WO2019176785A1 - Negative photosensitive coloring composition, cured film, and touch panel using same - Google Patents

Abstract

Provided is a negative photosensitive coloring composition comprising: (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, wherein the (B) siloxane resin comprises, at least, a repeating unit expressed by general formula (1) and/or a repeating unit expressed by general formula (2), and a repeating unit expressed by general formula (3), and the sum of the repeating unit expressed by general formula (1) and the repeating unit expressed by general formula (2) is 40-80 mol% with respect to all the repeating units in the (B) siloxane resin. In general formulae (1)-(3), R1 represents an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group having 1-10 carbon atoms in which hydrogen is partially or entirely substituted with fluorine; R2 represents a single bond, -O-, -CH2-CO, -CO- or –O-CO-; R3 represents a monovalent organic group having 1-20 carbon atoms; and the R4s may be same or different, each representing a monovalent organic group having 1-20 carbon atoms. By using this negative photosensitive coloring composition, a cured film can be formed which exhibits high resolution and has high reflectivity and high heat-resistance even when the film is thick.

Description

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

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

In recent years, mobile devices using a projected capacitive touch panel such as smartphones and tablet PCs are rapidly spreading. In general, the projected capacitive touch panel has an ITO (Indium Tin Oxide) film pattern in the screen area, and further has a metal wiring portion such as molybdenum around the periphery thereof. From the viewpoint of design, in order to conceal such a metal wiring part, a black or white light-shielding pattern is often provided inside the cover glass of the projected capacitive touch panel. With the diversification of touch panel-equipped terminals, higher-definition light-shielding patterns are required, and as a method for forming such light-shielding patterns, lithography capable of processing with higher resolution is possible instead of the conventional printing method. The law is becoming mainstream (see, for example, Patent Document 1). In addition, with regard to the white light-shielding pattern, since the light-shielding property of the white pigment is generally low, thick film processing is required.

The touch panel system is 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 the liquid crystal panel, and an in-cell type in which a touch panel layer is formed inside the liquid crystal panel. Cell type and OGS (One Glass Solution) type that directly forms the touch panel layer on the cover glass. In recent years, OGS type touch panels have been actively developed because they can be made thinner and lighter than conventional ones.

Since the OGS type touch panel manufacturing method requires high-temperature processing such as ITO film formation, a light-shielding pattern material is required to have a high heat resistance with few cracks and color change in the high-temperature processing. ing. Accordingly, a negative photosensitive coloring composition (for example, see Patent Document 2) containing a white pigment, a polysiloxane having a specific structure, a polyfunctional acrylic monomer, a photo radical polymerization initiator, and an organic solvent, a white pigment, A negative photosensitive white composition for touch panel (for example, see Patent Document 3) containing an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator has been proposed.

In addition, a photosensitive white composition containing a white pigment can easily form a high-definition and highly reflective partition wall pattern on a substrate by a lithography method. Therefore, as a technique for improving the light extraction efficiency of a light emitter, a display device Application to brightness enhancement technology is under consideration.

JP 2012-242928 A International Publication No. 2014/126013 International Publication No. 2015/12228

However, since the composition described in Patent Document 2 has a high refractive index of polysiloxane and a small difference in refractive index from the white pigment, reflection at the interface between the polysiloxane and the white pigment is insufficient. The reflectance of the light shielding pattern was insufficient. On the other hand, although the reflectance of the white light-shielding pattern is improved by the composition described in Patent Document 3, further improvement has been demanded. Moreover, when the film thickness is large, cracks are likely to occur due to high-temperature treatment, and there is a problem that heat resistance is insufficient.

Therefore, 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 if it is a thick film. .

In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies by paying attention to the structure of a siloxane resin in a negative photosensitive coloring composition containing a white pigment. As a result, it has been found that the above problem can be solved by including a siloxane resin in which a structural unit derived from an alkoxysilane compound containing fluorine and a structural unit derived from a bifunctional alkoxysilane compound are contained. That is, the present invention has the following configuration.

A negative photosensitive coloring composition containing (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, ) The siloxane resin includes 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). Negative photosensitive material containing a 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) in all the repeating units of the (B) siloxane resin. Coloring composition.

In the general formulas (1) to (3), R ¹ represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms in which all or part of hydrogen is substituted with fluorine. R ² represents a single bond, —O—, —CH ₂ —CO—, —CO— or —O—CO—. R ³ represents a monovalent organic group having 1 to 20 carbon atoms. R ⁴ may be the same or different and represents a monovalent organic group having 1 to 20 carbon atoms.

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

It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a patterned partition. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has the layer containing the patterned partition and the color conversion light emitting material. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a low-refractive-index layer. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a low-refractive-index layer and the inorganic protective layer I. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a low-refractive-index layer and the inorganic protective layer II. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a color filter. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a color filter and the inorganic protective layer III. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has the inorganic protective layer IV. It is sectional drawing which shows the one aspect | mode of the board | substrate with a partition of this invention which has a light-shielding partition. It is the schematic which shows an example of the cross section of the touchscreen of this invention. It is the schematic which shows an example of the manufacturing method of the touchscreen of this invention.

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

(A) White pigment (A) By containing a white pigment, the reflectance of the cured film obtained can be improved.

(A) The white pigment includes, for example, a compound selected from titanium dioxide, zirconium oxide, zinc oxide, barium sulfate and a composite compound thereof. Two or more of these may be contained. Among these, titanium dioxide is preferable because of its high reflectance and easy industrial use.

The crystal structure of titanium dioxide is classified into anatase type, rutile type and brookite type. Among these, rutile type titanium oxide is preferable because of its low photocatalytic activity.

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

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

(A) Titanium dioxide pigments preferably used as white pigments include, for example, R960; manufactured by DuPont (rutile type, SiO ₂ / Al ₂ O ₃ treatment, median diameter 210 nm), CR-97; Ishihara Sangyo Co., Ltd. ) (Rutile type, Al ₂ O ₃ / ZrO ₂ treatment, median diameter 250 nm), JR-301; manufactured by Teika Co., Ltd. (rutile type, Al ₂ O ₃ treatment, median diameter 300 nm), JR-405; Co., Ltd. (rutile type, Al ₂ O ₃ treatment, median diameter 210 nm), JR-600A; Teika Corporation (rutile type, Al ₂ O ₃ treatment, median diameter 250 nm), JR-603; Teika Corporation ( Rutile type, Al ₂ O ₃ / ZrO ₂ treatment, median diameter 280 nm) and the like. Two or more of these may be contained.

(A) The refractive index of the white pigment at a wavelength of 587.5 nm is preferably 2.00 to 2.70. (A) By making the refractive index of a white pigment more than 2.00, the interface reflection of (A) white pigment and (B) siloxane resin can be increased, and a reflectance can be improved more. (A) The refractive index of the white pigment is more preferably 2.40 or more. On the other hand, by setting the refractive index of the (A) white pigment to 2.70 or less, excessive interface reflection between the (A) white pigment and (B) the siloxane resin can be suppressed, and the resolution can be further improved. Here, the refractive index of the (A) white pigment can be measured using the Becke method defined in JIS K7142-2014 (established date: 2014/04/20). The measurement wavelength is a standard 587.5 nm. (A) When containing 2 or more types of white pigments, it is preferable that at least 1 type of refractive index exists in the said range.

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 in the solid content, from the viewpoint of further improving the reflectance. More preferably by weight. On the other hand, the content of the (A) white pigment is preferably 65% by weight or less, and more preferably 60% by weight or less in the solid content from the viewpoint of suppressing development residue and forming a higher resolution pattern. Solid content here means all the components except volatile components, such as a solvent, among the components contained in a negative photosensitive coloring composition. The amount of solid content can be determined by heating the negative photosensitive coloring composition at 170 ° C. for 30 minutes and measuring the residue obtained by evaporating volatile components.

The negative photosensitive coloring composition of the present invention may contain a pigment dispersant together with (A) the white pigment, and can improve the dispersibility of the (A) white pigment in the negative photosensitive coloring composition. . The pigment dispersant can be appropriately selected depending on the type of white pigment used and the surface state. 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, 1155, 140, and 145 (above, trade names, manufactured by BYK Chemie Co., Ltd.). . Two or more of these may be contained.

(B) Siloxane resin By containing the (B) siloxane resin having the specific structure described above, the refractive index difference between the (A) white pigment and the (B) siloxane resin is expanded, and the resulting cured film has a reflectivity. Can be further improved. Moreover, the (B) siloxane resin having the specific structure described above is excellent in heat resistance and can suppress color change and cracks in the cured film. Furthermore, a high resolution pattern can be formed.

(B) Siloxane resin is a hydrolyzed / dehydrated condensate of organosilane. In the negative photosensitive coloring composition of the present invention, at least the repeating unit represented by the following general formula (1) and / or the repeating unit represented by the following general formula (2) and the following general formula (3): And the represented repeating unit. Furthermore, other repeating units may be 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, since the refractive index of (B) siloxane resin is reduced, the difference in refractive index from (A) white pigment is increased, and (A) between the white pigment and (B) siloxane resin. The reflectance of the cured film can be improved by light reflection at the interface.

Furthermore, by including the repeating unit derived from the bifunctional alkoxysilane compound represented by the general formula (3), the excessive thermal polymerization (condensation) of the (B) siloxane resin in the heat treatment is suppressed, and the heat resistance is improved. Can do. Thereby, the crack and color change of the cured film in heat processing can be suppressed.

In the present invention, the (B) siloxane resin contains a total of 40 to 80 mol% of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). When 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 (A) white pigment and the (B) siloxane resin becomes insufficient, Reflectivity 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, when the total content of the repeating unit represented by the general formula (1) and the general formula (2) exceeds 80 mol%, (B) the phase with other components in the composition due to the hydrophobization of the siloxane resin. Since the solubility decreases, 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. Further, 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, the cured film is not sufficiently crosslinked and the film characteristics are deteriorated. On the other hand, the content of the repeating unit represented by the general formula (3) is preferably 10 mol% or more. Since content of the repeating unit represented by General formula (3) is less than 10 mol%, since bridge | crosslinking of a cured film is formed excessively, crack tolerance falls. In addition, when a repeating unit other than the repeating units represented by the general formulas (1) to (3) is included, the content is preferably 10 to 50 mol%.

In the general formulas (1) to (3), R ¹ represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms in which all or part of hydrogen is substituted with fluorine. R ² represents a single bond, —O—, —CH ₂ —CO—, —CO— or —O—CO—. R ³ represents a monovalent organic group having 1 to 20 carbon atoms. R ⁴ may be the same or different and represents a monovalent organic group having 1 to 20 carbon atoms. R ¹ is preferably an alkyl group in which all or part of hydrogen is substituted with fluorine from the viewpoint of further reducing the refractive index of the siloxane resin. In this case, the alkyl group preferably has 1 to 6 carbon atoms. R ³ and R ⁴ are preferably groups selected from an alkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 10 carbon atoms from the viewpoint of further reducing the refractive index of the siloxane resin.

The repeating units represented by the general formulas (1) to (3) are derived from alkoxysilane compounds represented by the following general formulas (4) to (6), respectively. That is, the siloxane resin containing the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) A plurality of alkoxysilane compounds including an alkoxysilane compound represented by the formula (4) and / or an alkoxysilane compound represented by the following general formula (5) and an alkoxysilane compound represented by the following general formula (6) Can be obtained by hydrolysis and polycondensation. Further, other alkoxysilane compounds may be used.

In the general formulas (4) to (6), R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same groups as R ¹ , R ² , R ³ and R ^{4 in the} general formulas (1) to (3), respectively. Represents. R ⁷ may be the same or different and represents a monovalent 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, and tridecafluorooctyltri Examples include methoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and the like. Two or more of these may be used.

Examples of the alkoxysilane compound represented by the general formula (5) include bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, Examples include trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and the like. Two or more of these may be used.

Examples of the alkoxysilane compound represented by the general formula (6) include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldimethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, and diphenyldimethoxysilane. , Diphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acrylo Rupropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethylethyldimethoxysilane and the like. Two or more of these may be used.

Examples of other alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, Trifunctional alkoxysilane compounds such as 3-ureidopropyltriethoxysilane; tetramethoxysilane, tetraethoxysilane, Tetrafunctional alkoxysilane compounds such as Kate 51 (tetraethoxysilane oligomer); monofunctional alkoxysilane compounds such as trimethylmethoxysilane and triphenylmethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4 Epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylethyldimethoxysilane, 3-ethyl-3-{[3- (trimethoxysilyl) propoxy] methyl} oxetane, 3-ethyl-3- { Epoxy and / or oxetane group-containing alkoxysilane compounds such as 3- (triethoxysilyl) propoxy] methyl} oxetane: phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1-naphthyltrimethoxy Silane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2 -Phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3- Aromatic ring-containing alkoxysilane compounds such as dimethylmethoxysilylpropylphthalic anhydride and 3-dimethylethoxysilylpropylphthalic anhydride; styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltri Radical-polymerizable group-containing alkoxysilane compounds such as methoxysilane, allyltriethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane; 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropio Acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 5-dimethylmethoxy Silylvaleric acid, 5-dimethylethoxysilylvaleric acid, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, 3-dimethylethoxy Silylpropyl succinic anhydride, 3-trimethoxysilylpropylcyclohexyl dicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyl dicarboxylic anhydride, 3-dimethylmethoxysilylpropylcyclohexyl dicarboxylic anhydride, 3-dimethylethoxysilyl Rupropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethylethoxysilylpropylphthalic anhydride Examples thereof include carboxyl group-containing alkoxysilane compounds.

(B) 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 the alkoxysilane compounds as raw materials for the siloxane resin is (B ) 40 mol% or more is preferable 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 siloxane resin within the above range. 50 mol% or more is more preferable. 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 70 mol% or less. More preferred. When only one of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) is included, the alkoxysilane compound may be included in the above range. When both the alkoxysilane compound represented by 4) and the alkoxysilane compound represented by the general formula (5) are included, the total of these may be included in the above range.

(B) The weight average molecular weight (Mw) of the siloxane resin is preferably 1,000 or more, and more preferably 2,000 or more, from the viewpoint of coating properties. On the other hand, from the viewpoint of developability, the Mw of the (B) siloxane resin is preferably 50,000 or less, and more preferably 20,000 or less. Here, Mw of the (B) siloxane resin in the present invention refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).

(B) The refractive index of the siloxane resin at a wavelength of 587.5 nm is preferably 1.35 to 1.55. By setting the refractive index of the (B) siloxane resin to 1.35 or more, excessive interface reflection between the (A) white pigment and the (B) siloxane resin can be suppressed, and the resolution can be further improved. (B) The refractive index of the siloxane resin is more preferably 1.40 or more. On the other hand, by setting the refractive index of the (B) siloxane resin to 1.55 or less, the interface reflection between the (A) white pigment and the (B) siloxane resin can be increased, and the reflectance can be further improved. (B) The refractive index of the siloxane resin is more preferably 1.50 or less. Here, the refractive index of (B) siloxane resin is 20 ° C. under atmospheric pressure using a prism coupler (PC-2000 (manufactured by Metricon)) for a cured film of siloxane resin formed on a silicon wafer. Under the conditions, the measurement is performed by irradiating light having a wavelength of 587.5 nm from the direction perpendicular to the cured film surface. However, the third decimal place will be rounded off. The cured film of siloxane resin is spin-coated on a silicon wafer with a siloxane resin solution prepared by dissolving the siloxane resin in an organic solvent so that the solid content concentration is 40% by weight, and dried on a hot plate at 90 ° C. for 2 minutes. Then, it is prepared by curing in an air at 230 ° C. for 30 minutes using an oven. When a negative photosensitive coloring composition contains 2 or more types of (B) siloxane resin, it is preferable that at least 1 type of refractive index exists in the said range.

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

In the negative photosensitive coloring composition of the present invention, the content of the (B) siloxane resin can be arbitrarily set depending on the desired film thickness and application, but in the negative photosensitive coloring composition, it is 10 to 60. % By weight is preferred. Further, the content of the (B) siloxane resin 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) siloxane 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 siloxane resin can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or without a solvent.

Various conditions in the hydrolysis can be set according to the physical properties suitable for the intended application in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. Examples of 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, polyvalent carboxylic acid or its anhydride, or an ion exchange resin can be used. Among these, an acidic aqueous solution containing formic acid, acetic acid and / or phosphoric acid is preferable.

When an acid catalyst is used for the hydrolysis reaction, the amount of the acid catalyst added is 0.05 wt. With respect to 100 parts by weight of the total alkoxysilane compound used for the hydrolysis reaction, from the viewpoint of allowing the hydrolysis to proceed more rapidly. Part or more is preferable, and 0.1 part by weight or more is more preferable. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the addition amount of the acid catalyst is preferably 20 parts by weight or less and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound. Here, the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate.

The hydrolysis reaction can be performed in an organic solvent. The organic solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the negative photosensitive coloring composition. Examples of the organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3- Alcohols such as methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; 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 Ethers such as glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; dimethylformamide, Amides such as dimethylacetamide; 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 , Acetates such as ethyl lactate and butyl lactate; toluene, xylene, hexane, Aromatic or aliphatic hydrocarbons such as hexane; .gamma.-butyrolactone, N- methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.

Among these, from the viewpoint of crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, 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.

When an organic solvent is generated by a hydrolysis reaction, the hydrolysis can be performed without a solvent. After completion of the hydrolysis reaction, it is also preferable to adjust the concentration to an appropriate concentration for use as a negative photosensitive coloring composition by further adding an organic solvent to the obtained composition. It is also possible to distill and remove all or part of the produced alcohol and the like after heating and / or under reduced pressure, and then add a suitable organic solvent.

In the case of using an organic solvent for the hydrolysis reaction, the amount of the organic solvent added is preferably 50 parts by weight or more, and 80 parts by weight or more with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of suppressing gel formation. More preferred. On the other hand, the addition amount of the organic solvent is preferably 500 parts by weight or less and more preferably 200 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of allowing hydrolysis to proceed more rapidly.

Moreover, as the water used for the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be arbitrarily set, but is preferably 1.0 to 4.0 mol with respect to 1 mol of all alkoxysilane compounds.

Examples of the dehydration condensation method include a method of heating a silanol compound solution obtained by hydrolysis reaction of an organosilane compound as it is. The heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. In order to increase the degree of polymerization of the siloxane resin, reheating or addition of a base catalyst may be performed. Further, depending on the purpose, after hydrolysis, an appropriate amount such as the generated alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

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

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

(C) Any photopolymerization initiator may be used as long as it can be decomposed and / or reacted with light (including ultraviolet rays and electron beams) to generate radicals. For example, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl Α-aminoalkylphenone compounds such as -phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2,4,6-trimethylbenzoylphenyl Acylphosphine oxide compounds such as phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide; 1 -Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 1-phenyl-1,2-butadion-2- (O-methoxycarbonyl) oxime, 1,3-diphenylpropane Such as trione-2- (O-ethoxycarbonyl) oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) Oxime ester compounds; benzyl ketal compounds such as benzyldimethyl ketal; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydro Α-hydroxyketone compounds such as cyclohexyl-phenylketone; benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4, Benzophenone compounds such as 4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; 2 Acetophenone compounds such as 1,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, 4-azidobenzalacetophenone; Aromatic ketoester compounds such as methyl phenyl-2-oxyacetate; ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethyl) hexyl, ethyl 4-diethylaminobenzoate, methyl 2-benzoylbenzoate, etc. A benzoic acid ester compound etc. are mentioned. Two or more of these may be contained.

When the negative photosensitive coloring composition of the present invention does not contain (A) a colorant other than the white pigment, (C) 2,4,6-trimethylbenzoylphenyl is used to suppress coloring by the photopolymerization initiator. Acylphosphine oxide photopolymerization such as phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide Initiators are preferred.

The content of the (C) photopolymerization initiator in the negative photosensitive coloring composition of the present invention is preferably 0.01% by weight or more, preferably 1% by weight in the solid content from the viewpoint of effectively promoting radical curing. The above is more preferable. On the other hand, from the viewpoint of suppressing the elution of the remaining (C) photopolymerization initiator and improving yellowing, the content of (C) the photopolymerization initiator is preferably 20% by weight or less in the solid content, 10% by weight or less is more preferable.

(D) Photopolymerizable compound The photopolymerizable compound in the present invention refers to a compound having an ethylenically unsaturated double bond in the molecule. The photopolymerizable compound preferably has two or more ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, the (D) photopolymerizable compound preferably has a (meth) acrylic group. In addition, the double bond equivalent of the (D) photopolymerizable compound is preferably 400 g / mol or less from the viewpoint of further improving the sensitivity in pattern processing. On the other hand, the double bond equivalent of the (D) photopolymerizable compound is preferably 80 g / mol or more from the viewpoint of further improving the resolution in pattern processing.

(D) As a photopolymerizable compound, for example, 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 diacrylate 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta Acrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol Heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, “Megafuck” (registered trademark) RS-76-E, RS-56, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-76, RS-90 (above, trade name, manufactured by DIC Corporation) ) And the like. Two or more of these may be contained.

Among these, a compound having a fluorine atom is preferable from the viewpoint of further improving the reflectance. You may contain the photopolymerizable compound which has a fluorine atom, and another photopolymerizable compound.

The content of the (D) photopolymerizable compound in the negative photosensitive coloring composition of the present invention is preferably 1% by weight or more in the solid content from the viewpoint of effectively promoting radical curing. On the other hand, the content of the photopolymerizable compound (D) is preferably 40% by weight or less in the solid content from the viewpoint of suppressing radical excess reaction and further improving the resolution.

(E) Organic solvent By containing the (E) organic solvent, 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.

As the organic solvent, it is preferable to combine an organic solvent having a boiling point under atmospheric pressure of more than 150 ° C. and not more than 250 ° C. with an organic solvent having a boiling point of not more than 150 ° C. Since the negative photosensitive coloring composition contains an organic solvent having a boiling point of more than 150 ° C. and not more than 250 ° C., the organic solvent volatilizes appropriately at the time of coating, and the coating film is dried. The film thickness uniformity can be improved. Furthermore, by containing an organic solvent having a boiling point of 150 ° C. or lower under atmospheric pressure, it is possible to suppress the remaining of the organic solvent in the cured film of the present invention described later. From the viewpoint of suppressing the remaining of the organic solvent in the cured film and improving the chemical resistance and adhesion over a long period of time, an organic solvent having a boiling point of 150 ° C. or lower under atmospheric pressure is 50% by weight or more of the total organic solvent It is preferable to contain.

Examples of organic solvents having a boiling point of 150 ° C. or less under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl 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, lactic acid , Toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy-3-methyl-2-butanone, 4- Examples include hydroxy-3-methyl-2-butanone and 5-hydroxy-2-pentanone. Two or more of these may be used.

Examples of the organic solvent having a boiling point under atmospheric pressure of more than 150 ° C. and not more than 250 ° C. 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-t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 3-ethoxypropion Ethyl acetate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, Methylacetamide, .gamma.-butyrolactone, .gamma.-valerolactone, .delta.-valerolactone, propylene carbonate, N- methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether. Two or more of these may be used.

The content of the organic solvent can be arbitrarily set according to the application 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, if necessary.

By including an adhesion improver in the negative photosensitive coloring composition, the adhesion to the substrate is improved, and a highly reliable cured film can be obtained. Examples of the adhesion improver include alicyclic epoxy compounds and silane coupling agents. Among these, since an alicyclic epoxy compound has high heat resistance, it can suppress the color change of the cured film after a heating more.

Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-2,2-bis (hydroxymethyl) -1-butanol. 4- (2-oxiranyl) cyclohexane adduct, ε-caprolactone modified 3 ′, 4′-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid Tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether And hydrogenated bisphenol A bis (propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis (ethylene glycol glycidyl ether) ether, 1,4-cyclohexanedicarboxylate diglycidyl, 1,4-cyclohexanedimethanol diglycidyl ether, etc. It is done. Two or more of these may be contained.

As the silane coupling agent, a compound represented by the following general formula (7) is preferable.

In the general formula (7), each R ¹⁰ independently represents an alkyl group having 1 to 6 carbon atoms. From the viewpoint of reducing the refractive index, R ¹⁰ is preferably an alkyl group having 1 to 3 carbon atoms. p represents 0 or 1. From the viewpoint of further improving the adhesion with the substrate, p is preferably 0. R ¹¹ represents a trivalent organic group having 3 to 30 carbon atoms, preferably a trivalent hydrocarbon group having 3 to 10 carbon atoms. R ¹² each 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 reducing the refractive index, R ¹² is preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.

Examples of the silane coupling agent represented by the 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- (tri Methoxysilyl) pentanoic acid, 3- (isobutylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 3- (tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert- Pentylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 6- (dimethoxymethyl) Rusilyl) -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. Also good.

The content of the adhesion improving agent in the negative photosensitive coloring composition is preferably 0.1% by weight or more, more preferably 1% by weight or more in the solid content from the viewpoint of further improving the adhesion to the substrate. On the other hand, the content of the adhesion improver is preferably 20% by weight or less, and more preferably 10% by weight or less in the solid content from the viewpoint of further suppressing 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. UV absorbers include 2- (2H-benzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6-tert-pentyl from the viewpoint of further suppressing color change due to heating. Phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl Benzotriazole compounds such as phenol, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; 2- (4,6 -Diphenyl-1,3,5triazin-2-yl) -5-[(hexyl) oxy] -phenol Triazine compounds are preferably used. Two or more of these may be contained.

By containing a polymerization inhibitor in the negative photosensitive coloring composition, the resolution of the cured film obtained can be improved. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Commercially available polymerization inhibitors include “IRGANOX” (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (above, trade names, BASF Japan Ltd.). Two or more of these may be contained.

By containing a surfactant in the negative photosensitive coloring composition, the flowability at the time of application can be improved. Surfactants include, for example, fluorine-based surfactants such as “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (above, trade name, manufactured by DIC Corporation). Silicone surfactants such as “BYK” (registered trademark) -333, 301, 331, 345, 307 (above, trade name, manufactured by Big Chemie Japan Co., Ltd.); polyalkylene oxide surfactants; And a (meth) acrylate surfactant. Two or more of these may be contained.

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 film formation is performed 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 aforementioned components (A) to (E) and other components as necessary. More specifically, for example, first, a mixed liquid of (A) a white pigment, (B) a siloxane resin, and (E) an organic solvent is dispersed using a mill-type disperser filled with zirconia beads, thereby dispersing the pigment. It is preferable to obtain a liquid. On the other hand, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, (E) an organic solvent and, if necessary, other components are stirred and dissolved to obtain a diluted solution. Is preferred. And it is preferable to filter, after mixing and stirring a pigment dispersion and a diluent.

Next, the cured film of the present invention will be described. The cured film of the present invention is a cured product of the aforementioned 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 a cured film of the present invention will be described with examples. The method for producing a cured film of the present invention comprises (I) a step of applying a negative photosensitive coloring composition of the present invention on a substrate to form a coating film, (II) a step of exposing and developing the coating film, And (III) It is preferable to have a step of heating the coated film after the development. Below, each process is demonstrated.

(I) The process of apply | coating the negative photosensitive coloring composition of this invention on a board | substrate, and forming a coating film As a board | substrate, glass substrates, such as soda-lime glass and an alkali free glass, are mentioned, for example.

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

After forming the coating film, it is preferable to dry (pre-bake) the substrate coated with the negative photosensitive coloring composition. Examples of the drying method include reduced pressure drying and heat drying. Examples of the heating device include a hot plate and an oven. The heating temperature is preferably 60 to 150 ° C., and the heating time is preferably 30 seconds to 3 minutes. The film thickness of the coating film after pre-baking is preferably 5 to 20 μm.

(II) Step of exposing and developing the coating film By exposing and developing the coating film thus obtained, a substrate having a patterned coating film is obtained.

The exposure may be performed through a desired mask or may be performed without using a mask. Examples of the exposure machine include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (hereinafter referred to as “PLA”), and the like. The exposure intensity is preferably about 10 to 4000 J / m ² (wavelength 365 nm exposure amount conversion). Examples of the exposure light source include ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like.

Examples of the developing method include methods such as showering, dipping, and paddle. The immersion time in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates; amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; tetramethyl Examples thereof include aqueous solutions of quaternary ammonium salts such as ammonium hydroxide and choline. It is preferable to rinse with water after development. Subsequently, dry baking may be performed at 50 to 140 ° C.

(III) Step of heating the coated film after development By heating the substrate having the patterned coating film thus obtained, the coated film is cured to obtain a patterned processed substrate. Here, the patterned processed substrate refers to a substrate having a patterned cured film.

Examples of the heating device include a hot plate and an oven. The heating temperature is preferably 120 to 250 ° C., and the heating time is preferably 15 minutes to 2 hours.

Next, the patterned processed substrate of the present invention will be described. The patterned processed substrate of the present invention has a pattern made of the above-described cured film of the present invention on the substrate. Since such a pattern has high resolution and high reflectance, it can be suitably used as a white shading pattern for a touch panel.

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

For example, when the cured film pattern is used as a light shielding pattern for a touch panel, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) of the light shielding pattern is CIE 1976 (L *, a *, b *). In the color space, it is preferable that 82 ≦ L * ≦ 99, −5 ≦ b * ≦ 5, −5 ≦ a * ≦ 5, 82.5 ≦ L * ≦ 97, −2 ≦ b * ≦ 2, More preferably, −2 ≦ a * ≦ 2. The cured film pattern having the color characteristics can be obtained, for example, by pattern processing using the above-described preferable production method using the above-described negative photosensitive coloring composition of the present invention.

Next, the board | substrate with a partition of this invention is demonstrated. The substrate with a partition wall of the present invention has a patterned partition wall (hereinafter sometimes referred to as “partition wall (F-1)”) made of the above-described cured film on the substrate.

In the present invention, the partition wall refers to one having a repetitive pattern corresponding to the number of pixels of the image display device. Examples of the number of pixels of the image display device include 4000 vertically and 2000 horizontally. The number of pixels affects the resolution (fineness) of the displayed image. For this reason, it is necessary to form a number of pixels according to the required image resolution and the screen size of the image display device, and it is preferable to determine the pattern formation dimensions of the partition wall accordingly.

The substrate has a function as a support in the substrate with a partition wall. The partition has a function of preventing light color mixing between adjacent pixels when a layer containing a color conversion luminescent material, which will be described later, is formed between adjacent partitions and a pixel containing the color conversion luminescent material is configured. Have. In the present invention, the partition wall (F-1) preferably has a reflectance of 60% to 90% per 10 μm 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 utilizing the reflection on the side wall of (F-1) partition wall. On the other hand, from the viewpoint of improving pattern formation accuracy, the reflectance is preferably 90% or less.

FIG. 1 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a patterned partition wall. A patterned partition wall 2 is provided on a substrate 1.

<Board>
Examples of the substrate include a glass plate, a resin plate, a resin film, and the like. As the material of the glass plate, alkali-free glass is preferable. As the material for 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 1 mm or less, and preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less.

<Partition wall (F-1)>
The partition wall (F-1) preferably has a reflectance of 60 to 90% per 10 μm thickness at a wavelength of 550 nm. Here, the thickness of the partition wall (F-1) refers to the length of the partition wall (F-1) perpendicular to the substrate (in the 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 the symbol X. Note that the length of the partition wall (F-1) in the horizontal direction 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 represented by the symbol L. In the present invention, it is considered that the reflection on the side wall of the partition contributes to 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, the present invention focuses on the reflectance per partition wall thickness. As will be described later, the thickness of the partition wall (F-1) is preferably 0.5 to 50 μm, and the width is preferably 5 to 40 μm. Therefore, in the present invention, 10 μm is selected as the representative value of the thickness of the partition wall (F-1), and attention is paid to the reflectance per 10 μm thickness. When the reflectance per 10 μm thickness is less than 60%, the reflection on the side wall of the partition wall becomes small, and the luminance of the display device becomes insufficient. The higher the reflectance, the greater the reflection on the side wall of the partition wall, so that the luminance of the display device can be improved. Therefore, the reflectance is preferably 70% or more. On the other hand, from the viewpoint of improving pattern formation accuracy, the reflectance is preferably 90% or less. The reflectance per 10 μm thickness of the partition wall (F-1) at a wavelength of 550 nm is measured from the top surface of the partition wall (F-1) having a thickness of 10 μm in the height direction (for example, CM-2600d manufactured by Konica Minolta Co., Ltd.). ) To measure in the 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 and the composition of the partition wall (F-1) is known, the same composition as the partition wall (F-1) is obtained. A solid film having a thickness of 10 μm may be prepared, and the reflectance of the solid film may be measured instead of the partition wall (F-1). For example, using the material for forming the partition wall (F-1), forming a solid film under the same processing conditions as the formation of the partition wall (F-1) except that the thickness is 10 μm and no pattern is formed. The reflectance of the film may be similarly measured from the upper surface. In addition, as a means for making a reflectance into the said range, it can obtain by patterning a partition with the above-mentioned preferable manufacturing method, for example using the above-mentioned negative photosensitive coloring composition of this invention. .

The thickness of the partition wall (F-1) is such that the substrate with the partition wall contains a (G) color conversion luminescent material described later (hereinafter referred to as “layer containing a color conversion luminescent material (G)”). When it has, it is preferable that it is larger than the thickness of the layer (G) containing a color conversion luminescent material. Specifically, the thickness of the partition wall (F-1) is preferably 0.5 μm or more, and more preferably 10 μm or more. On the other hand, the thickness of the partition wall (F-1) is preferably 50 μm or less and more preferably 20 μm or less from the viewpoint of more efficiently extracting light emitted from the bottom of the layer (G) containing the color conversion light-emitting material. Further, the width of the partition wall (F-1) is sufficient to improve the luminance by utilizing light reflection on the side wall of the partition wall and to suppress the color mixture of the layer (G) containing the adjacent color conversion luminescent material due to light leakage. Anything is acceptable. 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, and more preferably 40 μm or less, from the viewpoint of securing a large light emitting region of the layer (G) containing the color conversion light emitting material and further improving the luminance.

The surface contact angle of the partition wall (F-1) with respect to propylene glycol monomethyl ether acetate is preferably 10 ° or more, and preferably 20 ° or more from the viewpoint of improving the ink-jet coating property and facilitating the color conversion light-emitting material. More preferably, it is 40 ° or more. On the other hand, from the viewpoint of improving the adhesion between the partition and the substrate, the surface contact angle of the partition (F-1) is preferably 70 ° or less, and more preferably 60 ° or less. Here, the surface contact angle of the partition wall (A-1) conforms to the wettability test method for the surface of the substrate glass defined in JIS R3257 (established date: 1999/04/20) with respect to the upper part of the partition wall. Can be measured. In addition, as a method for setting the surface contact angle of the partition wall (F-1) in the above range, for example, in the above-described negative photosensitive coloring composition of the present invention, a negative type containing a photopolymerizable compound having a fluorine atom is used. A photosensitive coloring composition can be obtained by patterning a partition wall by the above-mentioned preferable manufacturing method.

<Shading barrier (F-2)>
In the substrate with a partition wall of the present invention, the optical density per thickness of 1.0 μm is further 0.1 to 4.0 between the substrate and the partition wall (F-1). It is preferable to have a patterned light-shielding partition (hereinafter sometimes referred to as “light-shielding partition (F-2)”). By having the light-shielding partition (F-2), the light-shielding property can be improved, the light leakage of the backlight in the display device can be 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 shape as the partition (F-1).

FIG. 9 shows a cross-sectional view of one embodiment of a substrate with a partition wall according to the present invention having a light shielding partition wall. On the substrate 1, a patterned partition wall 2 and a patterned light shielding partition wall 10 are provided, and a layer 3 containing a color conversion light emitting material is arranged in a region separated 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 thickness. Here, the thickness of the light shielding partition (F-2) is preferably 0.5 to 10 μm, as will be described later. Therefore, in the present invention, 1.0 μm is selected as the representative value of the thickness of the partition wall (F-2), and attention is paid to the optical density per 1.0 μm thickness. By setting the optical density per thickness of 1.0 μm to 0.1 or more, the light shielding property can be further improved, and a clearer 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, when the optical density per 1.0 μm thickness is 4.0 or less, the pattern processability can be improved. 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 wall (F-2) was measured by measuring the intensity of incident light and transmitted light using an optical densitometer (361T (visual); manufactured by X-rite), and the following formula (11) Can be calculated.

OD value = log10 (I ₀ / I) (11)
I ₀ : Incident light intensity I: Transmitted light intensity.

As a means for setting the optical density within the above range, for example, the light shielding partition (F-2) may have a preferable composition described later.

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, from the viewpoint of improving flatness, the thickness of the light shielding partition (F-2) is preferably 10 μm or less, and more preferably 5 μm or less. 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 crack resistance and light resistance of the partition walls. The black pigment has a function of absorbing incident light and reducing emitted light.

Examples of the resin include epoxy resin, (meth) acrylic polymer, polyurethane, polyester, polyimide, polyolefin, polysiloxane, and the like. Two or more of these may be contained. Among these, polyimide is preferable because of excellent heat resistance and solvent resistance.

Examples of black pigments include black organic pigments, mixed color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black aniline black, and benzofuranone pigments. These may be coated with a resin. Examples of the mixed color organic pigment include those obtained by mixing two or more pigments such as red, blue, green, violet, yellow, magenta and / or cyan to be pseudo black. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver; metal oxides; metal composite oxides; metal sulfides; Metal oxynitrides; metal carbides and the like.

As a method for patterning the light shielding partition (F-2) on the substrate, for example, a photosensitive material described in JP-A-2015-1654 is used, and the photosensitive property is the same as that of the partition (F-1) described above. A method of forming a pattern by a paste method is preferred.

In the substrate with a partition wall of the present invention, it is preferable that a layer (G) containing a color conversion light-emitting material is formed between the adjacent partition walls (F-1). The layer containing the color conversion light-emitting material has a function of performing color display by converting at least part of the wavelength region of incident light and emitting emitted light in a wavelength region different from the incident light. In addition, when the substrate with a partition wall of the present invention is used for an image display device, the layer (G) containing a color conversion luminescent material may be generally called a pixel.

FIG. 2 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a patterned partition wall and a layer (G) containing a color conversion luminescent material. On the substrate 1, a patterned partition wall 2 is provided, and a layer 3 containing a color conversion luminescent material is arranged in a region separated by the partition wall 2.

The color conversion 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 that emits 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 is combined, a region corresponding to a red pixel Preferably contains a red phosphor that emits red fluorescence when excited by blue excitation light, and the region corresponding to the green pixel emits green fluorescence when excited by blue excitation light. It is preferable that the fluorescent material is contained, and it is preferable that the region corresponding to the blue pixel does not contain the fluorescent material. On the other hand, the substrate with a partition wall of the present invention can also be used for a display device using a blue micro LED corresponding to each pixel separated by a white partition wall as a backlight. Each pixel can be turned on / off by turning on / off the blue micro LED, and no liquid crystal is required. In this case, it is preferable to have two types of partition walls, a partition wall for separating each pixel on the substrate and a partition wall for separating the blue micro LED in the backlight.

The inorganic phosphor emits each color such as green and red depending on the peak wavelength of the emission spectrum. Examples of the inorganic phosphor include those excited by excitation light having a wavelength of 400 to 500 nm and having a peak in the region of the emission spectrum of 500 to 700 nm, and inorganic semiconductor fine particles called quantum dots. Examples of the shape of the former inorganic phosphor include a spherical shape and a columnar shape. Examples of such inorganic phosphors include YAG phosphors, TAG phosphors, sialon phosphors, and Mn ⁴⁺ activated fluoride complex phosphors. Two or more of these may be used.

Among these, quantum dots are preferable. Since the quantum dot has a smaller average particle diameter than other phosphors, the surface of the layer (G) containing the color conversion light-emitting material can be smoothed and light scattering on the surface can be suppressed. The extraction efficiency can be further improved and the luminance can be further improved.

Examples of the material of the quantum dots include II-IV, III-V, IV-VI, and IV group semiconductors. Examples of these 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 Examples thereof include SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si ₃ N ₄ , Ge ₃ N ₄ , and Al ₂ O ₃ . Two or more of these may be used.

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

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

Examples of the organic phosphor include a pyromethene derivative having a basic skeleton represented by the following structural formula (8), a phosphor that emits red fluorescence when excited by blue excitation light, and a green phosphor that is excited by blue excitation light. Examples of the fluorescent substance that emits fluorescence include a pyromethene derivative having a basic skeleton represented by the following structural formula (9). In addition, perylene derivatives, porphyrin derivatives, oxazine derivatives, pyrazine derivatives, and the like that emit red or green fluorescence by selecting a substituent. Two or more of these may be contained. Among these, pyromethene derivatives are preferable because of their high quantum yield. The pyromethene derivative can be obtained, for example, by the method described in JP2011-241160A.

Since the organic phosphor is soluble in a solvent, a layer (G) containing a color conversion light-emitting material having a desired thickness can be easily formed.

The thickness of the layer (G) containing the color conversion luminescent material is preferably 0.5 μm or more, 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 conversion luminescent material is preferably 30 μm or less, and more preferably 20 μm or less, from the viewpoint of thinning the display device and curved surface processability.

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

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

As a method for forming the layer (G) containing the color conversion luminescent material, for example, there is a method of filling the space separated by the partition wall (F-1) with the color conversion luminescent material coating liquid containing the color conversion luminescent material. Can be mentioned. The color conversion light emitting material coating liquid may further contain a resin or a solvent.

As a filling method of the color conversion luminescent material coating liquid, an inkjet coating method or the like is preferable from the viewpoint of easily applying different types of color conversion luminescent materials to each pixel.

The obtained coating film may be dried under reduced pressure and / or heat. In the case of drying under reduced pressure, the drying temperature under reduced pressure is preferably 80 ° C. or lower in order to prevent the drying solvent from recondensing on the inner wall of the vacuum chamber. The vacuum drying pressure is preferably not higher than the vapor pressure of the solvent contained in the coating film, and preferably 1 to 1000 Pa. The drying time under reduced pressure is preferably 10 to 600 seconds. In the case of heating and drying, examples of the heating and drying apparatus include an oven and a hot plate. The heating and drying temperature is preferably 60 to 200 ° C. The heat drying time is preferably 1 to 60 minutes.

The substrate with a partition wall of the present invention is further provided on a layer (G) containing a color-converting light-emitting material and (H) a low refractive index layer (hereinafter referred to as “a refractive index of 1.20 to 1.35 at a wavelength of 550 nm”). It may preferably be described as “low refractive index layer (H)”. 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 one embodiment of the substrate with a partition wall of the present invention having a low refractive index layer. On the substrate 1, a patterned partition wall 2 and a layer 3 containing a color conversion light emitting material are provided, and a low refractive index layer 4 is further provided thereon.

In the display device, the refractive index of the low-refractive index layer (H) is 1. from the viewpoint of allowing light to be efficiently incident on the layer (G) containing the color conversion light-emitting material with moderate reflection of light from the backlight. 20 or more is preferable, and 1.23 or more is more preferable. On the other hand, from the viewpoint of improving luminance, the refractive index of the low refractive index layer (H) is preferably 1.35 or less, and more preferably 1.30 or less. Here, the refractive index of the low refractive index layer (H) is perpendicular to the cured film surface using a prism coupler (PC-2000 (manufactured by Metricon)) at 20 ° C. under atmospheric pressure. To irradiate light with a wavelength of 550 nm.

The low refractive index layer (H) preferably contains polysiloxane and silica particles having no hollow structure. Polysiloxane is highly compatible with inorganic particles such as silica particles and functions as a binder capable of forming a transparent layer. In addition, by containing silica particles, it is possible to efficiently form minute voids in the low refractive index layer (H) to reduce the refractive index, and to easily adjust the refractive index to the above range. Can do. Furthermore, by using silica particles that do not have a hollow structure as silica particles, cracks can be suppressed because there is no hollow structure that is liable to cause cracks during curing shrinkage. In the low refractive index layer (H), the polysiloxane and the silica particles having no hollow structure may be contained independently, or the polysiloxane and the silica particles having no hollow structure are combined. It may be contained. From the viewpoint of uniformity of the low refractive index layer (H), the polysiloxane and the silica particles having no hollow structure are preferably contained in a combined state.

The polysiloxane contained in the low refractive index layer (H) preferably contains fluorine. When the polysiloxane contains fluorine, the refractive index of the low refractive index layer (H) can be easily adjusted to 1.20 to 1.35. The fluorine-containing polysiloxane can be obtained by hydrolysis and polycondensation of an alkoxysilane compound including a fluorine-containing alkoxysilane compound represented by the following general formula (10). Further, other alkoxysilane compounds may be used.

In the general formula (10), R ¹³ represents a fluoroalkyl group having 3 to 17 fluorine atoms. R ⁷ represents the same group as R ⁷ in formulas (4) to (6). m represents 1 or 2. 4-m R ⁷ and m R ¹³ may be the same or different.

Examples of the fluorine-containing alkoxysilane compound represented by the general formula (10) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, and trifluoro. Propyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltriisopropoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyl Trimethoxysilane, tridecafluorooctyltriisopropoxysilane, trifluoroethylmethyldimethoxysilane, trifluoroethylmethyldi Toxisilane, trifluoroethylmethyldiisopropoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldiisopropoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldiethoxy Silane, heptadecafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane, tridecafluorooctylmethyldiisopropoxysilane, trifluoroethylethyldimethoxysilane, trifluoroethylethyl Diethoxysilane, trifluoroethylethyldiisopropoxysilane, trifluoropropylethyldimeth Sisilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiisopropoxysilane, heptadecafluorodecylethyldimethoxysilane, heptadecafluorodecylethyldiethoxysilane, heptadecafluorodecylethyldiisopropoxysilane, tridecafluorooctyl Examples include ethyldiethoxysilane, tridecafluorooctylethyldimethoxysilane, and tridecafluorooctylethyldiisopropoxysilane. Two or more of these may be used.

The content of 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, the content of the polysiloxane is 32% by weight or less from the viewpoint of ensuring thixotropy due to the network between silica particles and maintaining a moderate air layer in the low refractive index layer (H) to further reduce the refractive index. preferable.

Examples of silica particles having no hollow structure in the low refractive index layer (H) include “Snowtex” (registered trademark) and “organosilica sol” (registered trademark) series (isopropyl alcohol dispersions) manufactured by Nissan Chemical Industries, Ltd. , 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, etc., such as PGM-ST, PMA-ST, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP). Two or more of these may be contained.

The content of silica particles having no hollow structure in the low refractive index layer (H) ensures thixotropy due to the network between the silica particles, and an air layer is appropriately kept in the low refractive index layer (H). From the viewpoint of further reducing the amount, 68% by weight or more is preferable. On the other hand, the content of 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, more preferably 0.5 μm or more, from the viewpoint of suppressing the generation of defects by covering the steps of the layer (G) containing the color conversion luminescent material. preferable. 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 stress that causes cracks in the low refractive index layer (H).

As a method for forming the low refractive index layer (H), a coating method is preferable because the forming method is easy. For example, a low refractive index resin composition containing polysiloxane and silica particles is applied on a layer (G) containing a color conversion light-emitting material, dried and then heated, whereby a low refractive index layer (H ) Can be formed.

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 1,000 nm on the low refractive index layer (H). By having the inorganic protective layer I, it becomes difficult for moisture in the atmosphere to reach the low refractive index layer (H), so that fluctuations in the refractive index of the low refractive index layer (H) can be suppressed and luminance degradation can be suppressed. it can.

FIG. 4 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer I. On the substrate 1, a patterned partition wall 2 and a layer 3 containing a color conversion luminescent material are provided, and a low refractive index layer 4 and an inorganic protective layer I (5) are further provided 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 1,000 nm under the low refractive index layer (H). By having the inorganic protective layer II, the raw material for forming the layer (G) containing the color conversion light-emitting material is less likely to move from the layer (G) containing the color conversion light-emitting material to the low refractive index layer. It is possible to suppress the refractive index variation of the low refractive index layer (H) and suppress the luminance deterioration.

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

Further, the substrate with a partition wall of the present invention is further provided with (J) a color filter having a thickness of 1 to 5 μm (hereinafter referred to as “color filter (J)”) between the substrate and the layer (G) containing the color conversion luminescent material. It may be preferred to have). The color filter (J) has a function of transmitting visible light in a specific wavelength range to make the transmitted light have a desired hue. By having the color filter (J), the color purity can be improved. By setting the thickness of the color filter (J) to 1 μm or more, the color purity can be further improved. On the other hand, the brightness of the display device can be further improved by setting the thickness of the color filter (J) to 5 μm or less.

FIG. 6 shows a cross-sectional view of one embodiment of the substrate with a partition wall of the present invention having a color filter. The substrate 1 has a patterned partition wall 2 and a color filter 7, and the color filter 7 has a layer 3 containing a color conversion luminescent material.

As the color filter, for example, a color filter using a pigment-dispersed material in which a pigment is dispersed in a photoresist used for a flat panel display such as a liquid crystal display can be used. More specifically, a blue color filter that selectively transmits wavelengths of 400 nm to 550 nm, a green color filter that selectively transmits wavelengths of 500 nm to 600 nm, a yellow color filter that selectively transmits wavelengths of 500 nm or more, Examples thereof include a red color filter that selectively transmits a wavelength of 600 nm or more. Moreover, the color filter may be laminated | stacked separately from the layer (G) containing a color conversion luminescent material, and may be laminated | stacked integrally.

The substrate with a partition wall of the present invention further comprises (I-3) an inorganic protective layer III having a thickness of 50 to 1,000 nm between the color filter (J) and the layer (G) containing a color conversion light emitting material. It is preferable to have. By containing the inorganic protective layer III, it is difficult for the color filter (J) forming material to reach the layer (G) containing the color conversion luminescent material from the color filter (J). The luminance fluctuation of the layer (G) to be performed can be suppressed.

FIG. 7 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a color filter and an inorganic protective layer III. On the substrate 1, a patterned partition wall 2 and a color filter 7 are provided, on which an inorganic protective layer III (8) is provided and separated by a partition wall 2 covered with the inorganic protective layer III (8). And having a layer 3 containing the arranged and color-converting luminescent material.

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 1,000 nm on the substrate. The inorganic protective layer IV acts as a refractive index adjusting layer, and can extract light emitted from the layer (G) containing the color conversion light-emitting material more efficiently and further improve the luminance of the display device. It is more preferable to have the inorganic protective layer IV between the substrate and the partition wall (F) and the layer (G) containing the color conversion luminescent material.

FIG. 8 shows a cross-sectional view of one embodiment of the substrate with a partition wall of the present invention having the inorganic protective layer IV. The substrate 1 has the inorganic protective layer IV (9), the partition wall 2 and the color filter 7 patterned thereon, and the patterned partition wall 2 and the color conversion light-emitting material formed thereon. A layer 3 containing

Examples of materials 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; fluorides such as magnesium fluoride, and the like. . Two or more of these may be contained. Among these, one or more selected from silicon nitride and silicon oxide is more preferable because of low water vapor permeability and high permeability.

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

For the thickness of the inorganic protective layers I to IV, use a polishing apparatus such as a cross section polisher to expose a cross section perpendicular to the substrate, and observe the cross section with a scanning electron microscope or a transmission electron microscope. Can be measured.

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

Next, the display device of the present invention will be described. The display apparatus of this invention has the said board | substrate with a partition and a light emission light source. The light source is preferably a light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell. An organic EL cell is more preferable because of its excellent emission characteristics.

The manufacturing method of the display device of the present invention will be described with reference to an example of the display device having the substrate with partition walls and the organic EL cell of the present invention. A photosensitive polyimide resin is applied on a glass substrate, and an insulating film is formed by a photolithography method. After aluminum is sputtered as the back electrode layer, patterning is performed by photolithography to form a back electrode layer in the opening having no insulating film. Subsequently, tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq3) was formed as an electron transporting layer by a vacuum evaporation method, and then, as a light emitting layer, dicyanomethylenepyran, quinacridone, 4,4′-bis (2 , 2-diphenylvinyl) biphenyl is formed to form a white light emitting layer. Next, N, N′-diphenyl-N, N′-bis (α-naphthyl) -1,1′-biphenyl-4,4′-diamine is deposited as a hole transport layer by vacuum deposition. Finally, ITO is formed as a transparent electrode by sputtering to produce an organic EL cell having a white light emitting layer. The organic EL cell obtained in this way was opposed to the above-mentioned substrate with a partition wall and bonded with a sealant to produce a display device.

Next, the touch panel of the present invention will be described. The touch panel of the present invention has the above-mentioned 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 the touch panel of the present invention. The glass substrate 11 has the white light-shielding cured film 12 made of the cured film of the present invention and the transparent electrode 13, and the transparent electrode 13 has the transparent insulating film 14 and the metal wiring 15.

As the transparent electrode, an ITO electrode or the like is preferable because it is difficult to be visually recognized.

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

As the transparent film, a transparent insulating film that prevents conduction due to contact between metal wirings is preferable. A negative photosensitive film containing an inorganic film such as silicon oxide or silicon nitride, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. And a cured film of the transparent conductive resin composition.

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

FIG. 11 shows an example of the touch panel manufacturing method of the present invention. FIG. 11 a is a top view of the patterned processed substrate of the present invention having the white light-shielding cured film 12 on the 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 sputtering, a photoresist is formed, a pattern is formed by etching, and the photoresist is peeled off. FIG. 11 b shows a top view after forming the transparent electrode. Next, the transparent insulating film 14 is formed at a predetermined position. As a manufacturing method of a transparent insulating film, when the transparent insulating film is an inorganic film, for example, a CVD (Chemical Vapor Deposition) method is exemplified. When the transparent insulating film is a cured film of a negative photosensitive transparent resin composition, for example, a method using a lithography method may be mentioned. FIG. 11c shows a top view after forming the transparent insulating film. Thereafter, the metal wiring 15 is formed. As a method for forming metal wiring, for example, after forming a metal for forming wiring by vapor deposition or sputtering, a photoresist is formed, a pattern is formed by etching, and the photoresist is peeled off, printing of silver paste Method and lithography method. FIG. 11d shows a top view after forming the metal wiring.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. Of the compounds used in the synthesis examples and examples, those using abbreviations are shown below.
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol BHT: dibutylhydroxytoluene.

The solid content concentrations of the siloxane resin solutions in Synthesis Examples 1 to 9 and the acrylic resin in Synthesis Example 10 were determined by the following method. 1.5 g of siloxane resin solution or acrylic resin solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the heated aluminum cup was weighed, and the solid content concentration of the siloxane resin solution or the acrylic resin solution was determined from the ratio to the weight before the heating.

The weight average molecular weights of the siloxane resins in Synthesis Examples 1 to 9 and the acrylic resin in Synthesis Example 10 were determined by the following method. Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and using tetrahydrofuran as a fluidized bed, GPC analysis was performed based on “JIS K7252-3 (established date: 2008/03/20)” The weight average molecular weight in terms of polystyrene was measured.

The content ratio of each repeating unit in the siloxane resins in Synthesis Examples 1 to 9 was determined by the following method. A siloxane resin solution is injected into an “Teflon” (registered trademark) NMR sample tube having a diameter of 10 mm to perform ²⁹ Si-NMR measurement, and Si derived from a specific organosilane with respect to the integrated value of the entire Si derived from organosilane. The content ratio of each repeating unit was calculated from the ratio of the integrated value of. ^{The 29} Si-NMR measurement conditions are shown below.
Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( ²⁹ Si nucleus)
Spectrum width: 20000Hz
Pulse width: 12μs (45 ° pulse)
Pulse repetition time: 30.0 seconds Solvent: Acetone-d6
Reference substance: Tetramethylsilane Measurement temperature: 23 ° C
Sample rotation speed: 0.0 Hz.

Synthesis Example 1 Siloxane Resin (B-1) Solution In a 1000 ml three-necked flask, 147.32 g (0.675 mol) of trifluoropropyltrimethoxysilane and 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane 26.23 g (0.1 mol) of 3-trimethoxysilylpropyl succinic anhydride, 12.32 g (0.05 mol) of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, and 0.808 g of BHT Then, 171.62 g of PGMEA was charged, and an aqueous phosphoric acid solution in which 2.265 g of phosphoric acid (1.0 wt% with respect to the charged monomer) was dissolved in 52.65 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the solution temperature (internal temperature) reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a siloxane resin solution. During the temperature rise and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter / minute. During the reaction, a total of 131.35 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (B-1) solution. The resulting siloxane resin (B-1) had a weight average molecular weight of 4,000 (polystyrene conversion). From the ²⁹ Si-NMR measurement results, trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3- ( The molar ratios of repeating units derived from 3,4-epoxycyclohexyl) propyltrimethoxysilane were 67.5 mol%, 17.5 mol%, 10 mol%, and 5 mol%, respectively.

Synthesis Example 2 Siloxane Resin (B-2) Solution In a 1000 ml three-necked flask, 81.84 g (0.375 mol) of trifluoropropyltrimethoxysilane and 60.66 g (0.3 mol) of trifluoropropylmethyldimethoxysilane, 3 -40.66 g (0.175 mol) of methacryloxypropylmethyldimethoxysilane, 26.23 g (0.1 mol) of 3-trimethoxysilylpropyl succinic anhydride, 3- (3,4-epoxycyclohexyl) propyltrimethoxy 12.32 g (0.05 mol) of silane, 0.78 g of BHT, and 174.95 g of PGMEA are charged, and 2.217 g of phosphoric acid is added to 44.55 g of water while stirring at room temperature (1.0% by weight based on the charged monomers). ) Was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 128.40 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-2) solution. The resulting siloxane resin (B-2) had a weight average molecular weight of 3,200 (in terms of polystyrene). From the ²⁹ Si-NMR measurement results, trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropyl succinate in the siloxane resin (B-2) The molar ratios of repeating units derived from acid anhydride and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane were 37.5 mol%, 30 mol%, 17.5 mol%, 10 mol%, and 5 mol%, respectively. .

Synthesis Example 3 Siloxane Resin (B-3) Solution In a 1000 ml three-necked flask, 103.67 g (0.475 mol) of trifluoropropyltrimethoxysilane and 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane were synthesized. 26.23 g (0.1 mol) of 3-trimethoxysilylpropyl succinic anhydride, 12.32 g (0.05 mol) of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, and methyltrimethoxysilane 27.24 g (0.2 mol), 0.808 g of BHT and 155.37 g of PGMEA were charged, and 2.101 g of phosphoric acid (1.0% by weight with respect to the charged monomer) was added to 52.65 g of water while stirring at room temperature. The dissolved aqueous phosphoric acid solution was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 131.35 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-3) solution. The resulting siloxane resin (B-3) had a weight average molecular weight of 3,500 (polystyrene conversion). From the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3- ( The molar ratios of the repeating units derived from 3,4-epoxycyclohexyl) propyltrimethoxysilane and methyltrimethoxysilane were 47.5 mol%, 17.5 mol%, 10 mol%, 5 mol% and 20 mol%, respectively.

Synthesis Example 4 Siloxane Resin (B-4) Solution In a 1000 ml three-necked flask, 103.67 g (0.475 mol) of trifluoropropyltrimethoxysilane, 24.04 g (0.20 mol) of dimethyldimethoxysilane, 3-methacryloxy 43.46 g (0.175 mol) of propyltrimethoxysilane, 26.23 g (0.1 mol) of 3-trimethoxysilylpropyl succinic anhydride, 12 of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane .32 g (0.05 mol), BHT 0.736 g, and PGMEA 161.28 g were charged, and 2.097 g of phosphoric acid (1.0 wt% with respect to the charged monomer) was dissolved in 50.85 g of water while stirring at room temperature. An aqueous phosphoric acid solution was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 130.05 g of methanol and water as by-products were distilled. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (B-4) solution. The resulting siloxane resin (B-4) had a weight average molecular weight of 3,800 (polystyrene conversion). In addition, from the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride in the siloxane resin (B-4) The molar ratio of repeating units derived from 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane was 47.5 mol%, 20 mol%, 17.5 mol%, 10 mol%, and 5 mol%, respectively.

Synthesis Example 5 Siloxane Resin (B-5) Solution In a 1000 ml three-necked flask, 147.32 g (0.675 mol) of trifluoropropyltrimethoxysilane and 43.46 g (0.175 mol) of 3-methacryloxypropyltrimethoxysilane. ), 26.23 g (0.1 mol) of 3-trimethoxysilylpropyl succinic anhydride, 12.32 g (0.05 mol) of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, and 0.2% of BHT. 810 g and 172.59 g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 2.293 g of phosphoric acid (1.0 wt% with respect to the charged monomer) in 54.45 g of water was added over 30 minutes while stirring at room temperature. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 140.05 g of methanol and water as by-products were distilled. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-5) solution. The resulting siloxane resin (B-5) had a weight average molecular weight of 4,100 (in terms of polystyrene). From the ²⁹ Si-NMR measurement results, trifluoropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3- ( The molar ratios of repeating units derived from 3,4-epoxycyclohexyl) propyltrimethoxysilane were 67.5 mol%, 17.5 mol%, 10 mol%, and 5 mol%, respectively.

Synthesis Example 6 Siloxane Resin (B-6) Solution In a 1000 ml three-necked flask, 76.93 g (0.35 mol) of trifluoropropyltrimethoxysilane and 41.00 g (0.175 mol) of 3-acryloxypropyltrimethoxysilane. ), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), methyltrimethoxysilane 51.08 g (0.375 mol), BHT 0.375 g, and PGMEA 136.95 g were charged at room temperature. Then, an aqueous phosphoric acid solution in which 2.070 g of phosphoric acid (1.0 wt% with respect to the charged monomer) was dissolved in 58.50 g of water was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 139.50 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-6) solution. The resulting siloxane resin (B-6) had a weight average molecular weight of 5,000 (polystyrene conversion). From the ²⁹ Si-NMR measurement results, trifluoropropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, methyltrimethyl siloxane resin (B-6) The molar ratio of the repeating units derived from methoxysilane was 35 mol%, 17.5 mol%, 10 mol%, and 37.5 mol%, respectively.

Synthesis Example 7 Siloxane Resin (B-7) Solution In a 1000 ml three-necked flask, 76.39 g (0.35 mol) of trifluoropropyltrimethoxysilane and 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane were prepared. 26.23 g (0.1 mol) of 3-trimethoxysilylpropyl succinic anhydride, 12.32 g (0.05 mol) of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, and methyltrimethoxysilane 44.27 g (0.325 mol), BHT 0.673 g, and PGMEA 145.22 g were charged, and 1.999 g of phosphoric acid (1.0 wt% with respect to the charged monomer) was added to 52.65 g of water while stirring at room temperature. The dissolved aqueous phosphoric acid solution was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 130.25 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (B-7) solution. The resulting siloxane resin (B-7) had a weight average molecular weight of 3,900 (polystyrene conversion). From the ²⁹ Si-NMR measurement results, trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3- ( The molar ratios of repeating units derived from 3,4-epoxycyclohexyl) propyltrimethoxysilane and methyltrimethoxysilane were 35 mol%, 17.5 mol%, 10 mol%, 5 mol% and 32.5 mol%, respectively.

Synthesis Example 8 Siloxane Resin (B-8) Solution In a 1000 ml three-necked flask, 185.51 g (0.85 mol) of trifluoropropyltrimethoxysilane and 17.43 g (0.075 mol) of 3-methacryloxypropylmethyldimethoxysilane , 19.67 g (0.075 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.779 g of BHT and 166.39 g of PGMEA were charged, and 2.226 g of phosphoric acid was added to 54.00 g of water while stirring at room temperature ( An aqueous phosphoric acid solution in which 1.0 wt% of the charged monomer was dissolved was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 136.90 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-8) solution. The resulting siloxane resin (B-8) had a weight average molecular weight of 4,600 (polystyrene conversion). In addition, from the results of ²⁹ Si-NMR measurement, the siloxane resin (B-8) was repeatedly derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. The molar ratio of the units was 85 mol%, 7.5 mol%, and 7.5 mol%, respectively.

Synthesis Example 9 Siloxane Resin (B-9) Solution In a 1000 ml three-necked flask, 164.94 g (0.675 mol) of diphenyldimethoxysilane, 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 3- 26.23 g (0.1 mol) of trimethoxysilylpropyl succinic anhydride, 12.32 g (0.05 mol) of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 0.974 g of BHT, and PGMEA An aqueous phosphoric acid solution prepared by dissolving 2.442 g of phosphoric acid (1.0 wt% with respect to the charged monomer) in 40.50 g of water was added over 30 minutes while stirring at room temperature. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 136.90 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-9) solution. The resulting siloxane resin (B-9) had a weight average molecular weight of 2,800 (polystyrene conversion). From the results of ²⁹ Si-NMR measurement, diphenyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3- (3,4) in the siloxane resin (B-9). The molar ratio of the repeating units derived from -epoxycyclohexyl) propyltrimethoxysilane was 67.5 mol%, 17.5 mol%, 10 mol%, 5 mol%, respectively.

The raw material compositions of the siloxane resins of Synthesis Examples 1 to 9 are shown in Tables 1 and 2.

Synthesis Example 10 Acrylic Resin (b) Solution In a 500 ml three-necked flask, 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGME were charged. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred at 5 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution. . PGMEA was added to the obtained acrylic resin solution so that the solid concentration was 40% by weight to obtain an acrylic resin (b) solution. The weight average molecular weight of the acrylic resin (b) was 10,000 (polystyrene conversion).

Synthesis Example 11 Silane Coupling Agent (G-1) Solution To 200 g of PGMEA was added 41.97 g (0.16 mol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (0.16 mol) of t-butylamine for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Thereafter, the temperature was raised to 80 ° C., and the mixture was heated and stirred for 6 hours. PGMEA was added to the obtained solution so that the solid content concentration was 20% by weight, and 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butyl) was added. A silane coupling agent (G-1) which is a mixed solution of amino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid was obtained.

Synthesis Example 12 Green organic phosphor 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g), carbonic acid Potassium (2.0 g) was placed in the flask and purged with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) 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 and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain a white solid of 3,5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g). Next, 3,5-bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were placed in a flask and dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 The mixture was stirred for 4 hours under a nitrogen atmosphere. A dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, then water (100 mL) was further added and stirred, and the organic layer was separated. did. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 0.4 g of a green powder (yield 17%). The results of ¹ H-NMR analysis of the obtained green powder are as follows, and it was confirmed that the green powder obtained above was [G-1] represented by the following structural formula.
¹ H-NMR (CDCl ₃ (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 Silica Particle-Containing Polysiloxane Solution (LS-1)
In a 500 ml three-necked flask, 0.05 g (0.4 mmol) of methyltrimethoxysilane, 0.66 g (3.0 mmol) of trifluoropropyltrimethoxysilane, and 0.10 g of trimethoxysilylpropyl succinic anhydride (0 .4 mmol), 7.97 g (34 mmol) of γ-acryloxypropyltrimethoxysilane, and an isopropyl alcohol dispersion of 15.6 wt% silica particles (IPA-ST-UP: manufactured by Nissan Chemical Industries, Ltd.) 224 .37 g was mixed, and 163.93 g of ethylene glycol mono-t-butyl ether was added. While stirring at room temperature, an aqueous phosphoric acid solution in which 0.088 g of phosphoric acid was dissolved in 4.09 g of water was added over 3 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a silica particle-containing polysiloxane solution (LS-1). During the temperature rise and heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 194.01 g of methanol and water as by-products were distilled out. The resulting silica particle-containing polysiloxane solution (LS-1) had a solid content concentration of 24.3% by weight, and the contents of polysiloxane and silica particles in the solid content were 15% by weight and 85% by weight, respectively. Polysiloxanes in the resulting silica particle-containing polysiloxane (LS-1) were converted to methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and γ-acryloxypropyltrimethoxysilane. The molar ratio of the derived repeating units was 1.0 mol%, 8.0 mol%, 1.0 mol%, and 90.0 mol%, respectively.

Preparation Example 1 Negative photosensitive coloring composition (P-1)
4. (A) Titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd.) 5.00 g as a white pigment, and (B) siloxane resin (B-1) solution obtained in Synthesis Example 1 as a siloxane resin. Dispersion was carried out using a mill type disperser filled with zirconia beads mixed with 00 g to obtain a pigment dispersion (MW-1).

Next, 10.00 g of pigment dispersion (MW-1), 1.15 g of siloxane resin (B-1) solution, (C) 2-methyl-1- (4-methylthiophenyl) -2 as a photopolymerization initiator -Morpholinopropan-1-one ("Irgacure" (registered trademark) -907 (trade name), manufactured by BASF Japan Ltd.) 0.100 g, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ( “Irgacure” -819 (trade name), manufactured by BASF Japan Ltd. 0.200 g, (D) As a photopolymerizable compound, pentaerythritol acrylate (“light acrylate” (registered trademark) PE-3A (trade name), 1.50 g, manufactured by Kyoeisha Chemical Co., Ltd., photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E (trade name) DIC Corporation) ) 40 wt% PGMEA diluted solution 1.00 g, Silane coupling agent (G1) 20 wt% PGMEA diluted solution 0.500 g, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“ Celoxide ”(registered trademark) -2021P (trade name), manufactured by Daicel Corporation) 0.200 g, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] ("Irganox" (registered trademark) -1010 (trade name), manufactured by BASF Japan Ltd.) 0.300 g, acrylic surfactant (trade name "BYK" (registered trademark) -352, Big Chemie Japan Ltd.) )) PGMEA 10 wt% diluted solution 0.100 g (corresponding to a concentration of 500 ppm) It was dissolved in a mixed solvent of 000g and PGMEA4.200G, and stirred. Next, the mixture was filtered through 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)
A negative photosensitive coloring composition (P) was prepared in the same manner as in Preparation Example 1, except that the siloxane resins (B-2) to (B-4) were used instead of the siloxane resin (B-1) solution. -2) to (P-4) were obtained.

Preparation Example 5 Negative photosensitive coloring composition (P-5)
Instead of 1.00 g of a 40 wt% PGMEA diluted solution of a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E), pentaerythritol acrylate (“light acrylate” (registered trademark) PE-3A) The negative photosensitive coloring composition (P-5) was obtained in the same manner as in Preparation Example 1 except that 1.00 g of a 40 wt% PGMEA diluent was used.

Preparation Example 6 Negative photosensitive coloring composition (P-6)
Instead of 1.00 g of a 40 wt% PGMEA diluted solution of a photoreactive fluorine-containing compound (“Megafac” (registered trademark) RS-76-E (trade name) manufactured by DIC Corporation), 2,2,2- The same procedure as in Preparation Example 1, except that 1.00 g of a 40 wt% PGMEA diluted solution of trifluoroethyl acrylate (“Biscoat” (registered trademark) -3F (trade name), manufactured by Osaka Organic Chemical Co., Ltd.) was used. A negative photosensitive coloring composition (P-6) was obtained.

Preparation Example 7 Negative photosensitive coloring composition (P-7)
Negative-type photosensitivity was obtained in the same manner as in Preparation Example 1 except that a titanium dioxide pigment (CR-97; manufactured by Ishihara Sangyo Co., Ltd.) was used instead of the titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd.). Sex coloring composition (P-7) was obtained.

Preparation Example 8 Negative photosensitive coloring composition (P-8)
Instead of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“Irgacure” -127), “Irgacure” (registered trademark) -MBF (trade name), BASF Japan ( Except for using 0.100 g), a negative photosensitive coloring composition (P-8) was obtained in the same manner as in Preparation Example 1.

Preparation Examples 9 to 13 Negative photosensitive coloring compositions (P-9) to (P-13)
A negative photosensitive coloring composition (P-) was prepared in the same manner as in Preparation Example 1, except that the siloxane resins (B-5) to (B-9) were used instead of the siloxane resin (B-1) solution. 9) to (P-13) were obtained.

Preparation Example 14 Negative 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 the acrylic resin (b) solution was used instead of the resin (B-1) solution.

Preparation Example 15 Negative photosensitive coloring composition (P-15)
8.00 g of pigment dispersion (MW-1), 1.615 g of the polysiloxane (B-1) solution obtained in Synthesis Example 1, and ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (“Irgacure” (registered trademark) OXE-02 (trade name) manufactured by BASF Japan Ltd. (hereinafter “OXE-02”) )) 0.160 g, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure” 819 (trade name), manufactured by BASF Japan Ltd. (hereinafter “IC-819”)) 0.160 g, As a photopolymerizable compound, dipentaerythritol hexaacrylate (“KAYARAD” (registered trademark) DPHA (trade name), manufactured by Shin Nippon Pharmaceutical Co., Ltd. (hereinafter “DPH”) )) 1.20 g, as a liquid repellent compound, a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E (trade name) manufactured by DIC Corporation (hereinafter “RS-76-E”) )) 40 wt% PGMEA diluted solution 0.100 g, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Celoxide” (registered trademark) 2021P (trade name), manufactured by Daicel Corporation (Hereinafter referred to as “Celoxide 2021P”) 0.160 g, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (“Irganox” (registered trademark) 1010 ( Product Name), BASF Japan K.K. (hereinafter “IRGANOX1010”)) 0.024 g, acrylic surfactant (“BY "(Registered trademark) 352 (trade name), manufactured by Big Chemie Japan Co., Ltd." PGMEA 10 wt% diluted solution 0.100 g (corresponding to a concentration of 500 ppm) is dissolved in a mixed solvent of DAA 1.200 g and PGMEA 7.281 g, Stir. Next, the mixture was filtered through 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 the polysiloxane (B-5) solution was used instead of the polysiloxane (B-1) solution.

Preparation Example 17 Negative photosensitive coloring composition (P-17)
Negative type as in Preparation Example 15 except that the amount of RS-76-E 40 wt% PGMEA diluted solution was changed to 0.01 g and the amount of polysiloxane (B-1) solution was changed to 1.705 g. A photosensitive colored composition (P-17) was obtained.

Preparation Example 18 Negative photosensitive coloring composition (P-18)
Negative photosensitive coloring similar to Preparation Example 15 except that 0.100 g of 40 wt% PGMEA diluted solution of RS-76-E was not added and the amount of polysiloxane (B-1) solution was changed to 1.715 g. A composition (P-18) was obtained.

Preparation Example 19 Negative photosensitive coloring composition (P-19)
The amount of addition of pigment dispersion (MW-1) was changed to 4.00 g, the amount of addition of polysiloxane (B-1) solution was changed to 8.615 g, and a mixed solvent of 1.200 g DAA and 1.881 g PGMEA was used. In the same manner as in Preparation Example 15, a negative photosensitive coloring composition (P-19) was obtained.

Preparation Example 20 Negative photosensitive coloring composition (P-20)
The addition amount of the pigment dispersion (MW-1) was changed to 3.20 g, the addition amount of the polysiloxane (B-1) solution was changed to 10.15 g, and a mixed solvent of 1.200 g DAA and 3.681 g PGMEA was used. In the same manner as in Preparation Example 15, a negative photosensitive coloring composition (P-20) was obtained.

Preparation Example 21 Negative photosensitive coloring composition (P-21)
The addition amount of the pigment dispersion (MW-1) was changed to 1.60 g, the addition amount of the polysiloxane (B-1) solution was changed to 12.815 g, and a mixed solvent of 1.200 g DAA and 2.481 g PGMEA was used. In the same manner as in Preparation Example 15, a negative photosensitive coloring composition (P-21) was obtained.

The compositions of Preparation Examples 1 to 21 are summarized in Table 3, Table 4, and Table 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 size 6.3 nm: manufactured by Aldrich), 45 parts by weight of DPHA, “Irgacure” (registered trademark) 907 ( 5 parts by weight of BASF Japan Co., Ltd.), 166 parts by weight of 30% by weight PGMEA solution of acrylic resin (SPCR-18 (trade name), Showa Denko Co., Ltd.) and 97 parts by weight of toluene are mixed and stirred. And dissolved uniformly. A color conversion luminescent material composition (CL-1) was prepared by filtration through a 0.45 μm syringe filter. Preparation Example 23 Color Conversion luminescent Material Composition (CL-2)
In the same manner as in Preparation Example 22, except that 0.4 part by weight of the green phosphor G-1 obtained in Synthesis Example 12 was used instead of the green quantum dot material, and the amount of toluene added was changed to 117 parts by weight. A converted luminescent material composition (CL-2) was prepared.

Preparation Example 24 Color filter forming material (CF-1)
C. I. 90 g of CI Pigment Green 59, C.I. I. 60 g of Pigment Yellow 150, 75 g of a polymeric dispersant (“BYK” (registered trademark) -6919 (trade name) manufactured by Big Chemie), and binder resin (“ADEKA ARKLES” (registered trademark) WR301 (trade name) (stock) ) 100 g of ADEKA) and 675 g of PGMEA were mixed to prepare a slurry. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and dispersion treatment was performed for 8 hours at a peripheral speed of 14 m / s. Was made.

Pigment Green 59 dispersion (GD-1) 56.54 g, acrylic resin ("Cyclomer" (registered trademark) P (ACA) Z250 (trade name) manufactured by Daicel Ornex Co., Ltd. (hereinafter "P (ACA) Z250") )) 3.14 g, DPHA 2.64 g, photopolymerization initiator (“Optomer” (registered trademark) NCI-831 (trade name) manufactured by ADEKA Corporation (hereinafter “NCI-831”)) 0.330 g, 0.04 g of a surfactant (BYK "(registered trademark) -333 (trade name) manufactured by Big Chemie), 0.01 g of BHT as a polymerization inhibitor, and 37.30 g of PGMEA as a solvent were added, and a color filter forming material ( CF-1) was produced.

Preparation Example 25 Resin Composition for Light-shielding Partition Carbon Black (MA100 (trade name) manufactured by Mitsubishi Chemical Corporation) 150 g, 75 g of polymer dispersant BYK (registered trademark) -6919, 100 g of P (ACA) Z250, PGMEA A slurry was prepared by mixing 675 g. Connect the beaker containing the slurry with a dyno mill and a tube, and use a zirconia bead with a diameter of 0.5 mm as the media to perform a dispersion treatment for 8 hours at a peripheral speed of 14 m / s to prepare a pigment dispersion (MB-1). did.

Pigment dispersion (MB-1) 56.54, P (ACA) Z250 3.14 g, DPHA 2.64 g, NCI-831 0.330 g, BYK (registered trademark) -333 0.04 g, polymerization prohibited As the agent, 0.01 g of tertiary butyl catechol and 37.30 g of PGMEA were added to prepare a resin composition for a light shielding partition.

Preparation Example 26 Low Refractive Index Layer-Forming Material 5.350 g of the silica particle-containing polysiloxane solution (LS-1) obtained in Synthesis Example 13 was mixed with 1.170 g of ethylene glycol mono-t-butyl ether and 3.48 g of DAA. Then, it filtered with a 0.45 micrometer syringe filter, and prepared the low refractive index layer forming material.

The evaluation methods in each example and comparative example are shown below.

<Refractive index of white pigment>
Among the methods for measuring the refractive index of plastics stipulated in JIS K7142-2014 (established date: 2014/04/20) for the white pigment (A) used in each example and comparative example, method B (microscope) The refractive index was measured by the immersion method (Becke line method) used. The measurement wavelength was 587.5 nm. However, instead of the immersion liquid used in JIS K7142-2014, a “contact liquid” manufactured by Shimadzu Device Manufacturing Co., Ltd. was used, and measurement was performed under the condition of immersion liquid temperature: 20 ° C. A polarizing microscope “Optiphoto” (manufactured by Nikon Corporation) was used as a microscope. (A) Thirty samples of white pigment were prepared, the respective refractive indexes were measured, and the average value was taken as the refractive index.

<Refractive index of siloxane resin or acrylic resin>
The refractive index of the siloxane resin or acrylic resin used in each example and comparative example was determined by the following method. On the silicon wafer, the siloxane resin solution in Synthesis Examples 1 to 9 or the acrylic resin solution in Synthesis Example 10 was applied with a spinner and dried on a hot plate at 90 ° C. for 2 minutes. Thereafter, using an oven (IHPS-222; manufactured by Espec Corp.), the film was cured in air at 230 ° C. for 30 minutes to prepare a cured film. Using a prism coupler (PC-2000 (manufactured by Metricon Co., Ltd.)), light at a wavelength of 587.5 nm is irradiated from the direction perpendicular to the cured film surface at 20 ° C. under atmospheric pressure to change the refractive index. Measured and rounded to the second decimal place.

<Resolution>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was cured on a 10 cm square alkali-free glass substrate. The film is spin-coated so that the film thickness becomes 10 μm, and prebaked at a temperature of 90 ° C. for 2 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). Was made.

Using the pre-baked film, a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) and an ultra-high pressure mercury lamp as a light source, lines of each width of 100 μm, 80 μm, 60 μm, 50 μm, 40 μm and 30 μm And it exposed with the gap of 100 micrometers with the exposure amount of 150 mJ / cm < ² > (i line) through the mask which has a space pattern. Thereafter, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed for 100 seconds using a 0.045 wt% aqueous potassium hydroxide solution, and then water is used for 30 seconds. Rinse for 2 seconds.

Using a microscope adjusted to a magnification of 100, the developed pattern was enlarged and observed, and the narrowest line width among the patterns in which no residue was observed in the unexposed area was defined as the resolution. However, if there is a residue even in an unexposed portion near the pattern having a width of 100 μm, “> 100 μm” was set.

<Visual reflectance>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was cured on a 10 cm square alkali-free glass substrate. The film was spin-coated so as to have a film thickness of 10 μm, and prebaked at a temperature of 90 ° C. for 2 minutes using a hot plate (SCW-636) to form a prebaked film. The prepared pre-baked film was exposed, developed and rinsed in the same manner as in the above-described <Resolution> evaluation method except that no mask was interposed. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corp.), curing was performed in air at a temperature of 230 ° C. for 30 minutes to prepare a cured film.

For a non-alkali glass substrate having a cured film, the reflection chromaticity of the cured film was measured from the glass substrate side using a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.), and the CIE Y value (Evaluation of luminous reflectance) However, when a crack occurred in the cured film, an accurate value could not be obtained due to the crack or the like, and thus the luminous reflectance was not measured.

<Reflectance>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was cured on a 10 cm square alkali-free glass substrate. The film was spin-coated so as to have a film thickness of 10 μm, and prebaked at a temperature of 90 ° C. for 2 minutes using a hot plate (SCW-636) to form a prebaked film. The prepared pre-baked film was exposed, developed and rinsed in the same manner as in the above-described <Resolution> evaluation method except that no mask was interposed. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corp.), curing was performed in air at a temperature of 230 ° C. for 30 minutes to prepare a cured film.

With respect to the alkali-free glass substrate having a cured film, the reflectance at a wavelength of 550 nm was measured in the SCI mode from the solid film side using a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.). However, when a crack was generated in the solid film, an accurate value could not be obtained due to the crack or the like, so the reflectance was not measured.

<Heat resistance-1 Crack resistance>
Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was applied to a 10 cm square non-alkali glass substrate after curing. The films were applied to a thickness of 5 μm, 10 μm, 15 μm, and 20 μm, respectively, and prebaked at a temperature of 90 ° C. for 2 minutes using a hot plate (SCW-636) to form a prebaked film. The prepared pre-baked film was exposed, developed and rinsed in the same manner as in the above-described <Resolution> evaluation method except that no mask was interposed. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corp.), curing was performed in air at a temperature of 230 ° C. for 30 minutes to prepare a cured film.

The produced cured film was visually observed to evaluate the occurrence of cracks. When even one crack was confirmed, it was judged that there was no crack resistance at that film thickness. For example, when there was no crack at a film thickness of 15 μm and there was a crack at a film thickness of 20 μm, the crack-resistant film thickness was determined as “≦ 15 μm”. Further, the crack-resistant film thickness when there is no crack even at 20 μm was determined as “≧ 20 μm”, and the crack-resistant film thickness when there was a crack even when 5 μm was determined as “<5 μm”, respectively.

The cured film with no cracks was further subjected to additional curing in air at a temperature of 240 ° C. for 2 hours using an oven (IHPS-222), and the presence or absence of cracks was similarly evaluated. Later resistance to cracking.

<Heat resistance-2 color change>
Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was applied to a 10 cm square non-alkali glass substrate after curing. The coating was applied so that the thickness was 10 μm, and a cured film was produced in the same manner as in the above-described evaluation method of <Heat resistance-1 Crack resistance>. However, when cracks occurred in the cured film, the remaining evaluation was not performed.

For the alkali-free glass substrate having the obtained cured film, the reflection chromaticity of the cured film was measured from the glass substrate side using a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.), and CIE1976. (L *, a *, b *) The yellowness was evaluated based on the value of b * when displayed in the color space, and the color characteristics before additional curing were used. A C light source was used as the light source.

The cured film whose color characteristics were evaluated was further subjected to additional curing for 2 hours at 240 ° C. in air using an oven (IHPS-222), and then the reflection chromaticity was measured in the same manner, and CIE 1976 (L * , A *, b *) The values displayed in the color space were compared with the color characteristics before additional curing, and the color difference (hereinafter referred to as “ΔEab”) was calculated by the following equation (I). The smaller ΔEab, the better the heat resistance. ΔEab is preferably 1.0 or less, and more preferably 0.7 or less.
ΔEab = (X1 ² + X2 ² + X3 ² ) ^0.5 ... 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)}
However, L * (0), a * (0), and b * (0) respectively indicate the values of L *, a *, and b * before additional curing, and L * (1), a * (1 ) And b * (1) indicate the values of L *, a *, and b * after additional curing, respectively.

<OD value>
As a model of the partition wall of the substrate with a partition wall obtained in each example and comparative example, a solid film was formed on a glass substrate in the same manner as the above-described evaluation method of <reflectance>. About the glass substrate which has the obtained solid film, the intensity | strength of incident light and transmitted light was measured using the optical densitometer (361T (visual); X-rite company make), and optical density ( OD value) was calculated.
OD value = log 10 (I ₀ / I) Expression (10)
I ₀ : Incident light intensity I: Transmitted light intensity.

<Surface contact angle>
As a model of the partition wall of the substrate with a partition wall obtained in each example and comparative example, a solid film was formed on a glass substrate in the same manner as the above-described evaluation method of <reflectance>. About the obtained solid film, DM-700 manufactured by Kyowa Interface Science Co., Ltd., Microsyringe: Teflon (registered trademark) coated needle 22G for contact angle meter manufactured by Kyowa Interface Science Co., Ltd., at 25 ° C. in the atmosphere. The surface contact angle with respect to propylene glycol monomethyl ether acetate was measured in accordance with a wettability test method for the surface of a substrate glass specified in JIS R3257 (Established date: 1999/04/20).

<Inkjet coating properties>
In the substrate with barrier ribs obtained before the formation of the layer (G) containing the color conversion light-emitting material obtained in each of the examples and comparative examples, PGMEA is used as an ink for the pixel portion surrounded by the grid-like barrier ribs. Inkjet coating was performed using an inkjet coating apparatus (InkjetLab, manufactured by Cluster Technology Co., Ltd.). 160 pL of PGMEA was applied per grid pattern, and the presence or absence of breakage (a phenomenon in which ink crosses the partition wall and enters the adjacent pixel portion) was observed, and the inkjet coating property was evaluated according to the following criteria. The liquid repellency is so high that it does not break, indicating that the ink jet coating property is excellent.
A: Ink did not overflow from inside the pixel.
B: In some portions, ink overflowed from the inside of the pixel to the upper surface of the partition wall.
C: Ink overflowed from the inside of the pixel to the upper surface of the partition wall on the entire surface.

<Thickness>
About the board | substrate with a partition obtained by each Example and the comparative example, the thickness of the structure before and behind formation of the layer (G) containing a color conversion luminescent material was measured using the surfcom stylus type film thickness measuring device, By calculating the difference, the thickness of the layer (G) containing the color conversion luminescent material was measured. For Examples 20 to 22, the thickness of the low refractive index layer (H) is further set. For Examples 23 to 24, the thickness of the color filter is set. For Example 26, the thickness (height) of the light shielding partition is set. It measured similarly.

In Examples 21 to 22 and 24 to 25, a cross section perpendicular to the substrate was exposed using a polishing apparatus such as a cross section polisher, and the cross section was enlarged and observed with a scanning electron microscope or a transmission electron microscope. As a result, the thickness of each of the inorganic protective layers I to IV was measured.

<Luminance>
Using a planar light emitting device equipped with a commercially available LED backlight (peak wavelength: 465 nm) as a light source, a substrate with a partition wall obtained by each Example and Comparative Example so that the layer containing the color conversion light emitting material is on the light source side It installed on the planar light-emitting device. A current of 30 mA is passed through the planar light emitting device to turn on the LED element, and using a spectral radiance meter (CS-1000, manufactured by Konica Minolta), luminance (unit: cd / m ² ) based on the CIE1931 standard is obtained. Measurement was made as the initial luminance. However, the evaluation of the luminance was performed by a relative value with the initial luminance of Comparative Example 9 being 100 as a standard. In addition, when the crack generate | occur | produced in the partition, since exact value cannot be obtained because of a crack etc., evaluation was not implemented.

Further, after the LED element was lit for 48 hours at room temperature (23 ° C.), the luminance was measured in the same manner, and the change with time of the luminance was evaluated. However, the evaluation of the luminance was performed by a relative value with the initial luminance of Comparative Example 9 as 100.

<Color characteristics>
On the commercially available white reflector, the partition-attached substrate obtained in each example and comparative example was placed so that the layer containing the color conversion luminescent material was disposed on the white reflector side. Using a spectrocolorimeter (CM-2600d, manufactured by Konica Minolta, measurement diameter φ8 mm), light was irradiated from the substrate side, and a spectrum including specular reflection light was measured.

Color standard BT. That can reproduce almost natural colors. The color gamut defined by 2020 is defined with the three primary colors red, green, and blue on the spectral locus shown in the chromaticity diagram, and the wavelengths of red, green, and blue correspond to 630 nm, 532 nm, and 467 nm, respectively. From the reflectance (R) of three wavelengths of 470 nm, 530 nm, and 630 nm of the obtained reflection spectrum, the emission color of the layer containing the color conversion luminescent material was evaluated according to the following criteria.
A: R ₅₃₀ / (R ₆₃₀ + R ₅₃₀ + R ₄₇₀ ) ≧ 0.55
B: 0.55> R ₅₃₀ / (R ₆₃₀ + R ₅₃₀ + R ₄₇₀ ).

<Display characteristics>
The display characteristics of the display device produced by combining the substrate with partition walls obtained in each Example and Comparative Example and the organic EL element were evaluated based on the following criteria.
A: The green display is a very colorful display device that is clear and excellent in contrast.
B: Although the color is somewhat unnatural, the display device has no problem.

Examples 1 to 13 and Comparative Examples 1 to 7
The negative colored photosensitive compositions of Preparation Examples 1 to 20 were evaluated for resolution, luminous reflectance and heat resistance according to the above evaluation methods. The evaluation results are shown in Tables 6 to 8.

Examples 14 to 26, Comparative Examples 8 to 9
For the substrate with barrier ribs obtained from the negative colored photosensitive compositions of Preparation Examples 15 to 21, the reflectance, OD value, surface contact angle, ink jet coatability, thickness, brightness, color characteristics and display characteristics were determined according to the above evaluation methods. evaluated. However, Comparative Example 8 was not evaluated because cracks occurred in the cured film and the partition walls and an accurate value could not be obtained. Table 9 shows the configuration of each example and comparative example, and Table 10 shows the evaluation results.

1: Substrate 2: Partition wall 3: Layer containing color conversion light emitting 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: light shielding partition X: partition thickness L: partition width a: top view of patterned substrate of the present invention b: top view after forming transparent electrode c: top view after forming transparent insulating film d: metal wiring formation Rear view 11: Glass substrate 12: White light-blocking cured film 13: Transparent electrode 14: Transparent insulating film 15: Metal wiring

Claims (28)

A negative photosensitive coloring composition containing (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, ) The siloxane resin includes 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). Negative photosensitive material containing a 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) in all the repeating units of the (B) siloxane resin. Coloring composition.

(In the above general formulas (1) to (3), R ¹ represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms in which all or part of hydrogen is substituted with fluorine. R ² represents a single bond, —O—, —CH ₂ —CO—, —CO— or —O—CO—, R ³ represents a monovalent organic group having 1 to 20 carbon atoms, R ⁴ May be the same or different and each represents a monovalent organic group having 1 to 20 carbon atoms.) The negative photosensitive coloring composition according to claim 1, wherein the photopolymerizable compound (D) includes a compound having an ethylenically unsaturated double bond and a fluorine atom. The negative photosensitive coloring composition according to claim 1 or 2, wherein the (B) siloxane resin has a refractive index of 1.35 to 1.55 at a wavelength of 587.5 nm. The negative photosensitive coloring composition according to any one of claims 1 to 3, wherein the white pigment (A) has a refractive index of 2.00 to 2.70 at a wavelength of 587.5 nm. 5. The negative photosensitive coloring composition according to claim 1, wherein a difference in refractive index between the white pigment (A) and the (B) siloxane resin at a wavelength of 587.5 nm is 1.16 to 1.26. 6. The method according to claim 1, wherein the white pigment (A) contains particles having a median diameter of 100 to 500 nm of a compound selected from titanium dioxide, zirconium oxide, zinc oxide, barium sulfate and a composite compound thereof. The negative photosensitive coloring composition as described. The negative according to any one of claims 1 to 6, wherein the content of the (B) siloxane resin in the solid content is 10 to 60% by weight, and the content of the (A) white pigment is 20 to 60% by weight. Type photosensitive coloring composition. The negative photosensitive coloring composition according to any one of claims 1 to 7, which is used for forming a partition having a reflectance of 60 to 90% per 10 µm thickness at a wavelength of 550 nm. A cured film of the negative photosensitive coloring composition according to any one of claims 1 to 7. (I) a step of applying a negative photosensitive coloring composition according to any one of claims 1 to 8 on a substrate to form a coating film;
The method for producing a cured film according to claim 9, comprising (II) a step of exposing and developing the coating film, and (III) a step of heating the coating film after the development. The processed substrate with a pattern which has the cured film of Claim 9 patterned on the board | substrate. A substrate with a barrier rib having a partition wall formed of the cured film according to claim 9 on the substrate, wherein the barrier rib has a reflectance of 60 to 90% per 10 μm thickness at a wavelength of 550 nm. The substrate with a partition according to claim 12, wherein the patterned partition has a surface contact angle with respect to propylene glycol monomethyl ether acetate of 10 ° to 70 °. 14. The partition wall according to claim 12, further comprising a patterned light-shielding partition wall having an optical density of 0.1 to 4.0 per 1.0 μm thickness between the substrate and the patterned partition wall. With board. The substrate with barrier ribs according to any one of claims 12 to 14, further comprising a layer containing a color conversion light-emitting material between adjacent barrier ribs. The board | substrate with a partition of Claim 15 in which the said color conversion light-emitting material contains an inorganic fluorescent substance and / or an organic fluorescent substance. The substrate with a partition wall according to claim 16, wherein the color conversion light-emitting material contains a phosphor that emits red or green fluorescence when excited by blue excitation light. The board | substrate with a partition of Claim 16 or 17 in which the said color conversion luminescent material contains a quantum dot. The partition-attached substrate according to claim 16 or 17, wherein the color conversion light-emitting material contains a pyromethene derivative. The partition-attached substrate 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 550 nm on the layer containing the color conversion luminescent material. The substrate with a partition wall according to claim 20, further comprising an inorganic protective layer I having a thickness of 50 to 1,000 nm on the low refractive index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm. The partition-attached substrate according to claim 20 or 21, further comprising an inorganic protective layer II having a thickness of 50 to 1,000 nm below the low refractive index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm. The substrate with a partition wall 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 the color conversion light-emitting material. The substrate with a partition wall according to claim 23, further comprising an inorganic protective layer III having a thickness of 50 to 1,000 nm between the color filter and the layer containing the color conversion luminescent material. 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 1,000 nm on the substrate. The partition-attached substrate 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 include one or more selected from silicon nitride and silicon oxide. A display device comprising: the substrate with partition walls according to any one of claims 12 to 26; and a light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell. The touchscreen which has a processed substrate with a pattern of Claim 11, a transparent electrode, metal wiring, and a transparent film.

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