereby measuring the thickness of the color-conversion luminescent material-containing layer (G) on the partition-equipped substrates obtained in examples and comparative examples. The thickness of the low refractive index layer (H) was measured in the same manner in examples 20 to 22, the thickness of the color filter was measured in the same manner in examples 23 to 24, and the thickness (height) of the light-shielding partition was measured in the same manner in example 26.

In examples 21 to 22 and 24 to 25, the thicknesses of the inorganic protective layers I to IV were measured by exposing a cross section perpendicular to the substrate using a polishing apparatus such as a cross-section polisher, and observing the cross section under magnification using a scanning electron microscope or a transmission electron microscope.

< Brightness >

The substrate with the partition wall obtained in each of examples and comparative examples was mounted on a planar light-emitting device as a light source, the planar light-emitting device having a commercially available LED backlight (peak wavelength 465nm) mounted thereon, and the layer containing the color-converting luminescent material was disposed on the light source side. The LED element was turned on by passing a current of 30mA through the planar light-emitting device, and the luminance (unit: cd/m) according to the CIE1931 standard was measured using a spectral radiance meter (CS-1000, manufactured by コニカミノルタ Co., Ltd.)²) And set as the initial brightness. However, the evaluation of luminance was performed by taking the initial luminance of comparative example 9 as a relative value of the standard 100. In addition, when cracks are generated in the partition walls, accurate values cannot be obtained due to cracks or the like, and therefore, evaluation is not performed.

Further, after the LED elements were turned on at room temperature (23 ℃) for 48 hours, the luminance was measured in the same manner, and the change in luminance with time was evaluated. However, the evaluation of luminance was performed by taking the initial luminance of comparative example 9 as a relative value of 100.

< color characteristics >

On a commercially available white reflection plate, the partition-equipped substrates obtained in each of examples and comparative examples were provided such that a layer containing a color conversion light-emitting material was disposed on the white reflection plate side. A spectrum including a regular reflection light was measured by irradiating the substrate with light from a spectrophotometer (CM-2600d, manufactured by コニカミノルタ, having a diameter of 8 mm).

The color gamut set by the color specification bt.2020, which can substantially reproduce colors of nature, is specified with red, green, and blue on the spectral locus shown in the chromaticity diagram as three primary colors, the wavelengths of red, green, and blue corresponding to 630nm, 532nm, and 467nm, respectively. From the reflectance (R) at 3 wavelengths of 470nm, 530nm and 630nm of the obtained reflectance spectrum, the luminescent color of the layer containing the color-converting luminescent material was evaluated by the following criteria.

A：R₅₃₀/(R₆₃₀+R₅₃₀+R₄₇₀)≧0.55

B：0.55＞R₅₃₀/(R₆₃₀+R₅₃₀+R₄₇₀)。

< display Property >

The display characteristics of the display devices fabricated by combining the partition-wall-provided substrates obtained in the examples and comparative examples with organic EL elements were evaluated based on the following criteria.

A: the display device has a vivid green display color and excellent contrast.

B: although the color is observed to be slightly unnatural, it is a display device without problems.

Examples 1 to 13 and comparative examples 1 to 7

The negative-type colored photosensitive compositions of preparation examples 1 to 20 were evaluated for resolution, visual reflectance, and heat resistance according to the evaluation methods described above. The evaluation results are shown in tables 6 to 8.

Examples 14 to 26 and comparative examples 8 to 9

The substrates with partition walls obtained by preparing the negative colored photosensitive compositions of examples 15 to 21 were evaluated for reflectance, OD value, surface contact angle, inkjet coatability, thickness, brightness, color characteristics and display characteristics according to the evaluation methods described above. However, in comparative example 8, cracks were generated in the cured film and the partition wall, and an accurate value could not be obtained, and therefore, evaluation was not performed. The structures of the examples and comparative examples are shown in table 9, and the evaluation results are shown in table 10.

[ Table 9]

Description of the symbols

1: substrate

2: partition wall

3: layer comprising a color-converting luminescent material

4: low refractive index layer

5: inorganic protective layer I

6: inorganic protective layer II

7: color filter

8: inorganic protective layer III

9: inorganic protective layer IV

10: shading partition wall

X: thickness of the partition wall

L: width of the partition wall

a: plan view of the processing substrate with pattern of the present invention

b: top view of transparent electrode after formation

c: top view of transparent insulating film after formation

d: top view after metal wiring is formed

11: glass substrate

12: white shading cured film

13: transparent electrode

14: transparent insulating film

15: and a metal wiring.

Claims

1. A negative photosensitive coloring composition comprising (A) a white pigment, (B) a silicone resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent,

the (B) silicone resin contains at least:

a repeating unit represented by the following general formula (1) and/or a repeating unit represented by the following general formula (2), and

a repeating unit represented by the following general formula (3),

the siloxane resin (B) contains 40 to 80 mol% of a total of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2),

in the general formulae (1) to (3), R¹An alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 10 carbon atoms, wherein all or a part of the hydrogen atoms are substituted with fluorine atoms; r²Represents a single bond, -O-, -CH₂-CO-, -CO-or-O-CO-; r³A 1-valent organic group having 1 to 20 carbon atoms; r⁴The organic groups may be the same or different and each represents a 1-valent organic group having 1 to 20 carbon atoms.

2. The negative photosensitive coloring composition according to claim 1, wherein the (D) photopolymerizable compound comprises a compound having an ethylenically unsaturated double bond and a fluorine atom.

3. The negative photosensitive coloring composition according to claim 1 or 2, wherein the refractive index of the silicone resin (B) at a wavelength of 587.5nm is 1.35 to 1.55.

4. The negative photosensitive coloring composition according to any one of claims 1 to 3, wherein the refractive index of the (A) white pigment at a wavelength of 587.5nm is 2.00 to 2.70.

5. The negative-type photosensitive coloring composition according to any one of claims 1 to 4, wherein the difference in refractive index between the (A) white pigment and the (B) silicone resin at a wavelength of 587.5nm is 1.16 to 1.26.

6. The negative-type photosensitive coloring composition according to any one of claims 1 to 5, wherein the (A) white pigment contains particles having a median particle diameter of 100 to 500nm of a compound selected from the group consisting of titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and a composite compound thereof.

7. The negative-type photosensitive coloring composition according to any one of claims 1 to 6, wherein the content of the (B) silicone resin in the solid content is 10 to 60% by weight, and the content of the (A) white pigment in the solid content is 20 to 60% by weight.

8. The negative photosensitive coloring composition according to any one of claims 1 to 7, which is used for forming a partition wall having a reflectance of 60 to 90% per 10 μm thickness at a wavelength of 550 nm.

9. A cured film of the negative photosensitive coloring composition according to any one of claims 1 to 7.

10. The method for producing a cured film according to claim 9, comprising the steps of:

(I) a step of coating the negative photosensitive coloring composition according to any one of claims 1 to 8 on a substrate to form a coating film;

(II) exposing and developing the coating film; and

(III) heating the developed coating film.

11. A patterned processing substrate having the cured film according to claim 9 patterned thereon.

12. A substrate with a partition wall, comprising a patterned partition wall comprising the cured film according to claim 9 on a substrate, wherein the partition wall has a reflectance of 60 to 90% per 10 μm of a thickness at a wavelength of 550 nm.

13. The partition-provided substrate according to claim 12, wherein the partition-patterned has a surface contact angle of 10 ° to 70 ° with respect to propylene glycol monomethyl ether acetate.

14. The substrate with partition walls according to claim 12 or 13, further comprising patterned light-shielding partition walls having an optical density of 0.1 to 4.0 per 1.0 μm thickness between the substrate and the patterned partition walls.

15. The substrate with partition walls according to any one of claims 12 to 14, which has a layer containing a color-converting luminescent material between adjacent partition walls.

16. The partition-wall-provided substrate according to claim 15, wherein the color-converting light-emitting material contains an inorganic phosphor and/or an organic phosphor.

17. The partition-wall-provided substrate according to claim 16, wherein the color-converting luminescent material contains a phosphor that emits red or green fluorescence when excited by blue excitation light.

18. The substrate with a barrier according to claim 16 or 17, wherein the color-converting luminescent material comprises quantum dots.

19. The substrate with a barrier according to claim 16 or 17, wherein the color-converting luminescent material comprises a methylene pyrrole derivative.

20. The substrate with a partition according to any one of claims 15 to 19, further comprising a low refractive index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550nm on the layer containing the color-converting luminescent material.

21. The substrate with partition walls according to claim 20, further comprising an inorganic protective layer I having a thickness of 50 to 1,000nm on the low refractive index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm.

22. The substrate with partition walls according to claim 20 or 21, further comprising an inorganic protective layer II having a thickness of 50 to 1,000nm under the low refractive index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm.

23. The substrate with a partition according to any one of claims 15 to 22, further comprising a color filter having a thickness of 1 to 5 μm between the substrate and the layer containing a color-converting luminescent material.

24. The partition-wall-provided substrate according to claim 23, further comprising an inorganic protective layer III having a thickness of 50 to 1,000nm between the color filter and the layer containing a color-converting luminescent material.

25. The substrate with a partition wall according to any one of claims 12 to 24, further comprising an inorganic protective layer IV having a thickness of 50 to 1,000nm on the substrate.

26. The substrate with partition walls according to any one of claims 20 to 25, wherein the inorganic protective layer I, the inorganic protective layer II, the inorganic protective layer III and the inorganic protective layer IV contain 1 or more selected from silicon nitride and silicon oxide.

27. A display device comprising the substrate with a partition wall according to any one of claims 12 to 26, and a light source selected from the group consisting of a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.

28. A touch panel having the patterned processing substrate of claim 11, a transparent electrode, a metal wiring, and a transparent film.