JP2019113613A - Thermosetting color composition and method for manufacturing color filter for solid-state image sensor - Google Patents

Abstract

To provide a thermosetting color composition for a color filter for a solid-state image sensor, which can suppress damages in an organic film layer when a photoresist is stripped, and a method for manufacturing a color filter using the above composition.SOLUTION: A thermosetting color composition is provided, to be used for manufacturing a color filter for a solid-state image sensor that includes a color pattern formed by patterning a color layer by dry etching. The composition comprises an organic pigment (A), a dispersant (B), a thermosetting compound (C), a solvent (D) and a dye derivative (E), in which the percentage of the organic pigment (A) in the whole solid content of the thermosetting color composition is 50 mass% or more; the dispersant (B) comprises a dispersant (b1) having an acidic functional group and/or a dispersant (b2) having a basic functional group; and the thermosetting compound (C) comprises a glycidyl esterified epoxy compound of sorbitol.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermosetting coloring composition for color filters used in a solid-state imaging device, and more particularly to a thermosetting coloring composition useful for thin films and high definition. The present invention also relates to a method of producing a color filter formed using the thermosetting coloring composition for color filter.

  The solid-state imaging device is provided with a color filter in which organic pixels of plural colors such as red pixels, green pixels and blue pixels are two-dimensionally arrayed on a substrate such as a semiconductor substrate. In this solid-state imaging device, as the pixel size is reduced in recent years, the performance requirement of color separation becomes severe, and thin film formation, rectangle for performance required for color filter to maintain device characteristics such as color shading characteristics and color mixing prevention. And performance such as eliminating overlapping regions where colors overlap between organic pixels are required.

  Specifically, in a color filter for a solid-state imaging device, for example, the thickness is 1 μm or less for thinning of the organic pattern, and 2 μm or less (for example, 0.5 to 2.0 μm) for the pixel pattern size. It tends to be sized.

  Particularly in recent years, the formation ability of, for example, a 1.0 μm pattern or less has come to be questioned because of the demand for further high definition of color filters for solid-state imaging devices. In the conventional photolithography method, thin films and resolution of color filters It is becoming difficult to avoid the tradeoffs of

On the other hand, processing of the organic pattern by dry etching has been proposed (see Patent Documents 1 and 2).
However, in the case of processing by dry etching, it is necessary to peel off the photoresist remaining after the dry etching treatment with a peeling solution, and there is a problem that the organic film layer is damaged by the peeling solution.

Unexamined-Japanese-Patent No. 2003-332310 JP 2008-216970 A

  The present invention has been made in view of the above problems, and a color filter thermosetting coloring composition for a solid-state imaging device capable of suppressing damage to an organic film layer at the time of photoresist peeling, and a color using the same It aims at providing a manufacturing method of a filter.

  As a result of intensive studies to solve the above problems, the present inventors have found that a color filter thermosetting coloring composition for a solid-state imaging device, which comprises a specific thermosetting compound (C) and a dye derivative (E). It has been found that it is possible to sufficiently provide stripping solution resistance by using the above, and the present invention has been made based on this finding.

It is a thermosetting coloring composition used for manufacture of a color filter for solid imaging devices provided with a coloring pattern which carries out patterning of <1> coloring layer by dry etching,
An organic pigment (A), a dispersant (B), a thermosetting compound (C), a solvent (D) and a pigment derivative (E),
The proportion of the organic pigment (A) in the total solid content of the thermosetting coloring composition is 50% by mass or more, and the dispersant (B) has an acidic functional group and / or a dispersant (b1) and / or A thermosetting coloring composition comprising a dispersant (b2) having a basic functional group, and wherein the thermosetting compound (C) contains a glycidyl esterified epoxy compound of sorbitol.

  <2> The thermosetting coloring composition as described above, wherein the organic pigment (A) contains a green pigment (a1).

  <3> The thermosetting coloring composition as set forth above, wherein the green pigment contains at least one selected from pigment green 7, pigment green 36 and pigment green 58.

  <4> The thermosetting coloring composition as described above, wherein the solvent (D) contains a solvent (d1) having a boiling point of 160 ° C. or higher.

  <5> The thermosetting coloring composition as described above, wherein the solvent (d1) having a boiling point of 160 ° C. or more is either cyclohexanol acetate or ethyl 3-ethoxypropionate.

  <6> The ethylenically unsaturated monomer in which the dispersant (B) contains a dispersant (b1) having an acidic functional group, and the dispersant (b1) having an acidic functional group contains (meth) acrylate The thermosetting coloring composition as described above, which has a site (b1-A) formed by polymerization, and the theoretical value of the glass transition temperature of the site (b1-A) is 40 ° C. or higher.

  The <7> above-mentioned acidic functional group is an aromatic carboxyl group, The above-mentioned thermosetting coloring composition characterized by the above-mentioned.

  The theoretical value of the glass transition temperature of the <8> site | part (b1-A) is 80 degreeC or more, The said thermosetting coloring composition characterized by the above-mentioned.

  <9> The thermosetting coloring composition as set forth above, wherein the green pigment is pigment green 36.

  <10> (X) A step of forming a colored layer using the thermosetting coloring composition, and (Y) a step of patterning the colored layer by dry etching How to make a filter.

  <11> The step of forming the (X) colored layer, (X-1) a step of forming a coating film containing the thermosetting coloring composition, and (X-2) heat curing the coating film The step of obtaining the colored layer, wherein the step of patterning by the (Y) dry etching comprises (Y-1) forming a photoresist layer on the colored layer, (Y-2) exposing and developing Thereby patterning the photoresist layer to obtain a resist pattern, (Y-3) patterning the colored layer by dry etching using the resist pattern as an etching mask to form a colored pattern, and (Y -4) The above-mentioned solid-state image pickup device characterized in that it comprises a step of bringing a stripping solution into contact with the resist pattern to remove the resist pattern from the colored pattern. Only method of producing a color filter.

  <12> The method for producing a color filter for a solid-state imaging device as described above, wherein the peeling solution contains at least one member selected from the group consisting of N-methyl pyrrolidone, dimethyl sulfoxide and monoethanolamine.

  The color filter thermosetting coloring composition for solid-state imaging devices of the present invention can provide an organic film having high resistance to the stripping solution in the stripping step of the photoresist, and the production of color filters for solid-state imaging devices by dry etching It becomes possible.

It is a figure which shows 1 process of the formation construction method patterned by dry etching. It is a figure which shows 1 process of the formation construction method patterned by dry etching. It is a figure which shows 1 process of the formation construction method patterned by dry etching. It is a figure which shows 1 process of the formation construction method patterned by dry etching. It is a figure which shows 1 process of the formation construction method patterned by dry etching.

  Hereinafter, embodiments of the present invention will be described in detail.

  In addition, in this specification, when it describes with "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", Unless otherwise stated, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It represents ".

  In addition, “CI” listed in the present specification means a color index (CI).

  Further, in the present specification, the “color filter for solid-state imaging device” means a color filter used for a solid-state imaging device provided with a coloring pattern formed by patterning a coloring layer by dry etching.

  The color filter thermosetting coloring composition for solid-state imaging devices of the present invention comprises a pigment (A), a dispersing agent (B), a thermosetting compound (C), a solvent (D) and a dye derivative (E). A coloring composition, wherein the proportion of the pigment (A) in the total solid content of the thermosetting coloring composition is 50% by mass or more, and the dispersing agent (B) has an acidic functional group ( b1) and / or a dispersant (b2) having a basic functional group, and characterized in that the thermosetting compound (C) contains a glycidyl esterified epoxy compound of sorbitol.

<Organic pigment (A)>
The organic pigment (A) used in the present invention can be a combination of a plurality of organic pigments such as red pigment, blue pigment, green pigment, yellow pigment and purple pigment. Specifically, diketopyrrolopyrrole-based pigments, azo-based pigments such as azo, disazo or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, anthraquinone such as biolanthrone Based pigments, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, srene pigments, metal complex pigments and the like can be mentioned.

Specifically as these organic pigments,
As a red pigment, for example, C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 01 1
, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263 264, 265, 266, 267, 268, 269, 270, 271, 272, Or the like can be mentioned 73,274,275,276. it can.

  As an orange pigment which works similarly to a red pigment, for example, C.I. I. Orange pigments such as pigment orange 36, 38, 43, 51, 55, 59, 61 can be used.

  Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment red 254, C.I. I. It is particularly preferable to use pigment red 177.

  Examples of blue pigments include C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 6.

  As a green pigment, for example, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 or 59 can be mentioned. . Among these, from the viewpoint of obtaining high coloring power, C.I. I. It is preferable to use at least one selected from the group consisting of C.I. Pigment Green 7, 36 and 58.

  Examples of yellow pigments include C.I. I. Pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining high coloring power, preferably C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 185.

  Examples of purple pigments include C.I. I. Pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 25, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of obtaining high coloring power, preferably C.I. I. Pigment violet 19 or 23, and more preferably C.I. I. Pigment violet 23.

  In particular, it is preferable to combine a blue pigment, a yellow pigment and a purple pigment as the organic pigment in the present invention, and as a combination ratio, 32 to 45% by weight of a blue pigment with respect to the whole organic pigment (A) 30 to 40% by weight, and 20 to 30% by weight purple pigment are preferred.

  In the color filter thermosetting coloring composition for solid-state imaging devices of the present invention, the colorant concentration relative to all nonvolatile components is preferably 50% by weight or more, more preferably 60 to 85, from the viewpoint of obtaining sufficient color characteristics. It is weight%. When the concentration of the colorant component is less than 50% by weight, sufficient color characteristics may not be obtained, and when it exceeds 90% by weight, the concentration of the colorant carrier such as the binder resin becomes low, and the coloring composition The stability may be worse.

<Finening of pigment>
When a pigment is used in the present invention, it is preferable to use it in a finely divided form, but the method of making it finely divided is not particularly limited. For example, any of wet grinding, dry grinding and solution deposition methods can be used. Thus, it is possible to carry out salt milling by a kneader method, which is one of wet grinding. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. In addition, since a color filter having a high contrast ratio can be formed, the thickness is preferably 100 nm or less. The particularly preferred range is in the range of 25 to 85 nm. The primary particle diameter of the pigment was determined by a method of directly measuring the size of the primary particles from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was defined as the particle size of the pigment particles. Next, with respect to 100 or more pigment particles, the volume of each particle is determined by approximating to the cube of the determined particle diameter, and the volume average particle diameter is taken as the average primary particle diameter.

  The coloring composition of the present invention is excellent in resistance even in the case of using such a finely-divided pigment by containing an epoxy compound together with a specific pigment dispersant containing a thermally crosslinkable functional group. And a color composition for color filters having high brightness and contrast ratio.

  In the salt milling process, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated while using a kneader such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill etc. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used in terms of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is easily evaporated, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

  When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid at room temperature, preferably water insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Other colorants>
The thermosetting coloring composition of this invention can contain other coloring agents other than an organic pigment (A) as a coloring agent. As another coloring agent, a well-known inorganic pigment, dye, etc. are mentioned, and it can also be used in combination of 2 or more types.

(Inorganic pigment)
As inorganic pigments, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthesis Examples thereof include metal oxide powders such as iron black, titanium oxide and iron tetraoxide, metal sulfide powders, metal powders and the like. Inorganic pigments may be used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between chroma and lightness.

(dye)
The coloring composition according to the embodiment of the present invention can also use a dye as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, architectural dyes, sulfur dyes and the like can be used. In addition, these may be in the form of derivatives or laked lakes of dyes.

Furthermore, acid dyes having an acidic group such as sulfonic acid and carboxylic acid, and in the case of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or a salt forming compound with a nitrogen-containing compound such as a primary amine compound, or using as a salt forming compound by using a resin component having these functional groups as a salt forming compound, or using it as a sulfone amide compound In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable.
Further, a salt forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in fastness, and more preferably, the compound having an onium base is a resin having a cationic group in a side chain.

  In the case of the form of a basic dye, it can be used by using an organic acid or perchloric acid or a metal salt thereof to form a salt. The salt forming compound of the basic dye is preferable because it is excellent in resistance and compatibility with the pigment, and the basic dye and the organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound which is a counter component which works as a counter ion It is more preferable to use a salt forming compound obtained by forming a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is a thing.

Moreover, when it has a polymeric unsaturated group in pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.
When the dye has an oxetane group, the coloring composition containing the dye is excellent in heat resistance after curing. The dye having an oxetane group can be achieved, for example, by using an ethylenically unsaturated monomer containing an oxetane structure in a resin constituting a salt forming compound containing the dye. By having an oxetane group, the coloring composition containing the colorant is excellent in heat resistance after curing.

  The chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, Pyridone dyes, etc., carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, diarylmethane dyes, triarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazines) Dyes, azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanines Dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, methine dyes, cationic dyes, perylene dyes, diketopyrrolopyrrole dyes , Quinacridone dyes, ansanthrone dyes, isoindolinone dyes, isoindoline dyes, indanthrone dyes, coumarin dyes, pyranthrone dyes, flavanthrone dyes, perinone dyes, and metal complex compounds thereof Although the pigment | dye structure derived from the dye chosen from dye etc. can be mentioned, it is not limited to these. Specific dye compounds that can form a dye structure are described in “New Dye Handbook” (Organic Synthetic Chemistry Association, edited by Maruzen, 1970), “The Society of Dyers and colourists”, “Dye Handbook” (Ogawara et al. Ed., Kodansha, 1986).

<Dispersing agent (B)>
The thermosetting coloring composition of the present invention further comprises a dispersant (B), which is a dispersant (b1) having an acidic functional group and / or a dispersant having a basic functional group ((B)) and b). By including the dispersant, the dispersion stability of the coloring composition of the present invention becomes better, and a thermosetting composition excellent in viscosity stability can be obtained. In addition, since the pigment is well dispersed in the organic film layer, the uniformity of the coating film is improved, so that the resistance to the stripping solution is increased, and it can be applied to the method for producing a color filter by dry etching. Become.

The dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and adsorbs to the additive colorant to stabilize the dispersion to the colorant carrier Work to The dispersant is preferably a resin-type dispersant from the viewpoint of the compatibility in the coloring composition.
Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

(Dispersant having an acidic functional group (b1), dispersant having a basic functional group (b2))
Among the above-mentioned dispersants, both the dispersant having an acidic functional group (b1) and the dispersant having a basic functional group (b2), because the viscosity of the dispersion becomes low and the viscosity stability is excellent when added in a small amount Is preferred.

  Among the dispersant (b1) having an acidic functional group and the dispersant (b2) having a basic functional group, the dispersant (B) may include only the dispersant (b1) having an acidic functional group, Only the dispersant (b2) having a basic functional group may be contained. The dispersant (B) may be composed of only the dispersant (b1) having an acidic functional group, or may be composed of only the dispersant (b2) having a basic functional group.

  The proportion of the total of the dispersant (b1) having an acidic functional group and the dispersant (b2) having a basic functional group in the dispersant (B) is, for example, in the range of 80% by mass to 100% by mass Preferably, it is in the range of 90% by mass to 100% by mass.

  The proportion of the dispersant having the acidic functional group (b1) in the total amount of the dispersant having the acidic functional group (b1) and the dispersant having the basic functional group (b2) is, according to one example, 30% by mass It is the above, Preferably it is 50 mass% or more. The proportion is, according to another example, in the range of 20% by mass to 80% by mass, preferably in the range of 30% by mass to 70% by mass.

  The dispersant having a basic functional group (b2) is a nitrogen atom-containing graft copolymer, or a nitrogen atom-containing graft group having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain. Acrylic block copolymers and urethane polymer dispersants are preferred.

  Acrylic-based ester copolymers, acrylic-based block copolymers, and urethane-based polymer dispersions having a functional group containing a carboxylic acid group, a phosphoric acid group, a sulfonic acid group and the like as the dispersant (b1) having an acidic functional group Agents are preferred. The dispersant (b1) having an acidic functional group has a site (b1-A) formed by polymerizing an ethylenically unsaturated monomer containing (meth) acrylate, and the glass transition of the (b1-A) site It is preferable that the theoretical value of the temperature is 40 ° C. or more because the resistance to the stripping solution can be improved, and particularly preferably 80 ° C. or more. A further preferable example of the polymer dispersant having an acidic functional group is a dispersant (b11) having an aromatic carboxyl group. When the dispersant (b11) having an aromatic carboxyl group is used as the dispersant (b1) having an acidic functional group, the resistance to the stripping solution is preferably high.

  The dispersant (b11) having an aromatic carboxyl group is one having an aromatic carboxyl group in its molecule. The production method thereof is, for example, a production method 1 wherein an aromatic tricarboxylic acid anhydride (F1) and / or an aromatic tetracarboxylic acid dianhydride (F2) is reacted with a polymer (E) having a hydroxyl group, an aromatic carboxyl Production method 2 of producing a polymer using a monomer having a group, an aromatic tricarboxylic acid anhydride (F1) and / or an aromatic tetracarboxylic acid dianhydride (F2) while polymerizing a monomer having a hydroxyl group And the like, or any of the production methods 3 and 4. Among these, from the viewpoint of pigment dispersibility, one prepared by the production method 1 in which the number of aromatic carboxyl groups in the dispersant (B) can be more easily controlled is preferable.

  That is, as the dispersant (b11) having an aromatic carboxyl group, a polymer (E) having a hydroxyl group, an aromatic tricarboxylic acid anhydride (F1) and / or an aromatic tetracarboxylic acid dianhydride (F2) It is preferable that it is a dispersing agent which makes it react, More preferably, the polymer (E) which has a hydroxyl group is a polymer which has a hydroxyl group at one end, More preferably, it is a polymer which has a hydroxyl group at one end The stability can be improved by using a dispersant in which (E) is a polymer having two hydroxyl groups at one end.

  The polymer having a hydroxyl group at one end is preferably a polyester having a hydroxyl group at one end and / or a polyether polymer, or a vinyl polymer having a hydroxyl group at one end, particularly preferably From the point of dispersion stability, a vinyl polymer having a hydroxyl group at one end is used.

  Further, as the aromatic tricarboxylic acid anhydride (F1) and / or the aromatic tetracarboxylic acid dianhydride (F2), particularly, the aromatic tetracarboxylic acid dianhydride (F2) can be added to the storage stability of the pigment dispersion. It is preferable because it is excellent.

  As a method of obtaining the dispersant (b11) having such an aromatic carboxyl group, the ethylenically unsaturated monomer is subjected to radical polymerization in the presence of a compound (e11) having two hydroxyl groups and one thiol group in the molecule. And a hydroxyl group in a polyol (e1) containing at least a vinyl polymer (e12) having two hydroxyl groups at one end, and a polycarboxylic acid anhydride containing at least an aromatic tetracarboxylic acid dianhydride (F2) And (f) reacting with the acid anhydride group in (f).

  Among the dispersants (b11) having such an aromatic carboxyl group, it is preferable to contain methyl methacrylate as a constituent monomer of the vinyl polymer (g2) site, because of the effect of increasing the resistance to the stripping solution, it is preferable. More preferably, the content of methyl methacrylate is 30% or more, more preferably 50% or more, and still more preferably 65% or more by weight ratio in the polymer. If it is less than 30%, the resistance to the stripping solution may be lowered.

  As the dispersant (b11) having an aromatic carboxyl group, known techniques described in WO 2008/007776 Pamphlet, JP 2009-185277 A, JP 2008-029901 A can be used. .

  As a commercially available dispersing agent (b1) having an acidic functional group, Disperbyk-101, 110, 111, 130, 140, 170, 171, 174, 180, 2001, 2020, 2025, 2070 or BYK manufactured by Big Chemie Japan Ltd. -P104, P104S, 220S, etc., SOLSPERSE-3000, 13240, 13650, 13940, 16000, 17000, 18000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 32600, 32600, 32600, 32600, 32600, 32600, 32600, 32600, 32500, 32600, 32500, 32600, etc. made by Japan Lubrizol Corporation 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, etc., BASF EFKA-4008, 4009, 4010, 4406, 50 0,5065,5066,5070, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB821, PB822, and the like.

  As a commercially available dispersant (b2) having a basic functional group, Disperbyk-101, 108, 116, 130, 140, 161, 162, 163, 164, 165, 166, 180, 182, manufactured by Big Chemie Japan Ltd. 183, 184, 185, 2000, 2001, 2020, 2025, 2050, 20150, 2150 or BYK-6919, etc., manufactured by Nippon Lubrizol, SOLSPERSE-13240, 13650, 13940, 20000, 24000, 26000, 31845, 32000, 32500 32550, 34750, 35100, etc., BASF EFKA-4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4 03,4406,4300,4330,4500,4510,4530,4550,4560,4800, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER, include the PB711, PB821, PB822 and the like.

  The resin type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the pigment, and more preferably in an amount of about 10 to 40% by weight from the viewpoint of film formability.

<Thermosetting compound (C)>
The thermosetting coloring composition for color filters of the present invention is characterized by containing a glycidyl esterified epoxy compound of sorbitol as a thermosetting compound. The inclusion of a glycidyl esterified epoxy compound of sorbitol has the effect of promoting the cross-linking of the coating film at the time of firing of the organic film layer using the colored composition of the present invention and increasing the resistance to the stripping solution. It becomes possible to apply to the manufacturing method of a color filter.

  Examples of glycidyl esterified epoxy compounds of sorbitol include commercially available Denacol EX-611, EX-612, EX-614, EX-614B, and EX-622 manufactured by Nagase ChemteX Corporation.

  The thermosetting coloring composition for color filters of the present invention may further contain other thermosetting compounds in combination. The ratio of the glycidyl-esterified epoxy compound of sorbitol to the thermosetting compound (C) is, for example, in the range of 1% by mass to 20% by mass, and preferably in the range of 5% by mass to 10% by mass. The thermosetting compound (C) may be composed of a glycidyl esterified epoxy compound of sorbitol.

  As other thermosetting compounds that can be used in combination with glycidyl esterified epoxy compounds of sorbitol, for example, epoxy compounds other than glycidyl esterified epoxy compounds of sorbitol, benzoguanamine compounds, rosin modified maleic acid compounds, rosin modified fumaric acid compounds And melamine compounds, urea compounds, cardo compounds and phenol compounds, but the present invention is not limited thereto. Among these, epoxy compounds other than glycidyl esterified epoxy compounds of sorbitol are preferable. At the time of firing of the organic film layer using the coloring composition of the present invention, the cross-linking of the coating film proceeds, and the effect of increasing the resistance to the peeling liquid is obtained.

  Commercial products of epoxy compounds other than glycidyl-esterified epoxy compounds of sorbitol include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P, Epicoat 1004, Epicoat 1256 (the above are trade names) Mitsubishi Chemical Co., Ltd. product, TECHMORE VG 3101L (trade name; Mitsui Chemical Co., Ltd. product), EPPN-501H, 502H (trade name; Nippon Kayaku Co., Ltd. product), JER 1032 H60, JER 157 S 65, 157 S 70 (Products Name: Mitsubishi Chemical Co., Ltd., EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), JER 152, JER 154 (trade name: Mitsubishi Chemical Co., Ltd.), EOCN-102S, EOCN-103S , EOCN-104 EOCN-1020 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (trade name; manufactured by Daicel Corporation), Denacol EX-810, EX-830, EX-851 , EX-611, EX-512, EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Co., Ltd.), etc., but are limited thereto is not.

  In the color filter thermosetting coloring composition for a solid-state imaging device of the present invention, the concentration of the thermosetting compound with respect to all nonvolatile components is preferably 1 to 30% by weight or more from the viewpoint of obtaining sufficient thermosetting. Preferably, it is 3 to 20% by weight. If the concentration of the thermosetting compound component is less than 1% by weight, sufficient crosslinking may not be obtained at the time of firing, and if it exceeds 30% by weight, the concentration of the colorant component becomes low, and sufficient color characteristics are obtained. You may not be able to get

<Solvent (D)>
The thermosetting coloring composition for color filters of the present invention has a coloring agent sufficiently dispersed in a pigment carrier such as a binder resin or a polyfunctional monomer, and a dry film thickness of 0.2 to 0.2 on a substrate such as a silicon wafer substrate. It is used to facilitate application to form a filter segment by 10 μm.

As the solvent, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene , N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal , N-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin alcohol, tripropylene, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  It is preferable that the solvent contains a solvent having a boiling point of 160 ° C. or more from the viewpoint of suppressing aggregation foreign matter on a substrate such as a silicon wafer substrate. Among them, it is particularly preferable that cyclohexanol acetate (boiling point: 177 ° C.) or ethyl 3-ethoxypropionate (boiling point: 165 ° C.) is contained from the viewpoint of suppressing aggregation foreign matter on a substrate such as a silicon wafer substrate.

  The solvent can be used in an amount of 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Dye derivative (E)>
The thermosetting coloring composition for color filter of the present invention suitably contains a dye derivative when dispersing the pigment in the pigment carrier. The pigment derivative has a large effect of preventing reaggregation of the pigment after dispersion, so the coloring composition formed by dispersing the pigment in the pigment carrier using the dispersion aid has good spectral characteristics and viscosity stability. Not only that, since it also has the effect of protecting the surface of the pigment which is weak in solvent resistance, the chemical resistance of the positive resist used for dry etching to the stripping solution becomes good.

  As dye derivatives used in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group and the like in the organic dye residue can be used. For example, compounds having an acidic functional group such as sulfo group, carboxy group, phosphoric acid group and the like, amine salts thereof, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, phenyl group or phthalimido The compound which has neutral functional groups, such as an alkyl group, is mentioned. JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP 2003-128669, JP 2004-091497, JP 2007-156395, JP 2008-094873, JP 2008-094986, JP 2008-095007, JP 2008 JP-195916-A, Patent No. 4585781-A, JP-2006-291194-A, JP-A-2007-226161, JP-A-2007-314681, JP-A-2007-314785, JP-A-2012-226110 JP-A-2017-165820 and JP-A-2005- 81383 JP, include known dye derivative according to such. In these documents, a dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant or simply a compound, etc. However, the organic dye residue described above may be an acidic group, a basic group, a neutral group, etc. The compound which has a functional group of is synonymous with a pigment derivative. Moreover, these can be used individually or in mixture of 2 or more types.

  Among the dye derivatives, specifically, compounds represented by the following formulas (130-1) to (140-5) are particularly preferable in view of viscosity stability and chemical resistance.

  The compounding amount of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more based on 100 parts by weight of the pigment from the viewpoint of improving the dispersibility of the additive pigment. . Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, with respect to 100 parts by weight of the pigment.

<< Leveling agent >>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 1.0 parts by weight with respect to 100 parts by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

  The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.

  Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

<< Production Method of Colored Composition for Color Filter >>
The coloring composition for a color filter of the present invention comprises a colorant, a colorant carrier such as a resin and / or a solvent, optionally together with a dispersion aid, a kneader, a 2-roll mill, a 3-roll mill, a ball mill It can be finely dispersed and manufactured using various dispersion means such as horizontal sand mill, vertical sand mill, annular bead mill, or attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.

  When the solubility of coloring agents such as dyes is high, specifically, the solubility in the solvent used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is observed, it is finely dispersed and manufactured as described above. There is no need.

(Dispersion aid)
When the colorant is dispersed in the colorant carrier, it may contain a dispersing aid such as a dye derivative or a surfactant as appropriate. Since the dispersion aid has a large effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has spectral characteristics and viscosity stability. Will be better. Dye derivatives are as described above.

  As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  The amount of the surfactant added is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, per 100 parts by weight of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1 parts by weight, the added effect is difficult to be obtained, and when the blending amount is more than 55 parts by weight, the dispersing agent is adversely affected by the excess dispersant. May affect.

  In the forming method of patterning by dry etching used in the present invention, a resin pattern in the shape of an object is formed on an object forming layer as a colored layer, and dry etching is performed using this resin pattern, ie, a resist pattern as a mask, This is a method of transferring the shape of an object to an object forming layer to perform patterning. Specifically, as shown in FIGS. 1 to 5, a color filter thermosetting coloring composition is used as a color filter layer 2 (colored layer 2) formed on a substrate 1, and a photosensitive resin is formed thereon. A resin pattern 4 (resist pattern 4) having a target shape, which is formed by patterning the layer 3 (photoresist layer 3), is formed of a photosensitive resin, and is used as a mask to form the resin pattern 4 as a color filter. Transfer to the layer 2 to form a color filter pattern 5 (colored pattern 5) which is an object.

The manufacturing method of the color filter for solid-state image sensors which concerns on embodiment is demonstrated more concretely.
First, as shown in FIG. 1, a coating film containing the thermosetting coloring composition according to the embodiment is formed on a substrate 1. Next, this coating film is thermally cured to form a colored layer 2.

  Subsequently, as shown in FIG. 2 and FIG. 3, after forming a photoresist layer 3 on the colored layer 2, the photoresist layer 3 is patterned by exposing and developing the photoresist layer 3 to form a resist Form pattern 4

Furthermore, as shown in FIG. 4 and FIG. 5, after the colored layer 2 is patterned by dry etching using the resist pattern 4 as an etching mask to form a colored pattern 5, a peeling solution is brought into contact with the resist pattern 4. And removing the resist pattern 4 from the colored pattern 5.
The color filter for a solid-state imaging device can be manufactured by the method described above.

The plasma source used for dry etching is CCP (Capacitively Coupled Plasma), EC
R (Electron Cyclotron resonance Plasma), HWP (Helicon Wave Plasma), ICP (Inductively Coupled Plasma), SWP (Surface Wave Plasma), etc. can be used, but ICP having high plasma stability and suitable for micro processing is particularly preferable. preferable.

  The gas used for dry etching is preferably a reactive (oxidative / reductive) gas, that is, an etchable gas, for example, a gas having a halogen element such as fluorine, chlorine or bromine in its structure, and the like For example, a gas having an element of oxygen or sulfur in its composition can be used. In the case of etching by ion bombardment, it is possible to use a Group 18 element (noble gas) such as helium or argon. Further, by mixing the reactive gas and the rare gas, it is possible to etch the material to be etched in a rectangular shape by the ion assist reaction, and it is particularly preferable to perform the etching with a mixed gas of the reactive gas and the rare gas.

  As the peeling solution, either an organic solvent or an inorganic solvent may be used, and one having high peelability and no damage to the thermosetting coloring composition is selected. For example, those containing at least one selected from the group consisting of N-methyl pyrrolidone, dimethyl sulfoxide and monoethanolamine are suitable.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. Also, "PGMAC" means methoxypropyl acetate.

  Moreover, the measuring method of the weight average molecular weight (Mw) of resin is as follows.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

  Then, the manufacturing method of the binder resin solution used by the Example and the comparative example, the manufacturing method of a refinement | miniaturization pigment, and the manufacturing method of a pigment dispersion are demonstrated.

<Method of producing binder resin solution>
(Acrylic resin solution 1)
196 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen and then dropped. From pipe, 24.0 parts of benzyl methacrylate, 20.2 parts of n-butyl methacrylate, 14.9 parts of 2-hydroxyethyl methacrylate, paracumyl phenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) 24.7 A mixture of 1 part and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of acrylic resin.
After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and PGMAC is added to the previously synthesized resin solution so that the non-volatile content is 20% by weight. Thus, an acrylic resin solution 1 was prepared. The weight average molecular weight (Mw) was 26,000.

<Method of producing dispersant>
[Method of producing dispersant (b1) having an acidic functional group]
(Dispersive agent having an acidic functional group (b1-1))
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 70.0 parts of methyl methacrylate, 10.0 parts of ethyl acrylate and 20.0 parts of t-butyl methacrylate were charged and purged with nitrogen gas. The reaction vessel is heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol, 0.1 parts of 2,2′-azobisisobutyronitrile, and 45.3 parts of methoxypropyl acetate Solution was added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. At this time, the weight average molecular weight was 4,000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 70.1 parts of methoxypropyl acetate, 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst 0.2 parts were added and allowed to react at 120 ° C. for 7 hours. The reaction was terminated after confirming that acidity of 98% or more was half-esterified by measurement of acid value. After completion of the reaction, methoxypropyl acetate is added to prepare a non-volatile content of 50% by weight, and a dispersant (b1-1) having an acidic functional group with an acid value of 43 mg KOH / g and a weight average molecular weight of 9,500 A solution was obtained.

(Dispersant having an acidic functional group (b1-2) to (b1-5))
The synthesis is carried out in the same manner as the dispersing agent (b1-1) except that the raw materials and charging amounts described in Table 3 are used, and methoxy of dispersing agents (b1-2) to (b1-5) having an acidic functional group A propyl acetate solution was obtained.

  The composition list of the obtained dispersants (b1-1) to (b1-5), and the glass transition temperature in a portion (b1-A) formed by polymerizing an ethylenically unsaturated monomer containing (meth) acrylate The theoretical value list of (Tg) is shown in Table 1. Here, the theoretical value of the glass transition temperature is a value calculated as the reciprocal of the sum of the weight ratio of each component of (b1-A) part and the inverse number of the Tg of the homopolymer of each component. .

  The raw materials used in Table 3 are listed below.

Ethylenically unsaturated monomer
MAA: methacrylic acid MMA: methyl methacrylate EA: ethyl acrylate t-BMA: tert-butyl acrylate [compound having two hydroxyl groups and one thiol group in the molecule]
Thioglycerol: 3-mercapto-1,2-propanediol (radical polymerization initiator)
-AIBN: 2,2'-azobisisobutyronitrile (organic solvent)
・ Methoxypropyl acetate (tetracarboxylic acid dianhydride)
PMA: pyromellitic dianhydride (made by Daicel Chemical Industries, Ltd.)
· TMA: trimellitic anhydride (esterification reaction catalyst)
· DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by San-Apro Co., Ltd.)

[Method of producing dispersant (b2) having basic functional group]
(Dispersant with basic functional group (b2-1))
Charge 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine (hereinafter referred to as TMEDA) into a reactor equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and flow nitrogen While stirring, the mixture was stirred at 50 ° C. for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed from conversion of non-volatile matter that the polymerization conversion rate was 98% or more.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were charged into the reactor, and the reaction was continued while maintaining the atmosphere at 110 ° C. under a nitrogen atmosphere. After 2 hours from the addition of dimethylaminoethyl methacrylate, the polymerization solution is sampled to measure the solid content, and the non-volatile component is converted to confirm that the polymerization conversion ratio of the second block is 98% or more. The polymerization was stopped by cooling.
Methoxypropyl acetate was added to the previously synthesized block copolymer solution so as to have a non-volatile content of 50% by weight. Thus, a poly (meth) acrylate skeleton having an amine value of 71.4 mg KOH / g, a weight average molecular weight of 9,900 (Mw) and a non-volatile content of 50 wt% per solid content, and having a tertiary amino group The dispersant (b2-1) having a basic functional group was obtained.

(Dispersant having basic functional group (b2-2) to (b2-5))
The synthesis is carried out in the same manner as the dispersant (b2-1) except that the raw materials and the preparation amounts described in Table 4 are used, and the methoxy of the dispersants (b2-2) to (b2-5) having a basic functional group A propyl acetate solution was obtained.

The raw materials used in Table 4 are listed below.
MMA: methyl methacrylate n-BMA: n-butyl methacrylate TMEDA: tetramethylethylenediamine PGMAc: methoxypropyl acetate DM: dimethylaminoethyl methacrylate

<Production of yellow finely divided pigment (Y1)>
Isoindolinone yellow pigment 3C. I. Pigment Yellow 139 (PY 139, "PALIOTOL YELLOW D 1819" manufactured by BASF Corporation), 100 parts of crushed sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C for 4 hours. The mixture is poured into 3000 parts of hot water and stirred for about 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtering and washing with water repeatedly to remove salt and solvent, and then 24 hours at 80 ° C. Drying gave 96 parts of a yellow finely divided pigment (Y1).

<Method of producing pigment dispersion>
(Green pigment dispersion (GP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed for 5 hours with a paint shaker SO400 (manufactured by Skandex) using zirconia beads of 1 mm in diameter. Thereafter, 30.0 parts of methoxypropyl acetate were added, and the mixture was filtered through a 5 μm filter to obtain a green pigment dispersion (GP-1).
C. I. Pigment green 58: 6.7 parts (manufactured by DIC "FASTOGEN GREEN A110")
C. I. Pigment yellow 150: 6.7 parts ("E4GN" manufactured by LANXESS Corporation)
Dye Derivative Formula (131-5): 1.6 parts Dispersant solution having an acidic functional group (b1-1): 5.0 parts Dispersant solution having a basic functional group (b2-1): 5.0 parts Methoxy propyl acetate: 75.0 parts

(Green pigment dispersion (GP-2 to 21))
Green pigment dispersions (GP-2 to 21) were obtained in the same manner as the green pigment dispersion (GP-1) except that the composition and the blending amount (parts by weight) described in Table 5 were changed.

The abbreviations in Table 5 are shown below.
[Pigment A]
PG 58-1: C.I. I. Pigment green 58 ("FASTOGEN GREEN A110" manufactured by DIC)
PG 58-2: C.I. I. Pigment green 58 ("FASTOGEN GREEN A210" manufactured by DIC)
PG 36: C.I. I. Pigment green 36 ("CF-G-6YK" manufactured by Toyo Color Co., Ltd.)
PG 7: C.I. I. Pigment green 7 ("Fastgen Green S" manufactured by DIC Corporation)
PY 150: C.I. I. Pigment Yellow 150 ("E4GN" manufactured by LANXESS Corporation)
PY 139: C.I. I. Pigment yellow 138 (yellow finely divided pigment (Y1))

<Method of producing thermosetting coloring composition>
Example 1
(Preparation of thermosetting coloring composition (GT-1))
The following mixture (total 100 parts) was stirred and mixed so as to be uniform, and then filtered with a 1.0 μm filter to obtain a thermosetting coloring composition (GT-1).
Pigment dispersion (GP-1): 77.2 parts thermosetting compound C: 1.6 parts manufactured by Nagase ChemteX "Denacol EX-611"
Leveling agent solution: 1.0 part "FZ-2122" manufactured by Toray Dow Corning
(A solution obtained by diluting 1 part of (100% by weight of non volatile matter) with 99 parts of cyclohexanone)
Solvent (D): 10.2 parts methoxypropyl acetate
Solvent (d1): 10.0 parts of cyclohexanol acetate

[Examples 2-24, Comparative Examples 1-8]
(Preparation of thermosetting coloring composition (GT-2 to 32))
Thermosetting coloring composition (GT-2 to 32) in the same manner as the thermosetting coloring composition (GT-1) except that the composition and the blending amount (parts by weight) described in Table 6-9 are changed. Got).

<Evaluation of Thermosetting Colored Composition>
The resulting thermosetting colored composition was evaluated for viscosity stability, release liquid resistance, and coating film foreign matter. The results are shown in Table 6-96.

<Viscosity stability evaluation>
The viscosity at 25 ° C. immediately after preparation of the thermosetting coloring composition and the viscosity after storage for 6 months in a thermostatic chamber at 13 ° C. were measured using an E-type viscometer (TUE-20L type manufactured by TOKI SANKGYO). It measured by 20 rPm. The viscosity of the colored composition on the day of preparation is the initial viscosity (η0: mPa · s) and the viscosity (粘度 1: mPa · s) after storage for 1 month in a thermostatic chamber at 13 ° C. It evaluated by the standard. X is a level which can not be put to practical use.
:: 1/1 / η0 is 1.10 or less ○: 1/1 / η0 is greater than 1.10 and less than 1.20 ×: 1/1 / η0 is 1.20 or more

<Peeling liquid resistance evaluation 1>
The thermosetting coloring composition obtained so that a dried coating film may be set to 0.7 μm is applied on three glass substrates of 100 mm × 100 mm and 1.1 mm thickness by using a spin coater, respectively, and then it is heated in an oven. Heated and fired at 230 ° C. for 30 minutes. The obtained three coated substrates are immersed in a peeling solution (a mixed solution of N-methylpyrrolidone / dimethyl sulfoxide = 4/6) for 1 minute, for 3 minutes or for 5 minutes, and then observed using an optical microscope. The evaluation was done. The ranks of the ratings are as follows. X is a level which can not be put to practical use.
◎: Good for all substrates soaked for 3 minutes, 3 minutes, 5 minutes with no change in appearance.
○: 1 minute, 3 minutes soaking does not change appearance, but 5 minutes soaking causes cracks, surface roughening, or foreign matter.
Δ: No change in appearance by immersion for 1 minute, but cracks, surface roughness, or foreign matter are generated by immersion for 3 minutes.
×: 1 minute soaking, cracks, surface roughening, or foreign matter

<Peeling liquid resistance evaluation 2>
The thermosetting coloring composition obtained so that a dried coating film may be set to 0.7 μm is applied on three glass substrates of 100 mm × 100 mm and 1.1 mm thickness by using a spin coater, respectively, and then it is heated in an oven. Heated and fired at 230 ° C. for 30 minutes. The obtained three coated substrates are immersed in a peeling solution (a mixed solution of N-methylpyrrolidone / monoethanolamine = 5/5) for 1 minute, for 3 minutes or for 5 minutes, and then using an optical microscope. It observed and evaluated. The ranks of the ratings are as follows. X is a level which can not be put to practical use.
◎: Good for all substrates soaked for 3 minutes, 3 minutes, 5 minutes with no change in appearance.
○: 1 minute, 3 minutes soaking does not change appearance, but 5 minutes soaking causes cracks, surface roughening, or foreign matter.
Δ: No change in appearance by immersion for 1 minute, but cracks, surface roughness, or foreign matter are generated by immersion for 3 minutes.
×: 1 minute soaking, cracks, surface roughening, or foreign matter

<Coating film foreign body evaluation>
On a glass substrate of 100 mm × 100 mm and 1.1 mm thickness, a spin coater is used to apply the thermosetting coloring composition obtained so that the dried coating film is 0.7 μm, and 70 using a hot plate. Dried for 1 minute. The substrate of the resulting dried coated film was visually evaluated for foreign matter. X is a level which can not be put to practical use.
:: no foreign matter on the substrate ○: one or more and less than three foreign particles on the substrate Δ: three or more and less than five foreign particles on the substrate x: five or more foreign particles on the substrate

  The raw materials used in Table 6-9 are shown in Table 10.

[Thermosetting compound C]

[Solvent d1]
・ EEP: Ethyl 3-ethoxypropionate ("Eucester EEP" manufactured by Dow Chemical Co.)

  From Table 4, it was shown that the thermosetting coloring composition within the scope of the present invention is excellent in viscosity stability, release liquid resistance, and coating film foreign matter.

Claims (12)

A thermosetting coloring composition for use in the manufacture of a color filter for a solid-state imaging device having a coloring pattern obtained by patterning a coloring layer by dry etching,
An organic pigment (A), a dispersant (B), a thermosetting compound (C), a solvent (D) and a pigment derivative (E),
The proportion of the organic pigment (A) in the total solid content of the thermosetting coloring composition is 50% by mass or more, and the dispersant (B) has an acidic functional group and / or a dispersant (b1) and / or A thermosetting coloring composition comprising a dispersant (b2) having a basic functional group, and wherein the thermosetting compound (C) contains a glycidyl esterified epoxy compound of sorbitol.   The heat-curable coloring composition according to claim 1, wherein the organic pigment (A) contains a green pigment (a1).   The heat-curable coloring composition according to claim 2, wherein the green pigment contains at least one selected from pigment green 7, pigment green 36 and pigment green 58.   The thermosetting coloring composition according to any one of claims 1 to 3, wherein the solvent (D) contains a solvent (d1) having a boiling point of 160 ° C or more.   The thermosetting coloring composition according to claim 4, wherein the solvent (d1) having a boiling point of 160 ° C or more is either cyclohexanol acetate or ethyl 3-ethoxypropionate.   The dispersant (B) contains a dispersant (b1) having an acidic functional group, and the dispersant (b1) having an acidic functional group polymerizes an ethylenically unsaturated monomer containing (meth) acrylate. The thermosetting according to any one of claims 1 to 5, characterized in that it has a site (b1-A) and the theoretical value of the glass transition temperature of the site (b1-A) is 40.degree. C. or higher. Coloring composition.   The thermosetting coloring composition according to claim 6, wherein the acidic functional group is an aromatic carboxyl group.   The thermosetting coloring composition according to claim 6 or 7, wherein the theoretical value of the glass transition temperature of the portion (b1-A) is 80 ° C or higher.   The thermosetting coloring composition according to claim 2 or 3, wherein the green pigment is pigment green 36.   (X) A step of forming a colored layer using the thermosetting coloring composition according to any one of claims 1 to 9, and (Y) a step of patterning the colored layer by dry etching Method of manufacturing a color filter for a solid-state imaging device In the step of forming the (X) colored layer, (X-1) forming a coating film containing the thermosetting coloring composition, and (X-2) thermally curing the coating film to form the colored layer Obtaining a layer,
In the step of patterning by dry etching (Y), the step of forming a photoresist layer on the colored layer (Y-1), patterning the photoresist layer by exposing and developing (Y-2), and resist A step of obtaining a pattern, (Y-3) patterning the colored layer by dry etching using the resist pattern as an etching mask to form a colored pattern, and (Y-4) contacting a stripping solution with the resist pattern The method for manufacturing a color filter for a solid-state imaging device according to claim 10, further comprising the step of removing the resist pattern from the colored pattern.   The method for manufacturing a color filter for a solid-state imaging device according to claim 11, wherein the peeling solution contains at least one selected from the group consisting of N-methyl pyrrolidone, dimethyl sulfoxide and monoethanolamine.