TW202407055A - Resin composition, method for producing resin composition, pigment derivative, film, optical filter, solid-state imaging element, and image display device - Google Patents
Resin composition, method for producing resin composition, pigment derivative, film, optical filter, solid-state imaging element, and image display device Download PDFInfo
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- TW202407055A TW202407055A TW112124993A TW112124993A TW202407055A TW 202407055 A TW202407055 A TW 202407055A TW 112124993 A TW112124993 A TW 112124993A TW 112124993 A TW112124993 A TW 112124993A TW 202407055 A TW202407055 A TW 202407055A
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- pigment
- resin composition
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- 239000000049 pigment Substances 0.000 title claims abstract description 283
- 239000011342 resin composition Substances 0.000 title claims abstract description 170
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000003384 imaging method Methods 0.000 title claims abstract description 23
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 189
- 239000011347 resin Substances 0.000 claims abstract description 189
- 238000000034 method Methods 0.000 claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims description 661
- 150000001875 compounds Chemical class 0.000 claims description 248
- 239000002253 acid Substances 0.000 claims description 77
- 239000002245 particle Substances 0.000 claims description 75
- 239000003999 initiator Substances 0.000 claims description 44
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 15
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical group C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 claims description 11
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical group C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 claims description 9
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical group C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 claims description 8
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical group N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 7
- HIYWOHBEPVGIQN-UHFFFAOYSA-N 1h-benzo[g]indole Chemical group C1=CC=CC2=C(NC=C3)C3=CC=C21 HIYWOHBEPVGIQN-UHFFFAOYSA-N 0.000 claims description 6
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical group C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 claims description 6
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 4
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical group S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 claims description 2
- -1 methimine structure Chemical group 0.000 description 106
- 239000000126 substance Substances 0.000 description 86
- 125000003118 aryl group Chemical group 0.000 description 77
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- 125000001424 substituent group Chemical group 0.000 description 68
- 125000000217 alkyl group Chemical group 0.000 description 62
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- 125000003277 amino group Chemical group 0.000 description 9
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical class O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229940067265 pigment yellow 138 Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000001042 pteridinyl group Chemical class N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- GGVMPKQSTZIOIU-UHFFFAOYSA-N quaterrylene Chemical group C12=C3C4=CC=C2C(C2=C56)=CC=C5C(C=57)=CC=CC7=CC=CC=5C6=CC=C2C1=CC=C3C1=CC=CC2=CC=CC4=C21 GGVMPKQSTZIOIU-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical group NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000001990 thiamine group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- QTOIMKAWTQBICF-UHFFFAOYSA-N trioxadiazole Chemical group O1ON=NO1 QTOIMKAWTQBICF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明有關一種含有顏料及顏料衍生物之樹脂組成物及其製造方法。又,本發明有關一種顏料衍生物、膜、濾光器、固體攝像元件及圖像顯示裝置。The present invention relates to a resin composition containing pigments and pigment derivatives and a manufacturing method thereof. Furthermore, the present invention relates to a pigment derivative, a film, an optical filter, a solid-state imaging element, and an image display device.
近年來,由於數位相機、附相機之移動電話等的普及,對電荷耦合元件(CCD)影像感測器等固體攝像元件的需求大幅增長。作為顯示器或光學元件的核心裝置,使用濾色器。In recent years, due to the popularity of digital cameras, camera-equipped mobile phones, etc., the demand for solid-state imaging components such as charge-coupled device (CCD) image sensors has increased significantly. As a central device in displays or optical components, color filters are used.
濾色器等濾光器使用含有色材和樹脂之樹脂組成物等來製造。在使用顏料作為色材之情況下,顏料與顏料衍生物及樹脂一起被分散而使用。Optical filters such as color filters are manufactured using resin compositions containing color materials and resin. When a pigment is used as a color material, the pigment is dispersed together with a pigment derivative and a resin.
在專利文獻1中記載有一種濾色器用紅色著色組成物,其含有:包含基於氮氣吸附法之BET比表面積為10m 2/g以上且50m 2/g以下的苯并咪唑酮顏料(a1)之著色劑(a)、樹脂(b)及溶劑(c)。 Patent Document 1 describes a red coloring composition for color filters, which contains a benzimidazolone pigment (a1) with a BET specific surface area of 10 m 2 /g or more and 50 m 2 /g or less based on the nitrogen adsorption method. Colorant (a), resin (b) and solvent (c).
[專利文獻1]日本特開2013-125265號公報[Patent Document 1] Japanese Patent Application Publication No. 2013-125265
關於含有顏料之樹脂組成物,近年來,對於顏料的分散穩定性,要求進一步提高性能。Regarding resin compositions containing pigments, in recent years, there has been a demand for further improvements in the dispersion stability of the pigments.
因此,本發明的目的在於提供一種顏料的分散穩定性優異的樹脂組成物及其製造方法。又,本發明的目的在於提供一種顏料衍生物、膜、濾光器、固體攝像元件及圖像顯示裝置。Therefore, an object of the present invention is to provide a resin composition excellent in pigment dispersion stability and a method for producing the same. Furthermore, an object of the present invention is to provide a pigment derivative, a film, an optical filter, a solid-state imaging element, and an image display device.
本發明提供以下內容。 <1>一種樹脂組成物,其含有: 顏料; 基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物; 樹脂;及 溶劑。 <2>如<1>所述之樹脂組成物,其中 上述顏料衍生物為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子。 <3>一種樹脂組成物,其含有: 顏料; 基於氮氣吸附法之BET比表面積為2~300m 2/g,並且具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子; 樹脂;及 溶劑。 <4>如<2>或<3>所述之樹脂組成物,其中 上述色素結構為選自由二酮吡咯并吡咯結構、吡咯并吡咯結構、甲亞胺結構、異吲哚啉結構、喹啉黃結構、偶氮結構、蒽醌結構、噻𠯤靛藍結構、喹吖酮結構、苯并吲哚結構、酞菁結構及二黃𠯤結構組成之群組中之至少1種。 <5>如<2>或<3>所述之樹脂組成物,其中 上述色素結構為甲亞胺結構。 <6>如<1>至<5>之任一項所述之樹脂組成物,其進一步含有光聚合起始劑和聚合性化合物。 <7>一種樹脂組成物的製造方法,其包括: 在溶劑中分散顏料、基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物及樹脂之步驟。 <8>如<7>所述之樹脂組成物的製造方法,其中 上述顏料衍生物為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子。 <9>一種顏料衍生物,其為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子,其中,基於氮氣吸附法之BET比表面積為2~300m 2/g。 <10>如<9>所述之顏料衍生物,其為分散助劑。 <11>一種膜,其使用<1>至<6>之任一項所述之樹脂組成物來獲得。 <12>一種濾光器,其具有<11>所述之膜。 <13>一種固體攝像元件,其具有<11>所述之膜。 <14>一種圖像顯示裝置,其具有<11>所述之膜。 [發明效果] The present invention provides the following. <1> A resin composition containing: a pigment; a pigment derivative with a BET specific surface area of 2 to 300 m 2 /g based on the nitrogen adsorption method; a resin; and a solvent. <2> The resin composition according to <1>, wherein the pigment derivative is a particle of a compound having at least one structure selected from the group consisting of a pigment structure and a tri-hydroxy structure and an acid group or a base. <3> A resin composition containing: a pigment; a BET specific surface area based on the nitrogen adsorption method of 2 to 300 m 2 /g, and having at least one structure selected from the group consisting of a pigment structure and a triangular structure; Particles of compounds with acidic or basic bases; resins; and solvents. <4> The resin composition as described in <2> or <3>, wherein the pigment structure is selected from the group consisting of diketopyrrolopyrrole structure, pyrrolopyrrole structure, methimine structure, isoindoline structure, and quinoline At least one of the group consisting of yellow structure, azo structure, anthraquinone structure, thiolindigo structure, quinacridone structure, benzindole structure, phthalocyanine structure and diyellow structure. <5> The resin composition according to <2> or <3>, wherein the pigment structure is a methimine structure. <6> The resin composition according to any one of <1> to <5>, further containing a photopolymerization initiator and a polymerizable compound. <7> A method for manufacturing a resin composition, which includes the steps of dispersing a pigment, a pigment derivative with a BET specific surface area of 2 to 300 m 2 /g based on a nitrogen adsorption method, and a resin in a solvent. <8> The method for producing a resin composition according to <7>, wherein the pigment derivative is a compound having at least one structure selected from the group consisting of a pigment structure and a tri-hydroxy structure and an acid group or a base. particle of. <9>A pigment derivative, which is a particle of a compound having at least one structure selected from the group consisting of a pigment structure and a tri-hydroxy structure and an acid group or a base, wherein the BET specific surface area based on the nitrogen adsorption method It is 2~300m 2 /g. <10> The pigment derivative according to <9>, which is a dispersion aid. <11> A film obtained using the resin composition according to any one of <1> to <6>. <12> An optical filter having the film according to <11>. <13> A solid-state imaging element having the film according to <11>. <14> An image display device having the film according to <11>. [Effects of the invention]
依據本發明,能夠提供一種顏料的分散穩定性優異的樹脂組成物及其製造方法。又,依據本發明,能夠提供一種顏料衍生物、膜、濾光器、固體攝像元件及圖像顯示裝置。According to the present invention, a resin composition excellent in pigment dispersion stability and a manufacturing method thereof can be provided. Furthermore, according to the present invention, it is possible to provide a pigment derivative, a film, an optical filter, a solid-state imaging element, and an image display device.
以下,對本發明的內容詳細地進行說明。 在本說明書中,“~”係指以將記載於其前後之數值作為下限值及上限值而包括之含義來使用。 本說明書中之基團(原子團)的標記中,未標有經取代及未經取代之標記包括不具有取代基之基團(原子團)的同時亦包括具有取代基之基團(原子團)。例如,“烷基”不僅包括不具有取代基之烷基(未經取代之烷基),亦包括具有取代基之烷基(經取代之烷基)。 在本說明書中,“曝光”只要沒有特別指定,則不僅包括使用光之曝光,使用電子束、離子束等粒子束之描繪亦包括在曝光中。又,作為曝光中所使用之光,可以列舉水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線(EUV光)、X射線、電子束等活性光線或放射線。 在本說明書中,“(甲基)丙烯酸酯”表示丙烯酸酯及甲基丙烯酸酯兩者或任一者,“(甲基)丙烯酸”表示丙烯酸及甲基丙烯酸兩者或任一者,“(甲基)丙烯醯基”表示丙烯醯基及甲基丙烯醯基兩者或任一者。 在本說明書中,結構式中的Me表示甲基,Et表示乙基,Bu表示丁基,Pr表示丙基,Ph表示苯基。 在本說明書中,重量平均分子量及數量平均分子量為利用GPC(凝膠滲透層析)法測定之聚苯乙烯換算值。 在本說明書中,近紅外線係指波長700~2500nm的光。 在本說明書中,總固體成分係指從組成物的所有成分中去除溶劑之成分的總質量。 在本說明書中,顏料係指不易溶解於溶劑中的色材。例如,顏料在23℃的水100g及23℃的丙二醇單甲醚乙酸酯100g中的溶解度均為0.1g以下為較佳,0.01g以下為更佳。 在本說明書中,染料係指不易溶解於溶劑中的色材。 在本說明書中,“步驟”這一用語,不僅包括獨立之步驟,即使在無法與其他步驟明確區分的情況下,只要達成該步驟所期待的作用,則亦包括在本用語中。 Hereinafter, the contents of the present invention will be described in detail. In this specification, "~" is used in the sense that the numerical values described before and after it are included as the lower limit and the upper limit. Among the labels for groups (atomic groups) in this specification, the labels indicating unsubstituted and unsubstituted include groups (atomic groups) without substituents as well as groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the bright line spectrum of a mercury lamp, active light or radiation such as far ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams represented by excimer lasers. In this specification, "(meth)acrylate" means both or either acrylate and methacrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, and "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid. "Meth)acrylyl" means both or either of acrylyl and methacrylyl. In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Pr represents a propyl group, and Ph represents a phenyl group. In this specification, the weight average molecular weight and the number average molecular weight are polystyrene-converted values measured by the GPC (gel permeation chromatography) method. In this specification, near-infrared rays refer to light with a wavelength of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of components excluding solvents from all components of the composition. In this specification, pigments refer to color materials that are not easily soluble in solvents. For example, the solubility of the pigment in 100 g of water at 23° C. and 100 g of propylene glycol monomethyl ether acetate at 23° C. is preferably 0.1 g or less, and more preferably 0.01 g or less. In this specification, dye refers to color materials that are not easily soluble in solvents. In this specification, the term "step" includes not only independent steps, but also includes them even when they cannot be clearly distinguished from other steps, as long as the expected effect of the step is achieved.
<樹脂組成物> 本發明的第1態樣的樹脂組成物的特徵為,含有: 顏料; 基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物; 樹脂;及 溶劑。 <Resin composition> The resin composition according to the first aspect of the present invention is characterized by containing: a pigment; a pigment derivative having a BET specific surface area of 2 to 300 m 2 /g based on the nitrogen adsorption method; a resin; and a solvent.
本發明的第2態樣的樹脂組成物的特徵為,含有: 顏料; 基於氮氣吸附法之BET比表面積為2~300m 2/g,並且具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子; 樹脂;及 溶劑。 The resin composition of the second aspect of the present invention is characterized by containing: a pigment; a BET specific surface area based on the nitrogen adsorption method of 2 to 300 m 2 /g, and having a pigment structure and a triangular structure selected from the group consisting of Particles of at least one compound with a structure and an acid group or a base; resin; and solvent.
以下,亦將第1態樣的樹脂組成物中的上述顏料衍生物和第2態樣的樹脂組成物中的上述粒子統稱為特定粒子。Hereinafter, the above-mentioned pigment derivative in the resin composition of the first aspect and the above-mentioned particles in the resin composition of the second aspect are also collectively referred to as specific particles.
本發明的樹脂組成物的顏料的分散穩定性優異。獲得此種效果之理由,推測出於以下。推測為,本發明的樹脂組成物由於含有BET比表面積為2~300m 2/g的上述特定粒子,因此顏料衍生物高效率地吸附於顏料的表面上,從而能夠在樹脂組成物中形成樹脂、顏料及顏料衍生物的強固的網路。因此,推測為,能夠抑制由於樹脂組成物的製造時的顏料的凝集或樹脂組成物的保管時的顏料的凝集等而引起之粗大粒子的產生,並且能夠抑制黏度的經時性的變化。推測為,由於此種理由,能夠製成顏料的分散穩定性優異的樹脂組成物。 The resin composition of the present invention has excellent pigment dispersion stability. The reason for obtaining this effect is speculated to be as follows. It is presumed that since the resin composition of the present invention contains the above-mentioned specific particles with a BET specific surface area of 2 to 300 m 2 /g, the pigment derivative is efficiently adsorbed on the surface of the pigment, thereby forming resin, Strong networks of pigments and pigment derivatives. Therefore, it is presumed that the generation of coarse particles caused by aggregation of the pigment during the production of the resin composition or the aggregation of the pigment during storage of the resin composition can be suppressed, and changes in the viscosity over time can be suppressed. It is presumed that for this reason, a resin composition having excellent pigment dispersion stability can be produced.
又,在使用本發明的樹脂組成物並且藉由光微影法形成了圖案之情況下,亦能夠抑制顯影殘渣的產生。獲得此種效果之理由,推測出於以下。推測為,若上述特定粒子作為單質存在,則作為粒子單質存在之特定粒子與支撐體吸附,存在顯影後亦容易作為顯影殘渣而殘留之傾向,但本發明的樹脂組成物中,特定粒子高效率地吸附於顏料,因此顏料衍生物不易作為粒子單質而殘留。推測為,由於此種理由,能夠抑制顯影殘渣的產生。當將本發明的樹脂組成物用作光微影用時,本發明的樹脂組成物進一步含有聚合性化合物和光聚合起始劑為較佳。又,樹脂包括具有酸基之樹脂為較佳。Furthermore, even when a pattern is formed by photolithography using the resin composition of the present invention, the generation of development residue can be suppressed. The reason for obtaining this effect is speculated to be as follows. It is speculated that if the specific particles are present as a single substance, the specific particles existing as simple particles are adsorbed to the support and tend to remain as development residues after development. However, in the resin composition of the present invention, the specific particles are highly efficient. It is adsorbed to the pigment, so the pigment derivative is less likely to remain as simple particles. It is presumed that for this reason, the generation of development residue can be suppressed. When the resin composition of the present invention is used for photolithography, it is preferred that the resin composition of the present invention further contains a polymerizable compound and a photopolymerization initiator. Furthermore, the resin preferably includes a resin having an acid group.
本發明的樹脂組成物可較佳地用作濾光器用樹脂組成物。作為濾光器,可以列舉濾色器、近紅外線透射濾波器、近紅外線截止濾波器等,濾色器為較佳。又,本發明的樹脂組成物可較佳地用作固體攝像元件用。更詳細而言,可較佳地作為用於固體攝像元件用之濾光器用樹脂組成物而使用,可更佳地作為用於固體攝像元件用之濾色器的著色像素形成用樹脂組成物而使用。The resin composition of the present invention can be preferably used as a resin composition for optical filters. Examples of the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cutoff filter, and the like, and a color filter is preferred. Furthermore, the resin composition of the present invention can be suitably used as a solid-state imaging element. More specifically, it can be used preferably as a resin composition for optical filters used in solid-state imaging devices, and more preferably as a resin composition for forming colored pixels used in color filters for solid-state imaging devices. use.
作為濾色器,可以列舉具有使特定波長的光透射之著色像素之濾波器。作為著色像素,可以列舉紅色像素、綠色像素、藍色像素、品紅色像素、青色像素、黃色像素等,紅色像素或綠色像素為較佳,紅色像素為更佳。濾色器的著色像素能夠使用包含彩色顏料之樹脂組成物來形成。Examples of the color filter include a filter having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. Red pixels or green pixels are preferred, and red pixels are more preferred. The colored pixels of the color filter can be formed using a resin composition containing a color pigment.
近紅外線截止濾波器的極大吸收波長存在於波長700~1800nm的範圍內為較佳,存在於波長700~1400nm的範圍內為更佳,存在於波長700~1200nm的範圍內為進一步較佳。又,近紅外線截止濾波器在波長400~650nm的整個範圍內的透射率為70%以上為較佳,80%以上為更佳,90%以上為進一步較佳。又,波長700~1800nm的範圍內的至少1處的透射率為20%以下為較佳。又,近紅外線截止濾波器在極大吸收波長下的吸光度Amax與波長550nm下的吸光度A550之比(吸光度Amax/吸光度A550)為20~500為較佳,50~500為更佳,70~450為進一步較佳,100~400為尤佳。近紅外線截止濾波器能夠使用包含近紅外線吸收顏料之樹脂組成物來形成。The maximum absorption wavelength of the near-infrared cutoff filter is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1400 nm, and still more preferably in the range of 700 to 1200 nm. In addition, the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. In addition, the transmittance at at least one location within the wavelength range of 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at the wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. More preferably, 100 to 400 is particularly preferred. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing pigment.
近紅外線透射濾波器為使近紅外線的至少一部分透射之濾波器。近紅外線透射濾波器可以為使可見光和近紅外線均透射之濾波器(透明膜),亦可以為遮蔽可見光的至少一部分而使近紅外線的至少一部分透射之濾波器。作為近紅外線透射濾波器,可較佳地列舉滿足在波長400~640nm的範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1100~1300nm的範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)的分光特性之濾波器等。近紅外線透射濾波器為滿足以下(1)至(5)中的任一項的分光特性之濾波器為較佳。 (1):在波長400~640nm的範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長800~1500nm的範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。 (2):在波長400~750nm的範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長900~1500nm的範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。 (3):在波長400~830nm的範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1000~1500nm的範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。 (4):在波長400~950nm的範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1100~1500nm的範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。 (5):在波長400~1050nm的範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1200~1500nm的範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。 The near-infrared transmission filter is a filter that transmits at least a part of near-infrared rays. The near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared rays, or may be a filter that blocks at least part of the visible light and transmits at least part of the near-infrared rays. Preferable examples of the near-infrared transmission filter include those that have a maximum value of transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a wavelength of 1100 nm. Filters with spectral characteristics such that the minimum value of transmittance in the range of ~1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). The near-infrared transmission filter is preferably a filter that satisfies the spectral characteristics of any one of the following (1) to (5). (1): The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 800 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (2): The maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 900 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (3): The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1000 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (4): The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1100 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (5): The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1200 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).
本發明的樹脂組成物亦能夠用於遮光膜等。The resin composition of the present invention can also be used for light-shielding films and the like.
本發明的樹脂組成物的固體成分濃度為5~30質量%為較佳。下限為7.5質量%以上為較佳,10質量%以上為更佳。上限為25質量%以下為較佳,20質量%以下為更佳,15質量%以下為進一步較佳。The resin composition of the present invention preferably has a solid content concentration of 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less.
以下,對本發明的樹脂組成物中所使用之各成分進行說明。Each component used in the resin composition of the present invention will be described below.
<<顏料>> 本發明的樹脂組成物含有顏料。作為顏料,可以列舉白色顏料、黑色顏料、彩色顏料、近紅外線吸收顏料。再者,在本說明書中,白色顏料不僅包括純白色,亦包括接近白色之淺灰色(例如灰白色、淡灰色等)的顏料等。 <<Pigment>> The resin composition of the present invention contains pigments. Examples of pigments include white pigments, black pigments, color pigments, and near-infrared absorbing pigments. Furthermore, in this specification, white pigments include not only pure white, but also light gray (such as off-white, light gray, etc.) pigments that are close to white.
當將樹脂組成物用作濾色器用時,使用彩色顏料作為顏料。彩色顏料可以為僅1種,亦可以包含2種以上。當將樹脂組成物用作近紅外線截止濾波器形成用時,使用近紅外線吸收顏料作為顏料。近紅外線吸收顏料可以為僅1種,亦可以包含2種以上。當將樹脂組成物用作近紅外線透射濾波器用時,組合使用2種以上的彩色顏料作為顏料,或者使用含有黑色顏料者。When the resin composition is used as a color filter, a color pigment is used as the pigment. The color pigment may be only one type, or may contain two or more types. When the resin composition is used for forming a near-infrared cut filter, a near-infrared absorbing pigment is used as the pigment. The number of near-infrared absorbing pigments may be only one type, or two or more types may be included. When the resin composition is used as a near-infrared transmission filter, two or more color pigments are used in combination as the pigment, or one containing a black pigment is used.
顏料的平均一次粒徑為1~200nm為較佳。下限為5nm以上為較佳,10nm以上為更佳,20nm以上為進一步較佳,30nm以上為更進一步較佳。上限為180nm以下為較佳,150nm以下為更佳,100nm以下為進一步較佳,90nm以下為更進一步較佳,80nm以下為尤佳。若顏料的平均一次粒徑在上述範圍內,則樹脂組成物中的顏料的分散穩定性良好。顏料的平均一次粒徑能夠按照後述之實施例中記載之方法來測定。The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, and still further preferably 30 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, still more preferably 90 nm or less, and particularly preferably 80 nm or less. If the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the resin composition will be good. The average primary particle size of the pigment can be measured according to the method described in the Examples described below.
基於顏料的氮氣吸附法之BET比表面積為1~300m 2/g為較佳。下限為10m 2/g以上為較佳,30m 2/g以上為更佳。上限為250m 2/g以下為較佳,200m 2/g以下為更佳。顏料的BET比表面積能夠依據基於氮氣吸附法之BET法(Brunauer、Emmett及Teller)來測定。 The BET specific surface area of the pigment-based nitrogen adsorption method is preferably 1 to 300 m 2 /g. The lower limit is preferably 10 m 2 /g or more, and more preferably 30 m 2 /g or more. The upper limit is preferably 250 m 2 /g or less, and more preferably 200 m 2 /g or less. The BET specific surface area of the pigment can be measured according to the BET method (Brunauer, Emmett, and Teller) based on the nitrogen adsorption method.
由源自在將顏料的CuKα線作為X射線源時的X射線繞射光譜中的任一結晶面之峰的半值寬求出之微晶尺寸為0.1nm~100nm為較佳,0.5nm~50nm為更佳,1nm~30nm為進一步較佳,5nm~25nm為尤佳。The crystallite size, calculated from the half-value width of the peak of any crystal plane in the X-ray diffraction spectrum when the CuKα ray of the pigment is used as the X-ray source, is preferably 0.1 nm to 100 nm, and 0.5 nm to 50nm is more preferred, 1nm to 30nm is further preferred, and 5nm to 25nm is particularly preferred.
在本發明中所使用之顏料為包含選自由二酮吡咯并吡咯顏料、吡咯并吡咯顏料、甲亞胺顏料、異吲哚啉顏料、喹啉黃顏料、偶氮顏料、蒽醌顏料、噻𠯤靛藍顏料、喹吖酮顏料、苯并吲哚顏料、酞菁顏料及二黃𠯤顏料組成之群組中之至少1種者為較佳。The pigments used in the present invention are selected from the group consisting of diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, methimine pigments, isoindoline pigments, quinoline yellow pigments, azo pigments, anthraquinone pigments, and thiophene pigments. At least one of the group consisting of indigo pigments, quinacridone pigments, benzindole pigments, phthalocyanine pigments and diyellow pigments is preferred.
以下,對本發明中所使用之顏料,進一步詳細地進行說明。Hereinafter, the pigment used in this invention is demonstrated in further detail.
(彩色顏料) 作為彩色顏料,並無特別限定,能夠使用公知的彩色顏料。作為彩色顏料,可以列舉在波長400~700nm的範圍內具有極大吸收波長之顏料。例如,可以列舉黃色顏料、橙色顏料、紅色顏料、綠色顏料、紫色顏料、藍色顏料等。從耐熱性的觀點而言,彩色顏料為紅色顏料、黃色顏料及藍色顏料為更佳,紅色顏料及藍色顏料為進一步較佳。作為該等的具體例,例如,可以列舉以下。 (color pigment) The color pigment is not particularly limited, and known color pigments can be used. Examples of color pigments include pigments having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, yellow pigments, orange pigments, red pigments, green pigments, purple pigments, blue pigments, etc. can be cited. From the viewpoint of heat resistance, the color pigment is more preferably a red pigment, a yellow pigment and a blue pigment, and further preferably a red pigment and a blue pigment. Specific examples of these include the following.
作為紅色顏料,可以列舉二酮吡咯并吡咯化合物、蒽醌化合物、偶氮化合物、萘酚化合物、甲亞胺化合物、口山口星化合物、喹吖啶酮化合物、苝化合物、硫靛藍化合物等,二酮吡咯并吡咯化合物、蒽醌化合物、偶氮化合物為較佳,二酮吡咯并吡咯化合物為更佳。Examples of red pigments include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, methimine compounds, Kouyamaguchi star compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. Ketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds are preferred, and diketopyrrolopyrrole compounds are more preferred.
作為紅色顏料的具體例,可以列舉C.I.(比色指數)顏料紅1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48:1、48:2、48:3、48:4、49、49:1、49:2、52:1、52:2、53:1、57:1、60:1、63:1、66、67、81:1、81:2、81:3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、269、270、272、279、291、294、295、296、297等。又,作為紅色顏料,亦能夠使用國際公開第2022/085485號的0034段中記載之化合物、日本特開2020-085947號公報中記載之溴化二酮吡咯并吡咯化合物。Specific examples of red pigments include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48 :1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66 , 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171 ,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254 , 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297, etc. In addition, as the red pigment, the compound described in paragraph 0034 of International Publication No. 2022/085485 and the brominated diketopyrrolopyrrole compound described in Japanese Patent Application Laid-Open No. 2020-085947 can also be used.
作為紅色顏料,C.I.顏料紅122、177、254、255、264、269、272為較佳,C.I.顏料紅254、264、272為更佳,C.I.顏料紅254、272為進一步較佳。As the red pigment, C.I. Pigment Red 122, 177, 254, 255, 264, 269, and 272 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 272 are further preferred.
作為綠色顏料,可以列舉酞菁化合物、方酸菁化合物等,酞菁化合物為較佳,酞菁顏料為更佳。又,綠色色材為顏料為較佳。Examples of green pigments include phthalocyanine compounds, squaraine compounds, and the like. Phthalocyanine compounds are preferred, and phthalocyanine pigments are more preferred. Furthermore, the green color material is preferably a pigment.
作為綠色顏料的具體例,可以列舉C.I.顏料綠7、10、36、37、58、59、62、63、64、65、66等。又,作為綠色顏料,亦能夠使用在1分子中的鹵素原子數平均為10~14個、溴原子數平均為8~12個、氯原子數平均為2~5個之鹵化鋅酞菁顏料。作為具體例,可以列舉國際公開第2015/118720號中記載之化合物。又,作為綠色顏料,亦能夠使用國際公開第2022/085485號的0029段中記載之化合物、日本特開2020-070426號公報中記載之鋁酞菁化合物等。Specific examples of green pigments include C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66, and the like. In addition, as the green pigment, it is also possible to use a halide zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms in one molecule of 8 to 12, and an average number of chlorine atoms in one molecule of 2 to 5. Specific examples include compounds described in International Publication No. 2015/118720. Moreover, as a green pigment, the compound described in paragraph 0029 of International Publication No. 2022/085485, the aluminum phthalocyanine compound described in Japanese Patent Application Publication No. 2020-070426, etc. can also be used.
作為綠色顏料,C.I.顏料綠7、36、58、62、63為較佳,C.I.顏料綠36、58為更佳。As the green pigment, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred, and C.I. Pigment Green 36 and 58 are more preferred.
作為橙色顏料的具體例,可以列舉C.I.顏料橙2、5、13、16、17:1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73等。Specific examples of orange pigments include C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc.
作為黃色顏料,可以列舉偶氮化合物、甲亞胺化合物、異吲哚啉化合物、蝶啶化合物、喹啉黃化合物及苝化合物。作為黃色顏料的具體例,可以列舉C.I.顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214、215、228、231、232、233、234、235、236等。Examples of yellow pigments include azo compounds, methimine compounds, isoindoline compounds, pteridine compounds, quinoline compounds, and perylene compounds. Specific examples of yellow pigments include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236, etc.
作為黃色顏料,能夠使用下述結構的偶氮巴比妥酸鎳錯合物。 [化學式1] As a yellow pigment, a nickel azobarbiturate complex having the following structure can be used. [Chemical formula 1]
作為黃色顏料,能夠使用國際公開第2022/085485號的0031~0033段中記載之化合物、日本特開2019-073695號公報中記載之次甲基染料、日本特開2019-073696號公報中記載之次甲基染料、日本特開2019-073697號公報中記載之次甲基染料、日本特開2019-073698號公報中記載之次甲基染料、日本特開2020-093994號公報中記載之偶氮化合物。As the yellow pigment, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022/085485, methine dyes described in Japanese Patent Application Laid-Open No. 2019-073695, and compounds described in Japanese Patent Application Laid-Open No. 2019-073696 can be used. Methine dye, methine dye described in Japanese Patent Application Publication No. 2019-073697, methine dye described in Japanese Patent Application Publication No. 2019-073698, azo dye described in Japanese Patent Application Publication No. 2020-093994 compound.
作為紫色顏料的具體例,可以列舉C.I.顏料紫1、19、23、27、32、37、42、60、61等。Specific examples of the purple pigment include C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 and the like.
作為藍色顏料的具體例,可以列舉C.I.顏料藍1、2、15、15:1、15:2、15:3、15:4、15:6、16、22、29、60、64、66、79、80、87、88等。又,作為藍色顏料,亦能夠使用具有磷原子之鋁酞菁化合物。作為具體例,可以列舉日本特開2012-247591號公報的0022~0030段、日本特開2011-157478號公報的0047段中記載之化合物。Specific examples of the blue pigment include C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66 , 79, 80, 87, 88, etc. Furthermore, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Laid-Open No. 2012-247591 and paragraph 0047 of Japanese Patent Application Laid-Open No. 2011-157478.
作為綠色顏料或藍色顏料,亦能夠使用日本特表2020-504758號公報中記載之二芳基甲烷化合物。As the green pigment or the blue pigment, the diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used.
關於各種顏料具有為較佳之繞射角,能夠參閱日本專利第6561862號公報、日本專利第6413872號公報、日本專利第6281345號公報、日本特開2020-026503號公報、日本特開2020-033526號公報的記載,該等內容被編入本說明書中。又,作為吡咯并吡咯顏料,使用在晶格面中(±1±1±1)的8個面中與X射線繞射圖案中的最大峰對應之面方向的微晶尺寸為140Å以下者亦較佳。又,關於吡咯并吡咯顏料的物理性質,設定為如日本特開2020-097744號公報的0028~0073段中所記載亦較佳。For various pigments with better diffraction angles, please refer to Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Publication No. 2020-026503, and Japanese Patent Publication No. 2020-033526. The records in the official gazette are incorporated into this manual. In addition, as the pyrrolopyrrole pigment, those having a crystallite size of 140 Å or less in the direction of the plane corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes of the lattice plane (±1±1±1) may also be used. Better. In addition, the physical properties of the pyrrolopyrrole pigment are preferably as described in paragraphs 0028 to 0073 of Japanese Patent Application Laid-Open No. 2020-097744.
彩色顏料可以組合使用2種以上。例如,當將本發明的樹脂組成物用作濾色器的綠色像素形成用時,併用綠色顏料和黃色顏料為較佳。又,當將本發明的樹脂組成物用作濾色器的紅色像素形成用時,併用紅色顏料和黃色顏料為較佳。Two or more types of color pigments can be used in combination. For example, when the resin composition of the present invention is used for forming green pixels in a color filter, it is preferable to use both a green pigment and a yellow pigment. Furthermore, when the resin composition of the present invention is used for forming red pixels in a color filter, it is preferable to use a red pigment and a yellow pigment in combination.
當組合使用2種以上的彩色顏料時,可以由2種以上的彩色顏料的組合來形成黑色。作為該等組合,例如可以列舉以下(1)~(7)的態樣。當樹脂組成物中含有2種以上的彩色顏料且以2種以上的彩色顏料的組合來呈現黑色時,本發明的樹脂組成物能夠較佳地用作近紅外線透射濾波器形成用樹脂組成物。 (1)含有紅色顏料及藍色顏料之態樣。 (2)含有紅色顏料、藍色顏料及黃色顏料之態樣。 (3)含有紅色顏料、藍色顏料、黃色顏料及紫色顏料之態樣。 (4)含有紅色顏料、藍色顏料、黃色顏料、紫色顏料及綠色顏料之態樣。 (5)含有紅色顏料、藍色顏料、黃色顏料及綠色顏料之態樣。 (6)含有紅色顏料、藍色顏料及綠色顏料之態樣。 (7)含有黃色顏料及紫色顏料之態樣。 When two or more kinds of color pigments are used in combination, black can be formed by the combination of two or more kinds of color pigments. Examples of such combinations include the following aspects (1) to (7). When the resin composition contains two or more color pigments and the combination of the two or more color pigments renders black, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. (1) Containing red pigment and blue pigment. (2) Containing red pigment, blue pigment and yellow pigment. (3) Containing red pigment, blue pigment, yellow pigment and purple pigment. (4) Containing red pigment, blue pigment, yellow pigment, purple pigment and green pigment. (5) Containing red pigment, blue pigment, yellow pigment and green pigment. (6) Containing red pigment, blue pigment and green pigment. (7) Contains yellow pigment and purple pigment.
(白色顏料) 作為白色顏料,可以列舉氧化鈦、鈦酸鍶、鈦酸鋇、氧化鋅、氧化鎂、氧化鋯、氧化鋁、硫酸鋇、二氧化矽、滑石、雲母、氫氧化鋁、矽酸鈣、矽酸鋁、中空樹脂粒子、硫化鋅等。白色顏料為具有鈦原子之粒子為較佳,氧化鈦為更佳。又,白色顏料為對於波長589nm的光之折射率為2.10以上的粒子為較佳。前述的折射率為2.10~3.00為較佳,2.50~2.75為更佳。 (white pigment) Examples of white pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, and silicic acid. Aluminum, hollow resin particles, zinc sulfide, etc. It is preferred that the white pigment is particles containing titanium atoms, and titanium oxide is even more preferred. Moreover, it is preferable that the white pigment is a particle whose refractive index with respect to light with a wavelength of 589 nm is 2.10 or more. The aforementioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.
又,白色顏料亦能夠使用“氧化鈦 物性和應用技術 清野學著 13~45頁 1991年6月25日發行,GIHIDO SHUPPAN CO.,Ltd.發行”中記載之氧化鈦。In addition, as the white pigment, titanium oxide described in "Titanium Oxide: Physical Properties and Application Technology, Kiyono Gakusho, pp. 13 to 45, issued on June 25, 1991, published by GIHIDO SHUPPAN CO., Ltd." can also be used.
白色顏料不僅可以使用由單一無機物構成者,亦可以使用與其他材料複合而成之粒子。例如,使用在內部具有空孔或其他材料之粒子、在核粒子上附著有多數無機粒子之粒子、包括由聚合物粒子構成之核粒子和由無機奈米微粒構成之殼層之核及殼複合粒子為較佳。作為上述包括由聚合物粒子構成之核粒子和由無機奈米微粒構成之殼層之核及殼複合粒子,例如,能夠參閱日本特開2015-047520號公報的0012~0042段的記載,該內容被編入本說明書中。The white pigment may not only be composed of a single inorganic substance, but may also be composed of particles compounded with other materials. For example, particles with pores or other materials inside, particles with a plurality of inorganic particles attached to the core particles, and core-shell composites including core particles composed of polymer particles and shells composed of inorganic nanoparticles are used. Particles are better. As the core-shell composite particles including core particles composed of polymer particles and shell layers composed of inorganic nanoparticles, for example, the description in paragraphs 0012 to 0042 of Japanese Patent Application Laid-Open No. 2015-047520 can be referred to. are incorporated into this manual.
白色顏料亦能夠使用中空無機粒子。中空無機粒子係指在內部具有空洞之結構且具有被外殼包圍之空洞之無機粒子。作為中空無機粒子,可以列舉日本特開2011-075786號公報、國際公開第2013/061621號、日本特開2015-164881號公報等中記載之中空無機粒子,該等內容被編入本說明書中。White pigments can also use hollow inorganic particles. Hollow inorganic particles refer to inorganic particles that have a hollow structure inside and are surrounded by a shell. Examples of the hollow inorganic particles include hollow inorganic particles described in Japanese Patent Application Publication No. 2011-075786, International Publication No. 2013/061621, Japanese Patent Application Publication No. 2015-164881, etc., and these contents are incorporated into this specification.
(黑色顏料) 作為黑色顏料並無特別限定,能夠使用公知者。作為無機黑色顏料,可以列舉碳黑、鈦黑、石墨等,碳黑、鈦黑為較佳,鈦黑為更佳。鈦黑係指含有鈦原子之黑色粒子,低次氧化鈦或氮氧化鈦為較佳。以提高分散性、抑制凝集性等為目的,視需要,能夠對鈦黑的表面進行修飾。例如,能夠用氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鎂或氧化鋯包覆鈦黑的表面。又,亦能夠用如日本特開2007-302836號公報中所示之撥水性物質進行處理。作為無機黑色顏料的具體例,可以列舉C.I.顏料黑1、7等。鈦黑的每個粒子的一次粒徑及平均一次粒徑均小為較佳。具體而言,平均一次粒徑為10~45nm為較佳。鈦黑亦能夠用作分散物。例如,可以列舉:含有鈦黑粒子和二氧化矽粒子且分散物中的Si原子與Ti原子的含有比被調整為0.20~0.50的範圍之分散物等。關於上述分散物,能夠參閱日本特開2012-169556號公報的0020~0105段的記載,該內容被編入本說明書中。作為鈦黑的市售品的例子,可以列舉鈦黑10S、12S、13R、13M、13M-C、13R-N、13M-T(商品名:Mitsubishi Materials Corporation製造)、Tilack D(商品名:Ako Kasei Co.,Ltd.製造)等。 (black pigment) The black pigment is not particularly limited, and known ones can be used. Examples of inorganic black pigments include carbon black, titanium black, graphite, etc. Carbon black and titanium black are preferred, and titanium black is more preferred. Titanium black refers to black particles containing titanium atoms, preferably low-order titanium oxide or titanium oxynitride. The surface of titanium black can be modified if necessary for the purpose of improving dispersibility, inhibiting aggregation, etc. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide. Furthermore, it can also be treated with a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. Specific examples of the inorganic black pigment include C.I. Pigment Black 1, 7, and the like. It is preferable that each particle of titanium black has a small primary particle size and an average primary particle size. Specifically, the average primary particle diameter is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silicon dioxide particles, and the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50. Regarding the above-mentioned dispersion, please refer to the description in paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556, and this content is incorporated into this specification. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (trade name: Mitsubishi Materials Corporation), Tilack D (trade name: Ako Manufactured by Kasei Co., Ltd.) etc.
作為有機黑色顏料,可以列舉二苯并呋喃酮化合物、甲亞胺化合物、苝化合物、偶氮化合物等。作為雙苯并呋喃酮化合物,可以列舉日本特表2010-534726號公報、日本特表2012-515233號公報、日本特表2012-515234號公報等中記載之化合物,例如,能夠作為BASF公司製“Irgaphor Black”獲得。作為苝化合物,可以列舉日本特開2017-226821號公報的0016~0020段中記載之化合物、C.I.顏料黑31、32等。作為甲亞胺化合物,可以列舉日本特開平01-170601號公報、日本特開平02-034664號公報等中記載之化合物,例如,能夠作為Dainichiseika Color & Chemicals Mfg.Co.,Ltd.製“CHROMO FINE BLACK A1103”獲得。又,作為黑色顏料,可以使用日本專利第6985715號公報中記載之黑色有機顏料、Lumogen Black FK4280、Paliogen Black S0084(BASF公司製造)。Examples of organic black pigments include dibenzofuranone compounds, imine compounds, perylene compounds, and azo compounds. Examples of the dibenzofuranone compound include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, etc., for example, " Irgaphor Black” obtained. Examples of the perylene compound include compounds described in paragraphs 0016 to 0020 of Japanese Patent Application Laid-Open No. 2017-226821, C.I. Pigment Black 31, 32, and the like. Examples of the methimine compound include compounds described in Japanese Patent Application Publication No. 01-170601, Japanese Patent Application Publication No. 02-034664, etc., for example, "CHROMO FINE" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. BLACK A1103" obtained. In addition, as the black pigment, the black organic pigment described in Japanese Patent No. 6985715, Lumogen Black FK4280, and Paliogen Black S0084 (manufactured by BASF Corporation) can be used.
(近紅外線吸收顏料) 近紅外線吸收顏料為有機顏料為較佳。又,近紅外線吸收顏料為在波長超過700nm且1800nm以下的範圍內存在極大吸收波長為較佳。又,近紅外線吸收顏料的極大吸收波長存在於1400nm以下為較佳,存在於1200nm以下為更佳,存在於1000nm以下為進一步較佳。又,近紅外線吸收顏料在波長550nm下的吸光度A550與極大吸收波長下的吸光度Amax之比A550/Amax為0.1以下為較佳,0.05以下為更佳,0.03以下為進一步較佳,0.02以下為尤佳。下限並無特別限定,例如,能夠設為0.0001以上,亦能夠設為0.0005以上。若上述吸光度的比在上述範圍內,則能夠使其成為可視透明性及近紅外線遮蔽性優異的近紅外線吸收顏料。 (Near infrared absorbing pigment) The near-infrared absorbing pigment is preferably an organic pigment. Moreover, it is preferable that the near-infrared absorbing pigment has a maximum absorption wavelength in the range of a wavelength exceeding 700 nm and not exceeding 1800 nm. In addition, the maximum absorption wavelength of the near-infrared absorbing pigment is preferably 1,400 nm or less, more preferably 1,200 nm or less, and still more preferably 1,000 nm or less. In addition, the ratio A550/Amax of the absorbance A550 of the near-infrared absorbing pigment at a wavelength of 550 nm and the absorbance Amax at the maximum absorption wavelength is preferably 0.1 or less, more preferably 0.05 or less, further preferably 0.03 or less, especially 0.02 or less. good. The lower limit is not particularly limited, and may be, for example, 0.0001 or more, or 0.0005 or more. If the absorbance ratio is within the above range, the near-infrared absorbing pigment can be excellent in visual transparency and near-infrared shielding properties.
作為近紅外線吸收顏料,可以列舉吡咯并吡咯化合物、花青化合物、方酸菁化合物、酞菁化合物、萘酞菁化合物、夸特銳烯(quaterrylene)化合物、部花青化合物、克酮鎓化合物、氧雜菁化合物、亞銨化合物、二硫醇化合物、三芳基甲烷化合物、吡咯亞甲基化合物、甲亞胺化合物、蒽醌化合物、二苯并呋喃酮化合物、二硫烯金屬錯合物、金屬氧化物、金屬硼化物等。作為該等的具體例,可以列舉國際公開第2022/065215號的0114段中記載之化合物中記載之化合物。又,作為近紅外線吸收色材,亦能夠使用國際公開第2022/065215號的0121段中記載之化合物、日本特開2020-075959號公報中記載之方酸菁化合物、韓國公開專利第10-2019-0135217號公報中記載之銅錯合物、日本特開2021-195515號公報中記載之克酮酸化合物、日本特開2022-022070號公報中記載之近紅外線吸收性色素。Examples of the near-infrared-absorbing pigment include pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, and ketonium compounds. Oxocyanine compounds, immonium compounds, dithiol compounds, triarylmethane compounds, pyrrromethylene compounds, methimine compounds, anthraquinone compounds, dibenzofuranone compounds, disulfene metal complexes, metal Oxides, metal borides, etc. Specific examples of these include compounds described in paragraph 0114 of International Publication No. 2022/065215. In addition, as the near-infrared absorbing color material, the compound described in paragraph 0121 of International Publication No. 2022/065215, the squaraine compound described in Japanese Patent Application Laid-Open No. 2020-075959, and Korean Patent Publication No. 10-2019 can also be used. The copper complex described in Japanese Patent Application Publication No. 2021-195515, the copper complex compound described in Japanese Patent Application Publication No. 2021-195515, and the near-infrared absorbing dye described in Japanese Patent Application Publication No. 2022-022070.
樹脂組成物的總固體成分中的顏料的含量為30~80質量%為較佳。下限為40質量%以上為較佳,50質量%以上為更佳。上限為75質量%以下為較佳,70質量%以下為更佳。The content of the pigment in the total solid content of the resin composition is preferably 30 to 80% by mass. The lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 75 mass% or less, and more preferably 70 mass% or less.
當將本發明的樹脂組成物用作濾色器用時,樹脂組成物中所含之顏料中的彩色顏料的含量為80質量%以上為較佳,90質量%以上為更佳,95質量%以上為進一步較佳,99質量%以上為更進一步較佳。When the resin composition of the present invention is used as a color filter, the content of the color pigment in the pigment contained in the resin composition is preferably 80 mass% or more, more preferably 90 mass% or more, and 95 mass% or more In order to be more preferable, 99 mass % or more is still more preferable.
當將本發明的樹脂組成物用作近紅外線截止濾波器用時,樹脂組成物中所含之顏料中的近紅外線吸收顏料的含量為80質量%以上為較佳,90質量%以上為更佳,95質量%以上為進一步較佳,99質量%以上為更進一步較佳。When the resin composition of the present invention is used as a near-infrared cutoff filter, the content of the near-infrared absorbing pigment in the pigment contained in the resin composition is preferably 80 mass% or more, and more preferably 90 mass% or more. More than 95 mass % is more preferably, and 99 mass % or more is still more preferably.
<<染料>> 本發明的樹脂組成物可以含有染料。作為染料,並無特別限制,能夠使用公知的染料。作為染料,可以列舉彩色染料、黑色染料、近紅外線吸收染料等。作為染料,能夠使用公知的染料。作為染料,亦能夠使用色素多聚體。色素多聚體為在一分子中具有2個以上的色素結構者,具有3個以上的色素結構為較佳。上限並無特別限定,但亦能夠設為100以下。一分子中所具有之複數個色素結構可以為相同的色素結構,亦可以為不同的色素結構。色素多聚體的重量平均分子量(Mw)為2000~50000為較佳。下限為3000以上為更佳,6000以上為進一步較佳。上限為30000以下為更佳,20000以下為進一步較佳。色素多聚體亦能夠使用日本特開2011-213925號公報、日本特開2013-041097號公報、日本特開2015-028144號公報、日本特開2015-030742號公報、日本特開2016-102191號公報、國際公開第2016/031442號等中記載之化合物。 <<Dye>> The resin composition of the present invention may contain a dye. The dye is not particularly limited, and known dyes can be used. Examples of dyes include color dyes, black dyes, near-infrared absorbing dyes, and the like. As the dye, a known dye can be used. As the dye, a pigment polymer can also be used. The dye multimer has two or more dye structures in one molecule, preferably three or more dye structures. The upper limit is not particularly limited, but it can also be set to 100 or less. The plurality of pigment structures in one molecule may be the same pigment structure or may be different pigment structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. It is more preferable that the lower limit is 3,000 or more, and it is further more preferable that it is 6,000 or more. It is more preferable that the upper limit is 30,000 or less, and it is further more preferable that it is 20,000 or less. The dye multimer can also be used as Japanese Patent Application Laid-Open Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, and 2016-102191. Compounds described in the official publication, International Publication No. 2016/031442, etc.
作為顏料或染料,能夠使用韓國公開專利第10-2020-0028160號公報中記載之三芳基甲烷染料聚合物、日本特開2020-117638號公報中記載之口山口星化合物、國際公開第2020/174991號中記載之酞菁化合物、日本特開2020-160279號公報中記載之異吲哚啉化合物或該等的鹽、韓國公開專利第10-2020-0069442號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069730號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069070號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069067號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069062號公報中記載之由式1表示之化合物、日本專利第6809649號中記載之鹵化鋅酞菁、日本特開2020-180176號公報中記載之異吲哚啉化合物、日本特開2021-187913號公報中記載之啡噻𠯤系化合物、國際公開第2022/004261號中記載之鹵化鋅酞菁、國際公開第2021/250883號中記載之鹵化鋅酞菁、韓國公開專利第10-2020-0030759號公報的由式1表示之喹啉黃化合物、韓國公開專利第10-2020-0061793號公報中記載之高分子染料、日本特開2022-029701號公報中記載之著色劑、國際公開第2022/014635號中記載之異吲哚啉化合物、國際公開第2022/024926號中記載之鋁酞菁化合物。顏料或染料可以為輪烷,色素骨架可以用於輪烷的環狀結構,亦可以用於棒狀結構,亦可以用於這兩種結構。As the pigment or dye, the triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, the Yamaguchi star compound described in Japanese Patent Application Laid-Open No. 2020-117638, and the International Publication No. 2020/174991 can be used. Phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2020-160279, isoindoline compounds or salts thereof, and compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069442 , the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070, Korean Patent Publication No. 10-2020 -The compound represented by Formula 1 described in Publication No. 0069067, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069062, the halide zinc phthalocyanine described in Japanese Patent No. 6809649, Japan Patent No. Isoindoline compounds described in Japanese Patent Application Publication No. 2020-180176, phenanthroline compounds described in Japanese Patent Application Publication No. 2021-187913, halogenated zinc phthalocyanine described in International Publication No. 2022/004261, International Publication No. Zinc halide phthalocyanine described in 2021/250883, quinoline yellow compound represented by Formula 1 in Korean Patent Publication No. 10-2020-0030759, polymer described in Korean Patent Publication No. 10-2020-0061793 Dyes, colorants described in Japanese Patent Application Publication No. 2022-029701, isoindoline compounds described in International Publication No. 2022/014635, and aluminum phthalocyanine compounds described in International Publication No. 2022/024926. The pigment or dye can be a rotaxane, and the pigment skeleton can be used for the ring structure of the rotaxane, the rod-like structure, or both structures.
樹脂組成物的總固體成分中的染料的含量為20質量%以下為較佳,10質量%以下為更佳,5質量%以下為進一步較佳。又,相對於顏料100質量份,樹脂組成物中的染料的含量為60質量份以下為較佳,40質量份以下為更佳,20質量份以下為進一步較佳。The content of the dye in the total solid content of the resin composition is preferably 20 mass% or less, more preferably 10 mass% or less, and further preferably 5 mass% or less. Moreover, the content of the dye in the resin composition is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 20 parts by mass or less based on 100 parts by mass of the pigment.
本發明的樹脂組成物實質上不含染料亦較佳。再者,在本說明書中,實質上不含染料之情況係指樹脂組成物的總固體成分中的染料的含量為0.1質量%以下,0.01質量%以下為較佳,不含染料為更佳。It is also preferred that the resin composition of the present invention contains substantially no dye. In addition, in this specification, the case of substantially no dye means that the content of the dye in the total solid content of the resin composition is 0.1 mass % or less, preferably 0.01 mass % or less, and more preferably no dye.
<<特定粒子>> 本發明的第1態樣的樹脂組成物含有基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物。 又,本發明的第2態樣的樹脂組成物含有基於氮氣吸附法之BET比表面積為2~300m 2/g且具有選自由色素結構及三𠯤結構組成之群組中之至少1種的結構和酸基或鹼基之化合物的粒子。 亦將第1態樣的樹脂組成物中的上述顏料衍生物和第2態樣的樹脂組成物中的上述粒子統稱為特定粒子。 <<Specific Particles>> The resin composition according to the first aspect of the present invention contains a pigment derivative with a BET specific surface area based on the nitrogen adsorption method of 2 to 300 m 2 /g. Furthermore, the resin composition according to the second aspect of the present invention has a BET specific surface area based on the nitrogen adsorption method of 2 to 300 m 2 /g and has at least one structure selected from the group consisting of a pigment structure and a ternary structure. Particles of compounds with acid or base groups. The pigment derivatives in the resin composition of the first aspect and the particles in the resin composition of the second aspect are also collectively referred to as specific particles.
特定粒子可以用作分散助劑。分散助劑係用於提高樹脂組成物中的顏料的分散性之材料。Certain particles can be used as dispersion aids. Dispersion aids are materials used to improve the dispersibility of pigments in resin compositions.
第1態樣的樹脂組成物中使用之特定粒子亦即基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子為較佳。 The specific particles used in the resin composition of the first aspect, that is, the pigment derivative with a BET specific surface area of 2 to 300 m 2 /g based on the nitrogen adsorption method, are selected from the group consisting of a pigment structure and a triangular structure. Particles containing at least one compound having a structure and an acid group or a base are preferred.
特定粒子的基於氮氣吸附法之BET比表面積為2~300m 2/g。特定粒子的BET比表面積的下限為3m 2/g以上為較佳,5m 2/g以上為更佳。特定粒子的BET比表面積的上限為250m 2/g以下為較佳,200m 2/g以下為更佳,150m 2/g以下為進一步較佳,100m 2/g以下為更進一步較佳。特定粒子的BET比表面積為依據基於氮氣吸附法之BET法(Brunauer、Emmett及Teller)測定之值。 The BET specific surface area of specific particles based on the nitrogen adsorption method is 2 to 300 m 2 /g. The lower limit of the BET specific surface area of specific particles is preferably 3 m 2 /g or more, and more preferably 5 m 2 /g or more. The upper limit of the BET specific surface area of specific particles is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less, further preferably 150 m 2 /g or less, and still more preferably 100 m 2 /g or less. The BET specific surface area of a specific particle is a value measured based on the BET method (Brunauer, Emmett, and Teller) based on the nitrogen adsorption method.
特定粒子的平均一次粒徑為5~200nm為較佳。上限為150nm以下為較佳,100nm以下為更佳。下限為10nm以上為較佳,20nm以上為更佳。若顏料衍生物的平均一次粒徑在上述範圍內,則能夠進一步提高顏料的分散穩定性。特定粒子的平均一次粒徑能夠按照後述之實施例中記載之方法來測定。The average primary particle size of the specific particles is preferably 5 to 200 nm. The upper limit is preferably 150 nm or less, and more preferably 100 nm or less. The lower limit is preferably 10 nm or more, and more preferably 20 nm or more. If the average primary particle diameter of the pigment derivative is within the above range, the dispersion stability of the pigment can be further improved. The average primary particle diameter of specific particles can be measured according to the method described in the Examples described later.
樹脂組成物中所含之特定粒子的平均一次粒徑與顏料的平均一次粒徑之差為0~100nm為較佳。上限為50nm以下為較佳,30nm以下為更佳。下限為2nm以上為較佳,5nm以上為更佳。若特定粒子的平均一次粒徑與顏料的平均一次粒徑之差在上述範圍內,則能夠進一步提高顏料的分散穩定性。The difference between the average primary particle diameter of the specific particles contained in the resin composition and the average primary particle diameter of the pigment is preferably 0 to 100 nm. The upper limit is preferably 50 nm or less, and more preferably 30 nm or less. The lower limit is preferably 2 nm or more, and more preferably 5 nm or more. If the difference between the average primary particle diameter of the specific particles and the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment can be further improved.
當特定粒子為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子時,特定粒子所具有之上述色素結構為選自由二酮吡咯并吡咯結構、吡咯并吡咯結構、甲亞胺結構、異吲哚啉結構、喹啉黃結構、偶氮結構、蒽醌結構、噻𠯤靛藍結構、喹吖酮結構、苯并吲哚結構、酞菁結構及二黃𠯤結構組成之群組中之至少1種為較佳,甲亞胺結構為更佳。When the specific particle is a compound having at least one structure selected from the group consisting of a pigment structure and a tri-hydroxy structure and an acid group or a base, the pigment structure of the specific particle is a compound selected from the group consisting of a diketopyrrolo Pyrrole structure, pyrrolopyrrole structure, methimine structure, isoindoline structure, quinoline yellow structure, azo structure, anthraquinone structure, thi𠯤indigo structure, quinacridone structure, benzindole structure, phthalocyanine At least one of the group consisting of the structure and the diyellow 𠯤 structure is preferred, and the methimine structure is even more preferred.
當特定粒子為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子時,作為特定粒子所具有之酸基,可以列舉羧基、磺基、磷酸基、硼酸基、醯亞胺酸基及該等的鹽等。作為構成鹽之原子或原子團,可以列舉鹼金屬離子(Li +、Na +、K +等)、鹼土類金屬離子(Ca 2+、Mg 2+等)、銨離子、咪唑鎓離子、吡啶鎓離子、鏻離子等。作為醯亞胺酸基,由-SO 2NHSO 2R X1、-CONHSO 2R X2、-CONHCOR X3或-SO 2NHCOR X4表示之基團為較佳,由-SO 2NHSO 2R X1、-CONHSO 2R X2或-SO 2NHCOR X4表示之基團為更佳,-SO 2NHSO 2R X1或-CONHSO 2R X2為進一步較佳。R X1~R X4分別獨立地表示烷基或芳基。R X1~R X4所表示之烷基及芳基可以具有取代基。作為取代基,鹵素原子為較佳,氟原子為更佳。R X1~R X4分別獨立地為含有氟原子之烷基或含有氟原子之芳基為較佳,含有氟原子之烷基為更佳。含有氟原子之烷基的碳數為1~10為較佳,1~5為更佳,1~3為進一步較佳。含有氟原子之芳基的碳數為6~20為較佳,6~12為更佳,6為進一步較佳。 When the specific particle is a compound having at least one structure selected from the group consisting of a pigment structure and a trivalent structure and an acid group or a base, examples of the acid group possessed by the specific particle include a carboxyl group and a sulfo group. , phosphate group, boric acid group, acyl imide acid group and their salts, etc. Examples of atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, and pyridinium ions. , phosphonium ions, etc. As the acylidine acid group , a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR The group represented by 2 R X2 or -SO 2 NHCOR X4 is more preferred, and -SO 2 NHSO 2 R X1 or -CONHSO 2 R R X1 to R X4 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R X1 to R X4 may have a substituent. As the substituent, a halogen atom is preferred, and a fluorine atom is more preferred. It is preferred that R X1 to R The carbon number of the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. The carbon number of the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and further preferably 6.
當特定粒子為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子時,作為特定粒子所具有之鹼基,可以列舉胺基、吡啶基及其鹽、銨基的鹽以及酞醯亞胺甲基。作為構成鹽之原子或原子團,可以列舉氫氧化物離子、鹵素離子、羧酸離子、磺酸離子、酚鹽離子(phenoxide ion)等。When the specific particles are particles having a compound having at least one structure selected from the group consisting of a pigment structure and a trivalent structure and an acid group or a base, examples of the base possessed by the specific particles include an amine group and a pyridine group. base and its salts, salts of ammonium groups and phthaloimide methyl. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonic acid ions, phenoxide ions, and the like.
作為胺基,可以列舉由-NR x11R x12表示之基團及環狀胺基。 Examples of the amino group include a group represented by -NR x11 R x12 and a cyclic amino group.
由-NR x11R x12表示之基團中,R x11及R x12分別獨立地表示氫原子、烷基或芳基,烷基為較佳。亦即,胺基為二烷基胺基為較佳。烷基的碳數為1~10為較佳,1~5為更佳,1~3為進一步較佳。烷基可以為直鏈狀、支鏈狀、環狀中的任一種,但直鏈狀或支鏈狀為較佳,直鏈狀為更佳。烷基可以具有取代基。作為取代基,可以列舉後述之取代基T。芳基的碳數為6~30為較佳,6~20為更佳,6~12為進一步較佳。芳基可以具有取代基。作為取代基,可以列舉後述之取代基T。 In the group represented by -NR x11 R x12 , R x11 and R x12 each independently represent a hydrogen atom, an alkyl group or an aryl group, with an alkyl group being preferred. That is, the amino group is preferably a dialkylamino group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred, and linear is more preferred. The alkyl group may have a substituent. Examples of the substituent include the substituent T described below. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms. The aryl group may have a substituent. Examples of the substituent include the substituent T described below.
作為環狀胺基,可以列舉吡咯啶基、哌啶基、哌𠯤基、𠰌啉基等。該等基團可以進一步具有取代基。Examples of the cyclic amino group include a pyrrolidinyl group, a piperidinyl group, a piperidinyl group, a pyridinyl group, and the like. These groups may further have substituents.
當特定粒子為具有色素結構和酸基或鹼基之化合物的粒子時,特定粒子為由式(B1)表示之化合物的粒子為較佳。 [化學式2] 式(B1)中,P表示色素結構,L表示單鍵或n+1價連結基,X表示酸基或鹼基,m表示1以上的整數,n表示1以上的整數,當m為2以上時,複數個L及X可以彼此不同,當n為2以上時,複數個X可以彼此不同。 When the specific particles are particles of a compound having a pigment structure and an acid group or a base, it is preferable that the specific particles are particles of a compound represented by formula (B1). [Chemical formula 2] In formula (B1), P represents the pigment structure, L represents a single bond or n+1 valent linking group, X represents an acid group or a base, m represents an integer above 1, n represents an integer above 1, and when m is 2 or above When n is 2 or more, a plurality of L and X may be different from each other. When n is 2 or more, a plurality of X may be different from each other.
式(B1)的P所表示之色素結構為二酮吡咯并吡咯結構、吡咯并吡咯結構、甲亞胺結構、異吲哚啉結構、喹啉黃結構、偶氮結構、蒽醌結構、噻𠯤靛藍結構、喹吖酮結構、苯并吲哚結構、酞菁結構或二黃𠯤結構為較佳,甲亞胺結構為更佳。The pigment structure represented by P in formula (B1) is a diketopyrrolopyrrole structure, a pyrrolopyrrole structure, a methimine structure, an isoindoline structure, a quinoline yellow structure, an azo structure, an anthraquinone structure, and a thiamine structure. The indigo structure, quinacridone structure, benzindole structure, phthalocyanine structure or diyellow 𠯤 structure is better, and the methimine structure is even better.
式(B1)的L所表示之n+1價連結基,可以列舉脂肪族烴基、芳香族烴基、雜環基、-O-、-S-、-CO-、-COO-、-OCO-、-SO 2-、-NR L-、-NR LCO-、-CONR L-、-NR LSO 2-、-SO 2NR L-及由該等的組合組成之基團。R L表示氫原子、烷基或芳基。脂肪族烴基的碳數為1~20為較佳,2~20為更佳,2~10為進一步較佳,2~5為尤佳。脂肪族烴基可以為直鏈狀、支鏈狀、環狀中的任一種。又,環狀的脂肪族烴基可以為單環、多環中的任一種。芳香族烴基的碳數為6~18為較佳,6~14為更佳,6~10為進一步較佳。芳香族烴基為單環或縮合數為2~4的縮合環的芳香族烴基為較佳。作為芳香族烴基,苯環基為較佳。雜環基為單環或縮合數為2~4的縮合環為較佳。構成雜環基的環之雜原子數為1~3為較佳。構成雜環基之雜原子為氮原子、氧原子或硫原子為較佳。構成雜環基的環之碳原子數為3~30為較佳,3~18為更佳,3~12為進一步較佳。作為雜環基,三𠯤環基為較佳。脂肪族烴基、芳香族烴基及雜環基可以具有取代基。作為取代基,可以列舉後述之取代基T。又,R L所表示之烷基的碳數為1~20為較佳,1~15為更佳,1~8為進一步較佳。烷基可以為直鏈狀、支鏈狀、環狀中的任一種,直鏈狀或支鏈狀為較佳,直鏈狀為更佳。R L所表示之烷基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。R L所表示之芳基的碳數為6~30為較佳,6~20為更佳,6~12為進一步較佳。R L所表示之芳基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 Examples of the n+1-valent linking group represented by L in formula (B1) include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2 -, -NR L -, -NR L CO-, -CONR L -, -NR L SO 2 -, -SO 2 NR L - and groups consisting of combinations thereof. R L represents a hydrogen atom, an alkyl group or an aryl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 20, still more preferably 2 to 10, and particularly preferably 2 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be either a monocyclic ring or a polycyclic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. The aromatic hydrocarbon group is preferably a monocyclic aromatic hydrocarbon group or an aromatic hydrocarbon group having a condensed ring with a condensation number of 2 to 4. As the aromatic hydrocarbon group, a phenyl ring group is preferred. The heterocyclic group is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms in the ring constituting the heterocyclyl group is preferably 1 to 3. The heteroatoms constituting the heterocyclic group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The number of carbon atoms of the ring constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. As the heterocyclic group, a tricyclocyclic group is preferred. The aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent include the substituent T described below. In addition, the number of carbon atoms of the alkyl group represented by R L is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. The alkyl group is preferably linear or branched, and is more preferably linear. The alkyl group represented by R L may further have a substituent. Examples of the substituent include the substituent T described below. The number of carbon atoms in the aryl group represented by R L is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group represented by R L may further have a substituent. Examples of the substituent include the substituent T described below.
作為式(B1)的X所表示之酸基及鹼基,可以列舉上述之酸基及鹼基。Examples of the acid group and base represented by X in Formula (B1) include the above-mentioned acid groups and bases.
式(B1)的m為1或2為較佳。 式(B1)的n為1或2為較佳。 It is preferable that m in formula (B1) is 1 or 2. It is preferable that n in formula (B1) is 1 or 2.
當特定粒子為具有三𠯤結構和酸基或鹼基之化合物的粒子時,作為此種特定粒子,可以列舉具有由式(A1)表示之基團之化合物的粒子等。 [化學式3] 式(A1)中,*表示鍵結鍵, Ya 1及Ya 2分別獨立地表示-N(Ra 1)-或-O-, Ra 1表示氫原子、烷基、烯基、炔基或芳基, B 1及B 2分別獨立地表示氫原子或取代基。 When the specific particles are particles of a compound having a triangular structure and an acid group or a base, examples of such specific particles include particles of a compound having a group represented by formula (A1). [Chemical formula 3] In the formula (A1), * represents a bond, Ya 1 and Ya 2 independently represent -N (Ra 1 )- or -O-, and Ra 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. , B 1 and B 2 each independently represent a hydrogen atom or a substituent.
式(A1)的Ya 1及Ya 2分別獨立地表示-N(Ra 1)-或-O-,-N(Ra 1)-為較佳。 Ya 1 and Ya 2 in the formula (A1) each independently represent -N(Ra 1 )- or -O-, preferably -N(Ra 1 )-.
Ra 1表示氫原子、烷基、烯基、炔基或芳基,氫原子或烷基為較佳,氫原子為更佳。 Ra 1所表示之烷基的碳數為1~20為較佳,1~15為更佳,1~8為進一步較佳。烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。Ra 1所表示之烷基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 Ra 1所表示之烯基的碳數為2~20為較佳,2~12為更佳,2~8為進一步較佳。烯基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。Ra 1所表示之烯基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 Ra 1所表示之炔基的碳數為2~40為較佳,2~30為更佳,2~25為尤佳。炔基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。Ra 1所表示之炔基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 Ra 1所表示之芳基的碳數為6~30為較佳,6~20為更佳,6~12為進一步較佳。Ra 1所表示之芳基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 Ra 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The number of carbon atoms in the alkyl group represented by Ra 1 is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkyl group represented by Ra 1 may further have a substituent. Examples of the substituent include the substituent T described below. The number of carbon atoms in the alkenyl group represented by Ra 1 is preferably 2 to 20, more preferably 2 to 12, and further preferably 2 to 8. The alkenyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkenyl group represented by Ra 1 may further have a substituent. Examples of the substituent include the substituent T described below. The number of carbon atoms in the alkynyl group represented by Ra 1 is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkynyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkynyl group represented by Ra 1 may further have a substituent. Examples of the substituent include the substituent T described below. The number of carbon atoms in the aryl group represented by Ra 1 is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group represented by Ra 1 may further have a substituent. Examples of the substituent include the substituent T described below.
式(A1)的B 1及B 2分別獨立地表示氫原子或取代基。作為取代基,可以列舉後述之取代基T,烷基、芳基及雜環基為較佳,芳基及雜環基為更佳。作為較佳之一態樣,可以列舉B 1及B 2中的一者為雜環基,另一者為芳基的態樣。作為雜環基,含氮雜環基為較佳,苯并咪唑酮(benzimidazolone)基為更佳。 B 1 and B 2 in formula (A1) each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent T described below. An alkyl group, an aryl group and a heterocyclic group are preferred, and an aryl group and a heterocyclic group are more preferred. As a preferred aspect, one of B 1 and B 2 is a heterocyclic group and the other is an aryl group. As the heterocyclic group, a nitrogen-containing heterocyclic group is preferred, and a benzimidazolone group is more preferred.
當特定粒子為具有三𠯤結構和酸基或鹼基之化合物的粒子時,特定粒子為由下述式(b1)表示之化合物的粒子為較佳。 A 1-L 1-Z 1・・・・・・(b1) When the specific particles are particles of a compound having a triangular structure and an acid group or a base, it is preferable that the specific particles are particles of a compound represented by the following formula (b1). A 1 -L 1 -Z 1 ・・・・・・(b1)
式(b1)的A 1表示由上述式(A1)表示之基團。 A 1 in formula (b1) represents a group represented by the above formula (A1).
式(b1)的L 1表示單鍵或二價連結基,二價連結基為較佳。作為L 1所表示之二價連結基,可以列舉伸烷基、伸芳基、雜環基、-O-、-NR L1-、-NHCO-、-CONH-、-OCO-、-COO-、-CO-、-SO 2NH-、-SO 2-及該等的組合。伸烷基的碳數為1~30為較佳,1~15為更佳,1~8為進一步較佳,1~5為尤佳。伸烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為尤佳。伸芳基的碳數為6~30為較佳,6~15為更佳。伸芳基為伸苯基為較佳。R L1表示氫原子、烷基、烯基、炔基或芳基,氫原子或烷基為較佳,氫原子為更佳。關於R L1所表示之烷基、烯基、炔基及芳基的較佳範圍,與作為Ra 1的烷基、烯基、炔基及芳基的較佳範圍進行說明之範圍相同。 L 1 in the formula (b1) represents a single bond or a bivalent linking group, and a divalent linking group is preferred. Examples of the divalent linking group represented by L 1 include an alkylene group, an aryl group, a heterocyclic group, -O-, -NR L1 -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO 2 NH-, -SO 2 - and combinations thereof. The number of carbon atoms in the alkylene group is preferably from 1 to 30, more preferably from 1 to 15, further preferably from 1 to 8, and particularly preferably from 1 to 5. The alkylene group may be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is particularly preferred. The carbon number of the aryl group is preferably 6 to 30, more preferably 6 to 15. The aryl group is preferably a phenylene group. R L1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The preferable ranges of the alkyl group, alkenyl group, alkynyl group and aryl group represented by R L1 are the same as those explained as the preferable ranges of the alkyl group, alkenyl group, alkynyl group and aryl group of Ra 1 .
L 1所表示之二價連結基為由下述式(L1)表示之基團為較佳。 -L 1A-L 1B-L 1C-・・・・・・(L1) 式中,L 1A及L 1C分別獨立地表示-O-、-NR L1-、-NHCO-、-CONH-、-OCO-、-COO-、-CO-、-SO 2NH-或-SO 2-,L 1B表示單鍵或二價連結基。 The bivalent linking group represented by L 1 is preferably a group represented by the following formula (L1). -L 1A -L 1B -L 1C -・・・・・・(L1) In the formula, L 1A and L 1C independently represent -O-, -NR L1 -, -NHCO-, -CONH-, -OCO -, -COO-, -CO-, -SO 2 NH- or -SO 2 -, L 1B represents a single bond or a divalent linking group.
作為L 1B所表示之二價連結基,可以列舉伸烷基、伸芳基、將伸烷基和伸芳基經由單鍵或-O-、-NR L1-、-NHCO-、-CONH-、-OCO-、-COO-、-CO-、-SO 2NH-、-SO 2-及由該等的組合組成之基團鍵結而成之基團、將伸烷基彼此或伸芳基彼此經由-O-、-NR L1-、-NHCO-、-CONH-、-OCO-、-COO-、-CO-、-SO 2NH-、-SO 2-及由該等的組合組成之基團鍵結而成之基團等。 Examples of the divalent linking group represented by L 1B include an alkylene group and an aryl group. The alkylene group and the aryl group are connected via a single bond or -O-, -NR L1 -, -NHCO-, -CONH-, - OCO-, -COO-, -CO-, -SO 2 NH-, -SO 2 - and groups composed of combinations of these are bonded together, with alkylene groups or aryl groups connected through -O-, -NR L1 -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO 2 NH-, -SO 2 - and group bonds composed of these combinations The groups formed by the knot, etc.
作為L 1的具體例,可以列舉下述結構的基團。 [化學式4] Specific examples of L 1 include groups having the following structures. [Chemical formula 4]
式(b1)的Z 1表示具有酸基或鹼基之基團。作為酸基及鹼基的種類,可以列舉上述之基團。 Z 1 in formula (b1) represents a group having an acid group or a base. Examples of the types of acidic groups and bases include the above-mentioned groups.
式(b1)的Z 1為由式(Z1)表示之基團或由式(Z10)表示之基團為較佳。 Z 1 of formula (b1) is preferably a group represented by formula (Z1) or a group represented by formula (Z10).
[化學式5] 式(Z1)中,*表示鍵結鍵, Yz 1表示-N(Ry 1)-或-O-, Ry 1表示氫原子、烷基、烯基、炔基或芳基, Lz 1表示二價連結基, Rz 1及Rz 2分別獨立地表示氫原子、烷基、烯基、炔基或芳基, Rz 1與Rz 2可以經由二價基團鍵結而形成環, m表示1~5的整數。 [化學式6] [Chemical Formula 5] In formula (Z1), * represents a bond, Yz 1 represents -N(Ry 1 )- or -O-, Ry 1 represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group or aryl group, Lz 1 represents a divalent Linking groups, Rz 1 and Rz 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, Rz 1 and Rz 2 can be bonded through a divalent group to form a ring, m represents 1 to 5 integer. [Chemical formula 6]
式(Z10)中,*表示鍵結鍵,Lc 1及Lc 2分別獨立地表示單鍵或連結基,Rc 1及Rc 2分別獨立地表示取代基,Rc 1及Rc 2中的至少一者表示酸基或鹼基。 In the formula (Z10), * represents a bond, Lc 1 and Lc 2 each independently represent a single bond or a connecting group, Rc 1 and Rc 2 each independently represent a substituent, and at least one of Rc 1 and Rc 2 represents Acid or base.
首先,對式(Z1)進行說明。 式(Z1)中,Yz 1表示-N(Ry 1)-或-O-,-N(Ry 1)-為較佳。Ry 1表示氫原子、烷基、烯基、炔基或芳基,氫原子或烷基為較佳,氫原子為更佳。關於Ry 1所表示之烷基、烯基、炔基及芳基的較佳範圍,與作為Ra 1的烷基、烯基、炔基及芳基的較佳範圍進行說明之範圍相同。 First, equation (Z1) will be explained. In formula (Z1), Yz 1 represents -N(Ry 1 )- or -O-, and -N(Ry 1 )- is preferred. Ry 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The preferable ranges of the alkyl group, alkenyl group, alkynyl group and aryl group represented by Ry 1 are the same as those explained as the preferable ranges of the alkyl group, alkenyl group, alkynyl group and aryl group of Ra 1 .
式(Z1)中,作為Lz 1所表示之二價連結基,可以列舉伸烷基、伸芳基、雜環基、-O-、-NR L1-、-NHCO-、-CONH-、-OCO-、-COO-、-CO-、-SO 2NH-、-SO 2-及該等的組合,伸烷基為較佳。伸烷基的碳數為1~30為較佳,1~15為更佳,1~8為進一步較佳,1~5為尤佳。伸烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為尤佳。 In the formula (Z1), examples of the bivalent linking group represented by Lz 1 include an alkylene group, an aryl group, a heterocyclic group, -O-, -NR L1 -, -NHCO-, -CONH-, and -OCO. -, -COO-, -CO-, -SO 2 NH-, -SO 2 - and combinations thereof, alkylene groups are preferred. The number of carbon atoms in the alkylene group is preferably from 1 to 30, more preferably from 1 to 15, further preferably from 1 to 8, and particularly preferably from 1 to 5. The alkylene group may be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is particularly preferred.
式(Z1)中,Rz 1及Rz 2分別獨立地表示氫原子、烷基、烯基、炔基或芳基,烷基或芳基為較佳,烷基為更佳。烷基的碳數為1~10為較佳,1~5為更佳,1~3為進一步較佳,1或2為尤佳。烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。烯基的碳數為2~10為較佳,2~8為更佳,2~5為尤佳。烯基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。炔基的碳數為2~10為較佳,2~8為更佳,2~5為尤佳。炔基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。芳基的碳數為6~30為較佳,6~20為更佳,6~12為進一步較佳。 In the formula (Z1), Rz 1 and Rz 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. An alkyl group or an aryl group is preferred, and an alkyl group is more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 1 or 2. The alkyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 to 5. The alkenyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The number of carbon atoms in the alkynyl group is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 to 5. The alkynyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms.
式(Z1)中,Rz 1與Rz 2可以經由二價基團鍵結而形成環。作為二價基團,可以列舉-CH 2-、-O-、-SO 2-。作為Rz 1與Rz 2經由二價基團形成之環的具體例,可以列舉以下。 [化學式7] In formula (Z1), Rz 1 and Rz 2 may be bonded via a divalent group to form a ring. Examples of the divalent group include -CH 2 -, -O-, and -SO 2 -. Specific examples of the ring formed by Rz 1 and Rz 2 via a divalent group include the following. [Chemical Formula 7]
式(Z1)中,m表示1~5的整數,1~4為較佳,1~3為更佳,2或3為進一步較佳,2為尤佳。In the formula (Z1), m represents an integer of 1 to 5, 1 to 4 is preferred, 1 to 3 is more preferred, 2 or 3 is further preferred, and 2 is particularly preferred.
由式(Z1)表示之基團為由下述式(Z2)表示之基團為較佳。 [化學式8] 式(Z2)中,*表示鍵結鍵, Yz 2及Yz 3分別獨立地表示-N(Ry 2)-或-O-, Ry 2表示氫原子、烷基、烯基、炔基或芳基, Lz 2及Lz 3分別獨立地表示二價連結基, Rz 3~Rz 6分別獨立地表示氫原子、烷基、烯基、炔基或芳基, Rz 3與Rz 4及Rz 5與Rz 6可以分別經由二價基團鍵結而形成環。 The group represented by formula (Z1) is preferably a group represented by the following formula (Z2). [Chemical formula 8] In formula (Z2), * represents a bond, Yz 2 and Yz 3 independently represent -N (Ry 2 )- or -O-, Ry 2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group , Lz 2 and Lz 3 each independently represent a divalent linking group, Rz 3 to Rz 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, Rz 3 and Rz 4 and Rz 5 and Rz 6 Each may be bonded via a divalent group to form a ring.
式(Z2)的Yz 2及Yz 3的含義與式(Z1)的Yz 1含義相同,較佳範圍亦相同。Ry 2表示氫原子、烷基、烯基、炔基或芳基,氫原子或烷基為較佳,氫原子為更佳。關於Ry 2所表示之烷基、烯基、炔基及芳基的較佳範圍,與作為Ra 1的烷基、烯基、炔基及芳基的較佳範圍進行說明之範圍相同。 Yz 2 and Yz 3 in the formula (Z2) have the same meaning as Yz 1 in the formula (Z1), and the preferred ranges are also the same. Ry 2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The preferable ranges of the alkyl group, alkenyl group, alkynyl group and aryl group represented by Ry 2 are the same as those explained as the preferable ranges of the alkyl group, alkenyl group, alkynyl group and aryl group of Ra 1 .
式(Z2)的Lz 2及Lz 3的含義與式(Z1)的Lz 1的含義相同,較佳範圍亦相同。式(Z2)的Rz 3~Rz 6的含義與式(Z1)的Rz 1及Rz 2含義相同,較佳範圍亦相同。 The meanings of Lz 2 and Lz 3 in the formula (Z2) are the same as the meaning of Lz 1 in the formula (Z1), and the preferred ranges are also the same. The meanings of Rz 3 to Rz 6 in the formula (Z2) are the same as those of Rz 1 and Rz 2 in the formula (Z1), and the preferred ranges are also the same.
接著,對式(Z10)進行說明。 式(Z10)中,Lc 1及Lc 2分別獨立地表示單鍵或連結基,二價連結基為較佳。作為二價連結基,可以列舉伸烷基、伸芳基、-O-、-NR L1-、-NHCO-、-CONH-、-OCO-、-COO-、-CO-、-SO 2NH-、-SO 2-及該等的組合。伸烷基的碳數為1~30為較佳,1~15為更佳,1~8為進一步較佳,1~5為尤佳。伸烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為尤佳。伸芳基的碳數為6~30為較佳,6~15為更佳。伸芳基為伸苯基為較佳。R L1表示氫原子、烷基或芳基,氫原子或烷基為較佳,氫原子為更佳。R L1所表示之烷基的碳數為1~20為較佳,1~15為更佳,1~8為進一步較佳。烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。R L1所表示之烷基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。R L1所表示之芳基的碳數為6~30為較佳,6~20為更佳,6~12為進一步較佳。R L1所表示之芳基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 Next, equation (Z10) will be explained. In the formula (Z10), Lc 1 and Lc 2 each independently represent a single bond or a connecting group, and a divalent connecting group is preferred. Examples of the divalent linking group include an alkylene group, an aryl group, -O-, -NR L1 -, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO 2 NH- , -SO 2 - and combinations thereof. The number of carbon atoms in the alkylene group is preferably from 1 to 30, more preferably from 1 to 15, further preferably from 1 to 8, and particularly preferably from 1 to 5. The alkylene group may be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is particularly preferred. The carbon number of the aryl group is preferably 6 to 30, more preferably 6 to 15. The aryl group is preferably a phenylene group. R L1 represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The number of carbon atoms in the alkyl group represented by R L1 is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkyl group represented by R L1 may further have a substituent. Examples of the substituent include the substituent T described below. The number of carbon atoms in the aryl group represented by R L1 is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group represented by R L1 may further have a substituent. Examples of the substituent include the substituent T described below.
式(Z10)中,Rc 1及Rc 2分別獨立地表示取代基。作為取代基,可以列舉烷基、芳基、雜環基、羥基、酸基及鹼基。其中,Rc 1及Rc 2中的至少一者表示酸基或鹼基。Rc 1及Rc 2中的至少一者為鹼基為較佳,Rc 1及Rc 2兩者為鹼基為更佳。作為酸基及鹼基,可以列舉上述者。烷基的碳數為1~30為較佳,1~15為更佳,1~8為進一步較佳。烷基可以為直鏈、支鏈、環狀中的任一種,直鏈或支鏈為較佳,直鏈為更佳。芳基的碳數為6~30為較佳,6~20為更佳,6~12為進一步較佳。雜環基可以為單環,亦可以為縮合環。雜環基為單環或縮合數為2~4的縮合環為較佳。構成雜環基的環之雜原子數為1~3為較佳。構成雜環基之雜原子為氮原子、氧原子或硫原子為較佳。構成雜環基的環之碳原子數為3~30為較佳,3~18為更佳,3~12為進一步較佳。烷基、芳基、雜環基可以進一步具有取代基。作為取代基,可以列舉後述之取代基T。 In formula (Z10), Rc 1 and Rc 2 each independently represent a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an acid group and a base group. Wherein, at least one of Rc 1 and Rc 2 represents an acid group or a base. It is preferred that at least one of Rc 1 and Rc 2 is a base, and it is more preferred that both Rc 1 and Rc 2 are bases. Examples of acidic groups and bases include those mentioned above. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group can be any one of straight chain, branched chain, and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms. The heterocyclyl group may be a single ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms in the ring constituting the heterocyclyl group is preferably 1 to 3. The heteroatoms constituting the heterocyclic group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The number of carbon atoms of the ring constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The alkyl group, aryl group, and heterocyclic group may further have a substituent. Examples of the substituent include the substituent T described below.
(取代基T) 作為取代基T,可以列舉以下基團。鹵素原子(例如,氟原子、氯原子、溴原子、碘原子)、烷基(較佳為碳數1~30的烷基)、烯基(較佳為碳數2~30的烯基)、炔基(較佳為碳數2~30的炔基)、芳基(較佳為碳數6~30的芳基)、雜芳基(較佳為碳數1~30的雜芳基)、烷氧基(較佳為碳數1~30的烷氧基)、芳氧基(較佳為碳數6~30的芳氧基)、雜芳氧基(較佳為碳數1~30的雜芳氧基)、醯基(較佳為碳數2~30的醯基)、烷氧基羰基(較佳為碳數2~30的烷氧基羰基)、芳氧基羰基(較佳為碳數7~30的芳氧基羰基)、雜芳氧基羰基(較佳為碳數2~30的雜芳氧基羰基)、醯氧基(較佳為碳數2~30的醯氧基)、醯胺基(較佳為碳數2~30的醯胺基)、胺基羰基胺基(較佳為碳數2~30的胺基羰基胺基)、烷氧基羰基胺基(較佳為碳數2~30的烷氧基羰基胺基)、芳氧基羰基胺基(較佳為碳數7~30的芳氧基羰基胺基)、胺磺醯基(較佳為碳數0~30的胺磺醯基)、胺磺醯基胺基(較佳為碳數0~30的胺磺醯基胺基)、胺甲醯基(較佳為碳數1~30的胺甲醯基)、烷硫基(較佳為碳數1~30的烷硫基)、芳硫基(較佳為碳數6~30的芳硫基)、雜芳硫基(較佳為碳數1~30的雜芳硫基)、烷基磺醯基(較佳為碳數1~30的烷基磺醯基)、烷基磺醯基胺基(較佳為碳數1~30的烷基磺醯基胺基)、芳基磺醯基(較佳為碳數6~30的芳基磺醯基)、芳基磺醯基胺基(較佳為碳數6~30的芳基磺醯基胺基)、雜芳基磺醯基(較佳為碳數1~30的雜芳基磺醯基)、雜芳基磺醯基胺基(較佳為碳數1~30的雜芳基磺醯基胺基)、烷基亞磺醯基(較佳為碳數1~30的烷基亞磺醯基)、芳基亞磺醯基(較佳為碳數6~30的芳基亞磺醯基)、雜芳基亞磺醯基(較佳為碳數1~30的雜芳基亞磺醯基)、脲基(較佳為碳數1~30的脲基)、羥基、硝基、羧基、磺基、磷酸基、羧酸醯胺基、磺酸醯胺基、醯亞胺基、膦基、巰基、氰基、烷基亞磺酸基、芳基亞磺酸基、芳基偶氮基、雜芳基偶氮基、矽基、肼基、亞胺基。當該等基團為能夠進一步取代之基團時,可以進一步具有取代基。作為取代基,可以列舉在上述之取代基T中說明之基團。 (Substituent T) Examples of the substituent T include the following groups. Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), Alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), aryl group (preferably an aryl group having 6 to 30 carbon atoms), heteroaryl group (preferably an aryl group having 1 to 30 carbon atoms), Alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), heteroaryloxy group (preferably an aryloxy group having 1 to 30 carbon atoms) Heteroaryloxy group), hydroxyl group (preferably a hydroxyl group with 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group with 2 to 30 carbon atoms), aryloxycarbonyl group (preferably a hydroxyl group with 2 to 30 carbon atoms) Aryloxycarbonyl group having 7 to 30 carbon atoms), heteroaryloxycarbonyl group (preferably heteroaryloxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably acyloxycarbonyl group having 2 to 30 carbon atoms) ), amide group (preferably a amide group with 2 to 30 carbon atoms), aminocarbonylamino group (preferably an aminocarbonylamino group with 2 to 30 carbon atoms), alkoxycarbonylamino group (more preferably Preferably, it is an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably it is an aryloxycarbonylamino group having 7 to 30 carbon atoms), or sulfamide group (preferably it is an alkoxycarbonylamino group having 7 to 30 carbon atoms). sulfonamide group (0 to 30), sulfonamide group (preferably sulfonamide group with 0 to 30 carbon atoms), carbamoformyl group (preferably amine methyl group with 1 to 30 carbon atoms) acylthio group), alkylthio group (preferably an alkylthio group with 1 to 30 carbon atoms), arylthio group (preferably an arylthio group with 6 to 30 carbon atoms), heteroarylthio group (preferably an arylthio group with 6 to 30 carbon atoms) 1 to 30 heteroarylthio group), alkylsulfonyl group (preferably an alkylsulfonyl group with 1 to 30 carbon atoms), alkylsulfonylamine group (preferably an alkyl group with 1 to 30 carbon atoms) arylsulfonylamine group), arylsulfonylamine group (preferably an arylsulfonylamine group with 6 to 30 carbon atoms), arylsulfonylamine group (preferably an arylsulfonyl group with 6 to 30 carbon atoms) acylamine group), heteroarylsulfonylamine group (preferably a heteroarylsulfonylamine group having 1 to 30 carbon atoms), a heteroarylsulfonylamine group (preferably a heteroaryl sulfonylamine group having 1 to 30 carbon atoms) sulfonylamine group), alkylsulfinyl group (preferably an alkylsulfinyl group with 1 to 30 carbon atoms), arylsulfinyl group (preferably an aryl group with 6 to 30 carbon atoms) sulfenyl group), heteroarylsulfenyl group (preferably a heteroarylsulfenyl group with 1 to 30 carbon atoms), urea group (preferably a urea group with 1 to 30 carbon atoms), hydroxyl group, Nitro group, carboxyl group, sulfo group, phosphate group, carboxylic acid amide group, sulfonate amide group, amide group, phosphine group, mercapto group, cyano group, alkyl sulfinic acid group, aryl sulfinic acid group, Aryl azo group, heteroarylazo group, silicon group, hydrazine group, imine group. When these groups are groups capable of further substitution, they may further have a substituent. Examples of the substituent include the groups described for the substituent T described above.
作為特定粒子的具體例,可以列舉後述之實施例中記載之化合物、日本特開昭56-118462號公報中記載之化合物、日本特開昭63-264674號公報中記載之化合物、日本特開平01-217077號公報中記載之化合物、日本特開平03-009961號公報中記載之化合物、日本特開平03-026767號公報中記載之化合物、日本特開平03-153780號公報中記載之化合物、日本特開平03-045662號公報中記載之化合物、日本特開平04-285669號公報中記載之化合物、日本特開平06-145546號公報中記載之化合物、日本特開平06-212088號公報中記載之化合物、日本特開平06-240158號公報中記載之化合物、日本特開平10-030063號公報中記載之化合物、日本特開平10-195326號公報中記載之化合物、國際公開第2011/024896號的0086~0098段中記載之化合物、國際公開第2012/102399號的0063~0094段中記載之化合物、國際公開第2017/038252號的0082段中記載之化合物、日本特開2015-151530號公報的0171段中記載之化合物、日本特開2011-252065號公報的0162~0183段中記載之化合物、日本特開2003-081972號公報中記載之化合物、日本專利第5299151號公報中記載之化合物、日本特開2015-172732號公報中記載之化合物、日本特開2014-199308號公報中記載之化合物、日本特開2014-085562號公報中記載之化合物、日本特開2014-035351號公報中記載之化合物、日本特開2008-081565號公報中記載之化合物、日本特開2019-109512號公報中記載之化合物、日本特開2019-133154號公報中記載之化合物、國際公開第2020/002106號中記載之具有硫醇連結基之二酮吡咯并吡咯化合物、日本特開2018-168244號公報中記載之苯并咪唑酮化合物、日本特開2020-160279號公報中記載之異吲哚啉化合物或該等的鹽、日本專利第6996282號中記載之具有由通式(1)表示之異吲哚啉骨架之化合物等。Specific examples of the specific particles include compounds described in the examples described below, compounds described in Japanese Patent Application Laid-Open No. Sho 56-118462, compounds described in Japanese Patent Application Laid-Open No. Sho 63-264674, and Japanese Patent Application Laid-Open No. 01 - Compounds described in Japanese Patent Application Publication No. 03-009961, Compounds described in Japanese Patent Application Publication No. 03-026767, Compounds described in Japanese Patent Application Publication No. 03-153780, Japanese Patent Application Publication No. 03-026767 Compounds described in Japanese Patent Application Publication No. 03-045662, compounds described in Japanese Patent Application Publication No. 04-285669, compounds described in Japanese Patent Application Publication No. 06-145546, compounds described in Japanese Patent Application Publication No. 06-212088, Compounds described in Japanese Patent Application Publication No. 06-240158, compounds described in Japanese Patent Application Publication No. 10-030063, compounds described in Japanese Patent Application Publication No. 10-195326, 0086 to 0098 of International Publication No. 2011/024896 Compounds described in paragraphs, compounds described in paragraphs 0063 to 0094 of International Publication No. 2012/102399, compounds described in paragraph 0082 of International Publication No. 2017/038252, and compounds described in paragraph 0171 of Japanese Patent Application Laid-Open No. 2015-151530 Compounds described, compounds described in paragraphs 0162 to 0183 of Japanese Patent Application Publication No. 2011-252065, compounds described in Japanese Patent Application Publication No. 2003-081972, compounds described in Japanese Patent Application Publication No. 5299151, Japanese Patent Application Laid-Open No. 2015 - Compounds described in Japanese Patent Application Publication No. 172732, compounds described in Japanese Patent Application Publication No. 2014-199308, compounds described in Japanese Patent Application Publication No. 2014-085562, compounds described in Japanese Patent Application Publication No. 2014-035351, Japanese Patent Application Publication No. 2014-035351 Compounds described in Japanese Patent Application Publication No. 2008-081565, compounds described in Japanese Patent Application Publication No. 2019-109512, compounds described in Japanese Patent Application Publication No. 2019-133154, compounds having thiols described in International Publication No. 2020/002106 The diketopyrrolopyrrole compound of the linking group, the benzimidazolone compound described in Japanese Patent Application Laid-Open No. 2018-168244, the isoindoline compound described in Japanese Patent Application Laid-Open No. 2020-160279, or their salts, Japan Compounds having an isoindoline skeleton represented by general formula (1) described in Patent No. 6996282, etc.
相對於顏料100質量份,特定粒子的含量為1~70質量份為較佳。下限為2質量份以上為較佳,3質量份以上為更佳,5質量份以上為進一步較佳。上限為60質量份以下為較佳,50質量份以下為更佳,40質量份以下為進一步較佳。特定粒子可以僅使用1種,亦可以併用2種以上。當併用2種以上時,該等的總量在上述範圍內為較佳。The content of the specific particles is preferably 1 to 70 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. The upper limit is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less. Only one type of specific particles may be used, or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably within the above range.
<<樹脂>> 本發明的樹脂組成物含有樹脂。例如,以在樹脂組成物中分散顏料等之用途、黏合劑的用途摻合樹脂。再者,亦將主要用於分散顏料而使用之樹脂稱為分散劑。然而,樹脂的此種用途為一例,亦能夠以此種用途以外的用途為目的使用。 <<Resin>> The resin composition of the present invention contains resin. For example, the resin is blended for the purpose of dispersing pigments in a resin composition and the purpose of a binder. Furthermore, resins used mainly for dispersing pigments are also called dispersants. However, this use of the resin is an example, and it can also be used for purposes other than this use.
作為樹脂,例如,可以列舉(甲基)丙烯酸樹脂、環氧樹脂、(甲基)丙烯醯胺樹脂、烯-硫醇樹脂、聚碳酸酯樹脂、聚醚樹脂、聚芳酯樹脂、聚碸樹脂、聚醚碸樹脂、聚苯樹脂、聚伸芳基醚氧化膦樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚烯烴樹脂、環狀烯烴樹脂、聚酯樹脂、苯乙烯樹脂、矽氧烷樹脂等。又,作為樹脂,亦能夠使用國際公開第2016/088645號的實施例中記載之樹脂、日本特開2017-057265號公報中記載之樹脂、日本特開2017-032685號公報中記載之樹脂、日本特開2017-075248號公報中記載之樹脂、日本特開2017-066240號公報中記載之樹脂、日本特開2017-167513號公報中記載之樹脂、日本特開2017-173787號公報中記載之樹脂、日本特開2017-206689號公報的0041~0060段中記載之樹脂、日本特開2018-010856號公報的0022~0071段中記載之樹脂、日本特開2016-222891號公報中記載之嵌段聚異氰酸酯樹脂、日本特開2020-122052號公報中記載之樹脂、日本特開2020-111656號公報中記載之樹脂、日本特開2020-139021號公報中記載之樹脂、日本特開2017-138503號公報中記載之含有在主鏈具有環結構之結構單元及在側鏈具有聯苯基之結構單元之樹脂、日本特開2020-186373號公報的0199~0233段中記載之樹脂、日本特開2020-186325號公報中記載之鹼可溶性樹脂、韓國公開專利第10-2020-0078339號公報中記載之由式1表示之樹脂、國際公開第2022/030445號中記載之含有環氧基和酸基之共聚物。Examples of the resin include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, and polystyrene resin. , polyether styrene resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, Siloxane resin, etc. In addition, as the resin, the resin described in the Examples of International Publication No. 2016/088645, the resin described in Japanese Patent Application Laid-Open No. 2017-057265, the resin described in Japanese Patent Application Laid-Open No. 2017-032685, and the Japanese Patent Application Publication No. 2017-032685 can also be used. The resin described in Japanese Patent Application Publication No. 2017-075248, the resin described in Japanese Patent Application Publication No. 2017-066240, the resin described in Japanese Patent Application Publication No. 2017-167513, the resin described in Japanese Patent Application Publication No. 2017-173787 , the resin described in paragraphs 0041 to 0060 of Japanese Patent Application Publication No. 2017-206689, the resin described in paragraphs 0022 to 0071 of Japanese Patent Application Publication No. 2018-010856, and the block described in Japanese Patent Application Publication No. 2016-222891 Polyisocyanate resin, resin described in Japanese Patent Application Publication No. 2020-122052, resin described in Japanese Patent Application Publication No. 2020-111656, resin described in Japanese Patent Application Publication No. 2020-139021, Japanese Patent Application Publication No. 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in the publication, resin described in paragraphs 0199 to 0233 of Japanese Patent Application Laid-Open No. 2020-186373, Japanese Patent Application Laid-Open No. 2020 -Alkali-soluble resin described in Publication No. 186325, resin represented by Formula 1 described in Korean Patent Publication No. 10-2020-0078339, resin containing an epoxy group and an acid group described in International Publication No. 2022/030445 copolymer.
樹脂的重量平均分子量(Mw)為3000~2000000為較佳。上限為1000000以下為較佳,500000以下為更佳。下限為4000以上為較佳,5000以上為更佳。The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and even more preferably 500,000 or less. A lower limit of 4,000 or more is preferred, and a lower limit of 5,000 or more is even better.
作為樹脂,使用具有酸基之樹脂為較佳。作為酸基,例如可以列舉羧基、磷酸基、磺基、酚性羥基等。As the resin, it is preferable to use a resin having an acid group. Examples of the acidic group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group.
具有酸基之樹脂的酸值為30~500mgKOH/g為較佳。下限為40mgKOH/g以上為更佳,50mgKOH/g以上為尤佳。上限為400mgKOH/g以下為更佳,300mgKOH/g以下為進一步較佳,200mgKOH/g以下為尤佳。具有與酸基之樹脂的重量平均分子量(Mw)為5000~100000為較佳,5000~50000為更佳。又,具有酸基之樹脂的數量平均分子量(Mn)為1000~20000為較佳。The acid value of the resin with acid groups is preferably 30 to 500 mgKOH/g. It is more preferable that the lower limit is 40 mgKOH/g or more, and it is particularly preferable that it is 50 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. In addition, the number average molecular weight (Mn) of the resin having an acidic group is preferably 1,000 to 20,000.
具有酸基之樹脂含有在側鏈上具有酸基之重複單元為較佳,在樹脂的總重複單元中,含有5~70莫耳%的在側鏈上具有酸基之重複單元為更佳。在側鏈上具有酸基之重複單元的含量的上限為50莫耳%以下為較佳,30莫耳%以下為更佳。在側鏈上具有酸基之重複單元的含量的下限為10莫耳%以上為較佳,20莫耳%以上為更佳。The resin having acidic groups preferably contains repeating units having acidic groups on the side chains, and it is more preferable that the resin contains 5 to 70 mol% of repeating units having acidic groups on the side chains of the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group on the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group on the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.
關於具有酸基之樹脂,例如,能夠參閱日本特開2012-208494號公報的0558~0571段(對應之美國專利申請公開第2012/0235099號說明書的0685~0700段)的記載、日本特開2012-198408號公報的0076~0099段的記載,該等內容被編入本說明書中。又,具有酸基之樹脂亦能夠使用市售品。又,作為向樹脂導入酸基的方法,並無特別限制,但例如,可以列舉日本專利第6349629號公報中記載之方法。此外,作為向樹脂導入酸基的方法,亦可以列舉使環氧基的開環反應中所生成之羥基與酸酐反應而導入酸基之方法。Regarding the resin having an acid group, for example, the description of paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of the specification of U.S. Patent Application Publication No. 2012/0235099) and Japanese Patent Application Publication No. 2012 -The descriptions in paragraphs 0076 to 0099 of Public Gazette No. 198408 are incorporated into this manual. In addition, commercially available resins having acidic groups can also be used. In addition, the method for introducing acid groups into the resin is not particularly limited, but an example thereof is the method described in Japanese Patent No. 6349629. Moreover, as a method of introducing an acid group into a resin, the method of reacting the hydroxyl group produced by the ring-opening reaction of an epoxy group with an acid anhydride, and introducing an acid group can also be mentioned.
作為樹脂,亦能夠使用具有鹼基之樹脂。具有鹼基之樹脂為含有在側鏈上具有鹼基之重複單元之樹脂為較佳,具有在側鏈上具有鹼基之重複單元和不含鹼基之重複單元之共聚物為更佳,具有在側鏈上具有鹼基之重複單元和不含鹼基之重複單元之嵌段共聚物為進一步較佳。具有鹼基之樹脂亦能夠用作分散劑。具有鹼基之樹脂的胺值為5~300mgKOH/g為較佳。下限為10mgKOH/g以上為較佳,20mgKOH/g以上為更佳。上限為200mgKOH/g以下為較佳,100mgKOH/g以下為更佳。As the resin, a resin having a base can also be used. The resin having a base is preferably a resin containing a repeating unit having a base on the side chain, and a copolymer having a repeating unit having a base on the side chain and a repeating unit without a base is even more preferred, and has Block copolymers having repeating units of bases and repeating units without bases on the side chains are further preferred. Resins with basic bases can also be used as dispersants. The amine value of the resin having a base is preferably 5 to 300 mgKOH/g. The lower limit is preferably 10 mgKOH/g or more, and more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, and more preferably 100 mgKOH/g or less.
作為具有鹼基之樹脂的市售品,可以列舉DISPERBYK-161、162、163、164、166、167、168、174、182、183、184、185、2000、2001、2050、2150、2163、2164、BYK-LPN6919(以上為BYK-Chemie GmbH製造)、SOLSPERSE 11200、13240、13650、13940、24000、26000、28000、32000、32500、32550、32600、33000、34750、35100、35200、37500、38500、39000、53095、56000、7100(以上為Japan Lubrizol Corporation製造)、Efka PX 4300、4330、4046、4060、4080(以上為BASF公司製造)等。又,具有鹼基之樹脂亦能夠使用日本特開2014-219665號公報的0063~0112段中記載之嵌段共聚物(B)、日本特開2018-156021號公報的0046~0076段中記載之嵌段共聚物A1、日本特開2019-184763號公報的0150~0153段中記載之具有鹼基之乙烯樹脂,該等內容被編入本說明書中。Commercially available resins having bases include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164 , BYK-LPN6919 (the above are manufactured by BYK-Chemie GmbH), SOLSPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 3750 0, 38500, 39000 , 53095, 56000, 7100 (the above are manufactured by Japan Lubrizol Corporation), Efka PX 4300, 4330, 4046, 4060, 4080 (the above are manufactured by BASF Corporation), etc. In addition, the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Laid-Open No. 2014-219665, and the block copolymer (B) described in paragraphs 0046 to 0076 of Japanese Patent Application Laid-Open No. 2018-156021 can also be used as the resin having a base. The block copolymer A1 and the vinyl resin having a base described in paragraphs 0150 to 0153 of Japanese Patent Application Laid-Open No. 2019-184763 are incorporated into this specification.
樹脂使用具有酸基之樹脂和具有鹼基之樹脂亦較佳。在併用具有酸基之樹脂和具有鹼基之樹脂之情況下,相對於具有酸基之樹脂100質量份,具有鹼基之樹脂的含量為20~500質量份為較佳,30~300質量份為更佳,50~200質量份為進一步較佳。It is also preferable to use a resin having an acidic group or a resin having an alkali group as the resin. When a resin having an acidic group and a resin having an alkali group are used together, the content of the resin having an alkali group is preferably 20 to 500 parts by mass, and 30 to 300 parts by mass relative to 100 parts by mass of the resin having an acidic group. It is more preferable, and it is further more preferable that it is 50-200 mass parts.
作為樹脂,使用含有源自以下單體成分之重複單元之樹脂亦較佳,該單體包含由下述式(ED1)表示之化合物及/或由下述式(ED2)表示之化合物(以下,有時將該等化合物亦稱為“醚二聚體”。)。As the resin, it is also preferable to use a resin containing a repeating unit derived from a monomer component including a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, These compounds are sometimes also called "ether dimers".).
[化學式9] [Chemical Formula 9]
式(ED1)中,R 1及R 2分別獨立地表示氫原子或可以具有取代基之碳數1~25的烴基。 [化學式10] 式(ED2)中,R表示氫原子或碳數1~30的有機基團。關於式(ED2)的詳細內容,能夠參閱日本特開2010-168539號公報的記載,該內容被編入本說明書中。 In the formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical formula 10] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), please refer to the description of Japanese Patent Application Laid-Open No. 2010-168539, and this content is incorporated into this specification.
關於醚二聚體的具體例,例如,能夠參閱日本特開2013-029760號公報的0317段的記載,該內容被編入本說明書中。Regarding specific examples of the ether dimer, for example, the description in paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-029760 can be referred to, and this content is incorporated into this specification.
作為樹脂,使用含有源自由式(X)表示之化合物之重複單元之樹脂亦較佳。 [化學式11] 式中,R 1表示氫原子或甲基,R 21及R 22分別獨立地表示伸烷基,n表示0~15的整數。R 21及R 22所表示之伸烷基的碳數為1~10為較佳,1~5為更佳,1~3為進一步較佳,2或3為尤佳。n表示0~15的整數,0~5的整數為較佳,0~4的整數為更佳,0~3的整數為進一步較佳。 As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X). [Chemical formula 11] In the formula, R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 each independently represent an alkylene group, and n represents an integer of 0 to 15. The number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n represents an integer of 0 to 15. An integer of 0 to 5 is preferred, an integer of 0 to 4 is more preferred, and an integer of 0 to 3 is further preferred.
作為由式(X)表示之化合物,可以列舉對異丙苯基苯酚(para-cumyl phenol)的環氧乙烷或環氧丙烷改質(甲基)丙烯酸酯等。作為市售品,可以列舉ARONIX M-110(TOAGOSEI CO.,LTD.製造)等。Examples of the compound represented by formula (X) include ethylene oxide or propylene oxide modified (meth)acrylate of para-cumyl phenol. Examples of commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.) and the like.
作為樹脂,使用具有交聯性基之樹脂亦較佳。作為交聯性基,可以列舉含有乙烯性不飽和鍵之基團及環狀醚基。作為含有乙烯性不飽和鍵之基團,可以列舉乙烯基、苯乙烯基、(甲基)烯丙基、(甲基)丙烯醯基等。作為環狀醚基,可以列舉環氧基、氧雜環丁烷基等,環氧基為較佳。環氧基可以為脂環式環氧基。再者,脂環式環氧基係指具有由環氧環和飽和烴環縮合而成之環狀結構之一價官能基。As the resin, it is also preferable to use a resin having a crosslinkable group. Examples of the crosslinkable group include a group containing an ethylenically unsaturated bond and a cyclic ether group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acrylyl group, and the like. Examples of the cyclic ether group include an epoxy group, an oxetanyl group, and the like, with an epoxy group being preferred. The epoxy group may be an alicyclic epoxy group. Furthermore, the alicyclic epoxy group refers to a monovalent functional group having a cyclic structure formed by condensation of an epoxy ring and a saturated hydrocarbon ring.
作為樹脂,使用具有芳香族羧基之樹脂(以下,亦稱為樹脂Ac)亦較佳。在樹脂Ac中,芳香族羧基可以包含在重複單元的主鏈中,亦可以包含在重複單元的側鏈中。芳香族羧基包含在重複單元的主鏈中為較佳。再者,在本說明書中,芳香族羧基係指具有在芳香族環上鍵結有1個以上羧基之結構的基團。在芳香族羧基中,鍵結於芳香族環上之羧基的數量為1~4個為較佳,1~2個為更佳。As the resin, it is also preferable to use a resin having an aromatic carboxyl group (hereinafter also referred to as resin Ac). In the resin Ac, the aromatic carboxyl group may be included in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferred that the aromatic carboxyl group is included in the main chain of the repeating unit. In addition, in this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. Among the aromatic carboxyl groups, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.
樹脂Ac為含有選自由式(Ac-1)表示之重複單元及由式(Ac-2)表示之重複單元中之至少1種重複單元之樹脂為較佳。 [化學式12] 式(Ac-1)中,Ar 1表示含有芳香族羧基之基團,L 1表示-COO-或-CONH-,L 2表示二價連結基。 式(Ac-2)中,Ar 10表示含有芳香族羧基之基團,L 11表示-COO-或-CONH-,L 12表示三價連結基,P 10表示聚合物鏈。 The resin Ac is preferably a resin containing at least one repeating unit selected from the repeating unit represented by the formula (Ac-1) and the repeating unit represented by the formula (Ac-2). [Chemical formula 12] In the formula (Ac-1), Ar 1 represents a group containing an aromatic carboxyl group, L 1 represents -COO- or -CONH-, and L 2 represents a bivalent linking group. In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, L 11 represents -COO- or -CONH-, L 12 represents a trivalent linking group, and P 10 represents a polymer chain.
在式(Ac-1)中,作為Ar 1所表示之含有芳香族羧基之基團,可以列舉源自芳香族三羧酸酐之結構、源自芳香族四羧酸酐之結構等。作為芳香族三羧酸酐及芳香族四羧酸酐,可以列舉下述結構的化合物。 [化學式13] In the formula (Ac-1), examples of the aromatic carboxyl group-containing group represented by Ar 1 include a structure derived from an aromatic tricarboxylic anhydride, a structure derived from an aromatic tetracarboxylic anhydride, and the like. Examples of aromatic tricarboxylic acid anhydrides and aromatic tetracarboxylic acid anhydrides include compounds with the following structures. [Chemical formula 13]
上述式中,Q 1表示單鍵、-O-、-CO-、-COOCH 2CH 2OCO-、-SO 2-、-C(CF 3) 2-、由下述式(Q-1)表示之基團或由下述式(Q-2)表示之基團。 [化學式14] In the above formula, Q 1 represents a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C (CF 3 ) 2 -, and is represented by the following formula (Q-1) or a group represented by the following formula (Q-2). [Chemical formula 14]
Ar 1所表示之含有芳香族羧基之基團可以具有交聯性基。交聯性基為含有乙烯性不飽和鍵之基團及環狀醚基為較佳,含有乙烯性不飽和鍵之基團為更佳。作為Ar 1所表示之含有芳香族羧基之基團的具體例,可以列舉由式(Ar-11)表示之基團、由式(Ar-12)表示之基團、由式(Ar-13)表示之基團等。 [化學式15] The aromatic carboxyl group-containing group represented by Ar 1 may have a crosslinking group. The crosslinkable group is preferably a group containing an ethylenically unsaturated bond and a cyclic ether group, and a group containing an ethylenically unsaturated bond is more preferably a group. Specific examples of the aromatic carboxyl group-containing group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), a group represented by formula (Ar-13) Represented groups, etc. [Chemical formula 15]
式(Ar-11)中,n1表示1~4的整數,1或2為較佳,2為更佳。 式(Ar-12)中,n2表示1~8的整數,1~4的整數為較佳,1或2為更佳,2為進一步較佳。 式(Ar-13)中,n3及n4分別獨立地表示0~4的整數,0~2的整數為較佳,1或2為更佳,1為進一步較佳。其中,n3及n4中的至少一者為1以上的整數。 式(Ar-13)中,Q 1表示單鍵、-O-、-CO-、-COOCH 2CH 2OCO-、-SO 2-、-C(CF 3) 2-、由上述式(Q-1)表示之基團或由上述式(Q-2)表示之基團。 式(Ar-11)~(Ar-13)中,*1表示與L 1的鍵結位置。 In formula (Ar-11), n1 represents an integer from 1 to 4, 1 or 2 is preferred, and 2 is more preferred. In formula (Ar-12), n2 represents an integer of 1 to 8, and an integer of 1 to 4 is preferred, 1 or 2 is more preferred, and 2 is further preferred. In the formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4. An integer of 0 to 2 is preferred, 1 or 2 is more preferred, and 1 is further preferred. Among them, at least one of n3 and n4 is an integer greater than 1. In the formula (Ar-13), Q 1 represents a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C (CF 3 ) 2 -. From the above formula (Q- The group represented by 1) or the group represented by the above formula (Q-2). In the formulas (Ar-11) to (Ar-13), *1 represents the bonding position with L 1 .
式(Ac-1)中L 1表示-COO-或-CONH-,表示-COO-為較佳。 In formula (Ac-1), L 1 represents -COO- or -CONH-, preferably -COO-.
在式(Ac-1)中,作為L 2所表示之二價連結基,可以列舉伸烷基、伸芳基、-O-、-CO-、-COO-、-OCO-、-NH-、-S-及組合該等中的2種以上而成之基團。伸烷基的碳數為1~30為較佳,1~20為更佳,1~15為進一步較佳。伸烷基可以為直鏈、支鏈、環狀中的任一種。伸芳基的碳數為6~30為較佳,6~20為更佳,6~10為進一步較佳。伸烷基及伸芳基可以具有取代基。作為取代基,可以列舉羥基等。L 2所表示之二價連結基為由-L 2a-O-表示之基團為較佳。L 2a可以列舉伸烷基;伸芳基;組合伸烷基和伸芳基而成之基團;組合選自伸烷基及伸芳基中之至少1種和選自-O-、-CO-、-COO-、-OCO-、-NH-及-S-中之至少1種而成之基團等,伸烷基為較佳。伸烷基的碳數為1~30為較佳,1~20為更佳,1~15為進一步較佳。伸烷基可以為直鏈、支鏈、環狀中的任一種。伸烷基及伸芳基可以具有取代基。作為取代基,可以列舉羥基等。 In the formula (Ac-1), examples of the bivalent linking group represented by L 2 include an alkylene group, an aryl group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and groups formed by combining two or more of these. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The alkylene group and the aryl group may have a substituent. Examples of the substituent include hydroxyl group and the like. The bivalent linking group represented by L 2 is preferably a group represented by -L 2a -O-. L 2a can include an alkylene group; an aryl group; a group formed by combining an alkylene group and an aryl group; a combination of at least one selected from the group consisting of an alkylene group and an aryl group and a group selected from -O-, -CO- , -COO-, -OCO-, -NH- and -S-, etc., preferably an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The alkylene group may be linear, branched, or cyclic. The alkylene group and the aryl group may have a substituent. Examples of the substituent include hydroxyl group and the like.
在式(Ac-2)中,作為Ar 10所表示之含有芳香族羧基之基團,其含義與式(Ac-1)的Ar 1的含義相同,較佳範圍亦相同。 In the formula (Ac-2), the aromatic carboxyl group-containing group represented by Ar 10 has the same meaning as Ar 1 in the formula (Ac-1), and the preferred range is also the same.
式(Ac-2)中,L 11表示-COO-或-CONH-,表示-COO-為較佳。 In the formula (Ac-2), L 11 represents -COO- or -CONH-, preferably -COO-.
在式(Ac-2)中,作為L 12所表示之三價連結基,可以列舉烴基、-O-、-CO-、-COO-、-OCO-、-NH-、-S-及組合該等中的2種以上而成之基團。烴基可以列舉脂肪族烴基、芳香族烴基。脂肪族烴基的碳數為1~30為較佳,1~20為更佳,1~15為進一步較佳。脂肪族烴基可以為直鏈、支鏈、環狀中的任一種。芳香族烴基的碳數為6~30為較佳,6~20為更佳,6~10為進一步較佳。烴基可以具有取代基。作為取代基,可以列舉羥基等。L 12所表示之三價連結基為由式(L12-1)表示之基團為較佳,由式(L12-2)表示之基團為更佳。 [化學式16] In the formula (Ac-2), examples of the trivalent connecting group represented by L 12 include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations thereof. A group consisting of two or more of the following. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include hydroxyl group and the like. The trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2). [Chemical formula 16]
式(L12-1)中,L 12b表示三價連結基,X 1表示S,*1表示與式(Ac-2)的L 11的鍵結位置,*2表示與式(Ac-2)的P 10的鍵結位置。作為L 12b所表示之三價連結基,可以列舉烴基;組合烴基和選自-O-、-CO-、-COO-、-OCO-、-NH-及-S-中之至少1種而成之基團等,烴基或組合烴基和-O-而成之基團為較佳。 In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, *1 represents the bonding position with L 11 of formula (Ac-2), and *2 represents the bonding position with L 11 of formula (Ac-2). P 10 bonding position. Examples of the trivalent linking group represented by L 12b include a hydrocarbon group; a combination of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- Groups such as a hydrocarbon group or a group formed by combining a hydrocarbon group and -O- are preferred.
式(L12-2)中,L 12c表示三價連結基,X 1表示S,*1表示與式(Ac-2)的L 11的鍵結位置,*2表示與式(Ac-2)的P 10的鍵結位置。作為L 12c所表示之三價連結基,可以列舉烴基;組合烴基和選自-O-、-CO-、-COO-、-OCO-、-NH-及-S-中之至少1種而成之基團等,烴基為較佳。 In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, *1 represents the bonding position with L 11 of formula (Ac-2), and *2 represents the bonding position with L 11 of formula (Ac-2) P 10 bonding position. Examples of the trivalent linking group represented by L 12c include a hydrocarbon group; a combination of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- groups, etc., hydrocarbon groups are preferred.
式(Ac-2)中P 10表示聚合物鏈。P 10所表示之聚合物鏈具有選自聚酯結構、聚醚結構、聚苯乙烯結構及聚(甲基)丙烯酸結構中之至少1種結構為較佳。聚合物鏈P 10的重量平均分子量為500~20000為較佳。下限為1000以上為較佳。上限為10000以下為較佳,5000以下為更佳,3000以下為進一步較佳。若P 10的重量平均分子量在上述範圍內,則組成物中的顏料的分散性良好。在具有芳香族羧基之樹脂為具有由式(Ac-2)表示之重複單元之樹脂的情況下,該樹脂可較佳地用作分散劑。 In formula (Ac-2), P 10 represents a polymer chain. The polymer chain represented by P 10 preferably has at least one structure selected from the group consisting of polyester structure, polyether structure, polystyrene structure and poly(meth)acrylic acid structure. The weight average molecular weight of the polymer chain P 10 is preferably 500 to 20,000. A lower limit of 1,000 or more is preferred. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 3,000 or less. If the weight average molecular weight of P10 is within the above range, the dispersibility of the pigment in the composition will be good. In the case where the resin having an aromatic carboxyl group is a resin having a repeating unit represented by formula (Ac-2), the resin can be preferably used as a dispersant.
P 10所表示之聚合物鏈可以含有交聯性基。作為交聯性基,可以列舉含有乙烯性不飽和鍵之基團及環狀醚基。 The polymer chain represented by P 10 may contain a crosslinking group. Examples of the crosslinkable group include a group containing an ethylenically unsaturated bond and a cyclic ether group.
作為樹脂,使用選自接枝聚合物、星形聚合物、嵌段共聚物、及聚合物鏈的至少一個末端被酸基封端而成之樹脂中之至少1種為較佳。此種樹脂可較佳地用作分散劑。As the resin, it is preferred to use at least one selected from the group consisting of graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is terminated with an acid group. This resin can be preferably used as a dispersant.
作為接枝聚合物,可以列舉具有含有接枝鏈之重複單元之樹脂及具有由上述之式(Ac-2)表示之重複單元之樹脂等。作為接枝鏈,可以列舉含有選自聚酯結構、聚醚結構、聚苯乙烯結構及聚(甲基)丙烯酸結構中之至少1種結構之接枝鏈。作為接枝鏈的末端結構,並無特別限定。可以為氫原子,亦可以為取代基。作為取代基,可以列舉烷基、烷氧基、烷硫基醚基等。其中,從提高顏料的分散性之觀點而言,具有空間排斥效果之基團為較佳,碳數5~30的烷基或烷氧基為較佳。烷基及烷氧基可以為直鏈狀、支鏈狀及環狀中的任一種,直鏈狀或支鏈狀為較佳。Examples of the graft polymer include a resin having a repeating unit containing a graft chain, a resin having a repeating unit represented by the above formula (Ac-2), and the like. Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic acid structure. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthioether group, and the like. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferred, and an alkyl group or alkoxy group having 5 to 30 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched are preferred.
作為接枝聚合物的具體例,可以列舉日本特開2012-255128號公報的0025~0094段、日本特開2009-203462號公報的0022~0097段、日本特開2012-255128號公報的0102~0166段中記載之樹脂。Specific examples of the graft polymer include paragraphs 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128, paragraphs 0022 to 0097 of Japanese Patent Application Laid-Open No. 2009-203462, and paragraphs 0102 to 0102 of Japanese Patent Application Laid-Open No. 2012-255128. Resins described in paragraph 0166.
作為星形聚合物,可以列舉在核部鍵結有複數個聚合物鏈之結構的樹脂。作為星形聚合物的具體例,可以列舉日本特開2013-043962號公報的0196~0209段中記載之高分子化合物C-1~C-31等。Examples of star-shaped polymers include resins having a structure in which a plurality of polymer chains are bonded to a core. Specific examples of the star polymer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Laid-Open No. 2013-043962, and the like.
作為嵌段共聚物,係具有含有酸基或鹼基之重複單元之聚合物的嵌段(以下,亦稱為嵌段A)與具有不含酸基及鹼基之重複單元之聚合物的嵌段(以下,亦稱為嵌段B)的嵌段共聚物為較佳。嵌段共聚物亦能夠使用日本特開2014-219665號公報的0063~0112段中記載之嵌段共聚物(B)、日本特開2018-156021號公報的0046~0076段中記載之嵌段共聚物A1,該等內容被編入本說明書中。The block copolymer is a block of a polymer having repeating units containing acidic groups or bases (hereinafter also referred to as block A) and a polymer having repeating units containing no acidic groups or bases. Block copolymers of blocks (hereinafter also referred to as block B) are preferred. As the block copolymer, the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Laid-Open No. 2014-219665 and the block copolymer described in paragraphs 0046 to 0076 of Japanese Patent Application Laid-Open No. 2018-156021 can also be used. Item A1, these contents are incorporated into this manual.
作為聚合物鏈的至少一個末端被酸基封端而成之樹脂,可以列舉含有選自聚酯結構、聚醚結構及聚(甲基)丙烯酸結構中之至少1種結構之聚合物鏈的至少一個末端被酸基封端而成之結構的樹脂。作為封端聚合物鏈的末端之酸基,可以列舉羧基、磺基、磷酸基。Examples of the resin in which at least one end of the polymer chain is blocked by an acid group include at least one polymer chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic acid structure. A resin with a structure in which one end is capped with an acid group. Examples of the acid group that blocks the end of the polymer chain include a carboxyl group, a sulfo group, and a phosphate group.
樹脂使用作為分散劑的樹脂為較佳。作為分散劑,可以列舉酸性分散劑(酸性樹脂)、鹼性分散劑(鹼性樹脂)。在此,酸性分散劑(酸性樹脂)表示酸基的量多於鹼基的量之樹脂。作為酸性分散劑(酸性樹脂),將酸基的量與鹼基的量的總量設為100莫耳%時,酸基的量為70莫耳%以上的樹脂為較佳。酸性分散劑(酸性樹脂)所具有之酸基為羧基為較佳。酸性分散劑(酸性樹脂)的酸值為10~105mgKOH/g為較佳。又,鹼性分散劑(鹼性樹脂)表示鹼基的量多於酸基的量之樹脂。作為鹼性分散劑(鹼性樹脂),將酸基的量與鹼基的量的總量設為100莫耳%時,鹼基的量超過50莫耳%的樹脂為較佳。鹼性分散劑所具有之鹼基為胺基為較佳。As the resin, it is preferable to use a resin that serves as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and alkaline dispersants (basic resins). Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is greater than the amount of base groups. As an acidic dispersant (acidic resin), when the total amount of acid groups and base groups is 100 mol%, a resin having an acid group amount of 70 mol% or more is preferred. It is preferable that the acidic group of the acidic dispersant (acidic resin) is a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, the alkaline dispersant (alkaline resin) means a resin in which the amount of base groups is greater than the amount of acid groups. As an alkaline dispersant (alkaline resin), when the total amount of acid groups and bases is 100 mol%, a resin in which the amount of bases exceeds 50 mol% is preferred. The alkaline dispersant preferably has an amine group as its base.
分散劑亦能夠作為市售品而獲得,作為此種具體例,可以列舉BYK-Chemie GmbH製Disperbyk系列(例如,Disperbyk-111、161、2001等)、Lubrizol Japan Ltd.製SOLSPERSE系列(例如,SOLSPERSE20000、76500等)、Ajinomoto Fine-Techno Co.,Inc.製Ajispar系列、A208F(DKS Co.Ltd.製造)、H-3606(DKS Co.Ltd.製造)、SANDET ET(SANYO KASEI CO.,LTD.製造)等。又,亦能夠使用日本特開2012-137564號公報的0129段中記載之產品、日本特開2017-194662號公報的0235段中記載之產品作為分散劑。Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK-Chemie GmbH (for example, Disperbyk-111, 161, 2001, etc.) and the SOLSPERSE series manufactured by Lubrizol Japan Ltd. (for example, SOLSPERSE20000 , 76500, etc.), Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc., A208F (manufactured by DKS Co. Ltd.), H-3606 (manufactured by DKS Co. Ltd.), SANDET ET (SANYO KASEI CO., LTD. manufacturing), etc. In addition, the products described in Paragraph 0129 of Japanese Patent Application Laid-Open No. 2012-137564 and the products described in Paragraph 0235 of Japanese Patent Application Laid-Open No. 2017-194662 can also be used as the dispersant.
樹脂組成物的總固體成分中的樹脂的含量為1~80質量%為較佳。下限為5質量%以上為較佳,10質量%以上為更佳,15質量%以上為進一步較佳,20質量%以上為尤佳。上限為60質量%以下為較佳,50質量%以下為更佳。 樹脂組成物的總固體成分中的具有酸基之樹脂的含量為1~80質量%為較佳。下限為5質量%以上為較佳,10質量%以上為更佳,15質量%以上為進一步較佳,20質量%以上為尤佳。上限為60質量%以下為較佳,50質量%以下為更佳。 The content of the resin in the total solid content of the resin composition is preferably 1 to 80% by mass. The lower limit is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, and particularly preferably 20 mass% or more. The upper limit is preferably 60 mass% or less, and more preferably 50 mass% or less. The content of the resin having an acid group in the total solid content of the resin composition is preferably 1 to 80% by mass. The lower limit is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, and particularly preferably 20 mass% or more. The upper limit is preferably 60 mass% or less, and more preferably 50 mass% or less.
又,相對於顏料100質量份,作為分散劑的樹脂的含量為10~150質量份為較佳。下限為15質量份以上為較佳,20質量份以上為更佳。上限為100質量份以下為較佳,80質量份以下為更佳。Moreover, the content of the resin as a dispersant is preferably 10 to 150 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.
<<溶劑>> 本發明的樹脂組成物含有溶劑。作為溶劑,可以列舉有機溶劑。溶劑的種類只要滿足各成分的溶解性或組成物的塗布性,則基本上並無特別限制。作為有機溶劑,可以列舉酯系溶劑、酮系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑、烴系溶劑等。關於該等的詳細內容,能夠參閱國際公開第2015/166779號的0223段,該內容被編入本說明書中。又,亦能夠較佳地使用環狀烷基經取代之酯系溶劑、環狀烷基經取代之酮系溶劑。作為有機溶劑的具體例,可以列舉聚乙二醇單甲醚、二氯甲烷、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基賽路蘇乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、3-戊酮、4-庚酮、環己酮、2-甲基環己酮、3-甲基環己酮、4-甲基環己酮、環庚酮、環辛酮、乙酸環己酯、環戊酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚、丙二醇單甲醚乙酸酯、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、丙二醇二乙酸酯、3-甲氧基丁醇、甲基乙基酮、γ-丁內酯、環丁碸、苯甲醚、1,4-二乙醯氧基丁烷、二乙二醇單乙醚乙酸酯、1,3-丁二醇二乙酸酯、二丙二醇甲醚乙酸酯、二丙酮醇(別名為雙丙酮醇、4-羥基-4-甲基-2-戊酮)、2-甲氧基丙基乙酸酯、2-甲氧基-1-丙醇、異丙醇等。然而,有時出於環境方面等理由,減少作為有機溶劑之芳香族烴類(苯、甲苯、二甲苯、乙苯等)為較佳(例如,相對於有機溶劑總量,能夠設為50質量ppm(parts per million:百萬分率)以下,亦能夠設為10質量ppm以下,亦能夠設為1質量ppm以下)。 <<Solvent>> The resin composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details, please refer to paragraph 0223 of International Publication No. 2015/166779, which is incorporated into this specification. Furthermore, ester solvents in which a cyclic alkyl group is substituted and ketone solvents in which a cyclic alkyl group is substituted can also be suitably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcelusu acetate, Ethyl lactate, diglyme, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone Hexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbitol Acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide , Propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cyclotetrane, anisole, 1,4-diethyloxybutane, diethylene glycol Alcohol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone ), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol, etc. However, sometimes it is preferable to reduce the number of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, it can be set to 50 mass based on the total amount of organic solvents). ppm (parts per million: parts per million) or less, it can also be set to 10 mass ppm or less, or it can be set to 1 mass ppm or less).
在本發明中,使用金屬含量少的有機溶劑為較佳,有機溶劑的金屬含量例如為10質量ppb(parts per billion:十億分率)以下為較佳。可以視需要使用質量ppt(parts per trillion:兆分率)級別的有機溶劑,此類有機溶劑例如由Toyo Gosei Co.,Ltd提供(化學工業日報,2015年11月13日)。In the present invention, it is preferable to use an organic solvent with a small metal content. The metal content of the organic solvent is, for example, 10 mass ppb (parts per billion: parts per billion) or less. Organic solvents with a quality of ppt (parts per trillion: parts per trillion) level can be used as needed, and such organic solvents are provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
作為從有機溶劑中去除金屬等雜質之方法,例如能夠列舉蒸餾(分子蒸餾、薄膜蒸餾等)或使用了過濾器之過濾。作為用於過濾之過濾器的過濾器孔徑,10μm以下為較佳,5μm以下為更佳,3μm以下為進一步較佳。過濾器的材質為聚四氟乙烯、聚乙烯或尼龍為較佳。Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
有機溶劑可以含有異構物(原子數相同,但結構不同的化合物)。又,可以僅含有1種異構物,亦可以含有複數種異構物。Organic solvents can contain isomers (compounds with the same number of atoms but different structures). In addition, only one type of isomer may be contained, or a plurality of types of isomers may be contained.
過氧化物在有機溶劑中的含有率為0.8mmol/L以下為較佳,實質上不含過氧化物為更佳。It is preferable that the content rate of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that it contains substantially no peroxide.
樹脂組成物中的溶劑的含量為10~95質量%為較佳,20~90質量%為更佳,30~90質量%為進一步較佳。The content of the solvent in the resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 90% by mass.
又,從環境管制的觀點而言,本發明的樹脂組成物實質上不含環境管制物質為較佳。再者,在本發明中,實質上不含環境管制物質係指樹脂組成物中的環境管制物質的含量為50質量ppm以下,30質量ppm以下為較佳,10質量ppm以下為進一步較佳,1質量ppm以下為尤佳。環境管制物質例如可以列舉苯;甲苯、二甲苯等烷基苯類;氯苯等鹵化苯類等。該等依據REACH(化學品註冊、評估、授權和限制(Registration Evaluation Authorization and Restriction of CHemicals))規則、PRTR(污染物排放與轉移登記(Pollutant Release and Transfer Register))法、VOC(揮發性有機化合物(Volatile Organic Compounds))管制等被註冊為環境管制物質,使用量或處理方法受到嚴格管制。該等化合物有時在製造樹脂組成物中使用之各成分等時用作溶劑,並且有時作為殘留溶劑而混入樹脂組成物中。從對人的安全性、對環境的考慮的觀點而言,盡量減少該等物質為較佳。作為減少環境管制物質的方法,可以列舉:加熱或減壓系統,使其達到環境管制物質的沸點以上,以從系統中蒸餾去除環境管制物質而減少的方法。又,在蒸餾去除少量的環境管制物質的情況下,為了提高效率,使其和與該溶劑具有同等的沸點之溶劑共沸亦為有用。又,在含有具有自由基聚合性之化合物的情況下,為了抑制在減壓蒸餾去除中進行自由基聚合反應而導致分子間的交聯,可以添加聚合抑制劑等進行減壓蒸餾去除。該等蒸餾去除方法能夠在原料階段、使原料反應之生成物(例如,聚合之後的樹脂溶液或多官能單體溶液)的階段、或將該等化合物混合而製作之樹脂組成物的階段等任一階段中進行。Furthermore, from the viewpoint of environmental control, it is preferable that the resin composition of the present invention substantially does not contain environmentally controlled substances. Furthermore, in the present invention, substantially free of environmentally regulated substances means that the content of environmentally regulated substances in the resin composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and further preferably 10 ppm by mass or less. 1 mass ppm or less is particularly preferred. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzene such as chlorobenzene. These regulations are based on REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds) (Volatile Organic Compounds) control, etc. are registered as environmentally controlled substances, and the usage amount and treatment methods are strictly controlled. These compounds may be used as solvents when producing components used in the resin composition, and may be mixed into the resin composition as residual solvents. From the viewpoint of human safety and environmental considerations, it is better to reduce these substances as much as possible. Examples of methods for reducing environmentally regulated substances include heating or depressurizing the system to a temperature above the boiling point of the environmentally regulated substances, and distilling and removing the environmentally regulated substances from the system. In addition, when removing a small amount of environmentally controlled substances by distillation, it is also useful to azeotrope the solvent with a solvent having the same boiling point as the solvent in order to improve efficiency. In addition, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added to perform vacuum distillation removal in order to suppress crosslinking between molecules due to radical polymerization reaction during the vacuum distillation removal. These distillation removal methods can be performed at any stage, such as the raw material stage, the stage of a product of reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a resin composition produced by mixing these compounds. carried out in one stage.
<<聚合性化合物>> 本發明的樹脂組成物含有聚合性化合物為較佳。作為聚合性化合物,可以列舉具有含有乙烯性不飽和鍵之基團之化合物等。作為含有乙烯性不飽和鍵之基團,可以列舉乙烯基、(甲基)烯丙基、(甲基)丙烯醯基等。聚合性化合物為自由基聚合性化合物為較佳。 <<Polymerizable compounds>> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include compounds having a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include vinyl, (meth)allyl, (meth)acrylyl, and the like. The polymerizable compound is preferably a radical polymerizable compound.
作為聚合性化合物,可以為單體、預聚物、寡聚物等化學形態的任一種,但單體為較佳。聚合性化合物的分子量為100~2500為較佳。上限為2000以下為較佳,1500以下為更佳。下限為150以上為較佳,250以上為更佳。The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, or an oligomer, but a monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 2,500. The upper limit is preferably 2,000 or less, and 1,500 or less is even better. The lower limit is preferably 150 or more, and 250 or more is even better.
聚合性化合物為含有3個以上的含有乙烯性不飽和鍵之基團之化合物為較佳,含有4個以上的含有乙烯性不飽和鍵之基團之化合物為更佳。從樹脂組成物的保存穩定性的觀點而言,含有乙烯性不飽和鍵之基團的上限為15個以下為較佳,10個以下為更佳,6個以下為進一步較佳。聚合性化合物為3官能以上的(甲基)丙烯酸酯化合物為較佳,3~15官能的(甲基)丙烯酸酯化合物為更佳,3~10官能的(甲基)丙烯酸酯化合物為進一步較佳,3~6官能的(甲基)丙烯酸酯化合物為尤佳。作為聚合性化合物的具體例,可以列舉日本特開2009-288705號公報的0095~0108段、日本特開2013-029760號公報的0227段、日本特開2008-292970號公報的0254~0257段、日本特開2013-253224號公報的0034~0038段、日本特開2012-208494號公報的0477段、日本特開2017-048367號公報、日本專利第6057891號公報、日本專利第6031807號公報中記載之化合物,該等內容被編入本說明書中。The polymerizable compound is preferably a compound containing three or more groups containing an ethylenically unsaturated bond, and more preferably a compound containing four or more groups containing an ethylenically unsaturated bond. From the viewpoint of storage stability of the resin composition, the upper limit of the groups containing ethylenically unsaturated bonds is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less. The polymerizable compound is preferably a (meth)acrylate compound with three or more functions, more preferably a (meth)acrylate compound with 3 to 15 functions, and still more preferably a (meth)acrylate compound with 3 to 10 functions. Preferred, especially 3-6 functional (meth)acrylate compounds. Specific examples of the polymerizable compound include Paragraphs 0095 to 0108 of Japanese Patent Application Laid-Open No. 2009-288705, Paragraph 0227 of Japanese Patent Application Laid-Open No. 2013-029760, Paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970, and Described in paragraphs 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, paragraph 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 compounds, these contents are incorporated into this specification.
作為聚合性化合物,亦能夠使用二新戊四醇三(甲基)丙烯酸酯(作為市售品為KAYARAD D-330;Nippon Kayaku Co.,Ltd.製造)、二新戊四醇四(甲基)丙烯酸酯(作為市售品為KAYARAD D-320;Nippon Kayaku Co.,Ltd.製造)、二新戊四醇五(甲基)丙烯酸酯(作為市售品為KAYARAD D-310;Nippon Kayaku Co.,Ltd.製造)、二新戊四醇六(甲基)丙烯酸酯(作為市售品為KAYARAD DPHA;Nippon Kayaku Co.,Ltd.製造,NK EsterA-DPH-12E;SHIN-NAKAMURA CHEMICAL Co.,Ltd.製造)、二甘油EO(環氧乙烷)改質(甲基)丙烯酸酯(作為市售品為M-460;TOAGOSEI CO., LTD.製造)、新戊四醇四丙烯酸酯(SHIN-NAKAMURA CHEMICAL Co.,Ltd.製造,NK EsterA-TMMT)、1,6-己二醇二丙烯酸酯(Nippon Kayaku Co.,Ltd.製造,KAYARAD HDDA)、RP-1040(Nippon Kayaku Co.,Ltd.製造)、ARONIX TO-2349(TOAGOSEI CO., LTD.製造)、NK Oligo UA-7200(SHIN-NAKAMURA CHEMICAL Co.,Ltd.製造)、8UH-1006、8UH-1012(Taisei Fine Chemical Co.,Ltd.製造)、LIGHT ACRYLATE POB-A0(KYOEISHA CHEMICAL Co.,LTD.製造)等。As the polymerizable compound, dipenterythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol tetra(meth)acrylate can also be used. ) acrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dineopenterythritol penta(meth)acrylate (commercially available product: KAYARAD D-310; Nippon Kayaku Co. ., Ltd.), dipenterythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK EsterA-DPH-12E; SHIN-NAKAMURA CHEMICAL Co. , Ltd.), diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), neopentyl tetraacrylate ( SHIN-NAKAMURA CHEMICAL Co., Ltd., NK EsterA-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (TOAGOSEI CO., LTD.), NK Oligo UA-7200 (SHIN-NAKAMURA CHEMICAL Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co. , Ltd.), LIGHT ACRYLATE POB-A0 (KYOEISHA CHEMICAL Co., LTD.), etc.
作為聚合性化合物,亦能夠使用三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧丙烷改質三(甲基)丙烯酸酯、三羥甲基丙烷環氧乙烷改質三(甲基)丙烯酸酯、異三聚氰酸環氧乙烷改質三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯等3官能的(甲基)丙烯酸酯化合物。作為3官能的(甲基)丙烯酸酯化合物的市售品,可以列舉ARONIX M-309、M-310、M-321、M-350、M-360、M-313、M-315、M-306、M-305、M-303、M-452、M-450(TOAGOSEI CO.,LTD.製造)、NK ESTER A9300、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、TMPT(SHIN-NAKAMURA CHEMICAL Co.,Ltd.製造)、KAYARAD GPO-303、TMPTA、THE-330、TPA-330、PET-30(Nippon Kayaku Co.,Ltd.製造)等。As the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and trimethylolpropane ethylene oxide-modified can also be used. Trifunctional (meth)acrylate compounds such as tri(meth)acrylate, ethylene oxide isocyanurate modified tri(meth)acrylate, and neopentylerythritol tri(meth)acrylate. Commercially available products of trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, and M-306. , M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A- TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Manufactured by Kayaku Co., Ltd.), etc.
作為聚合性化合物,亦能夠使用具有羧基、磺基、磷酸基等酸基之化合物。作為此種化合物的市售品,可以列舉ARONIX M-305、M-510、M-520、ARONIX TO-2349(TOAGOSEI CO.,LTD.製造)等。As the polymerizable compound, a compound having an acid group such as a carboxyl group, a sulfo group, or a phosphate group can also be used. Commercially available products of such compounds include ARONIX M-305, M-510, M-520, ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), and the like.
作為聚合性化合物,亦能夠使用具有己內酯結構之化合物。關於具有己內酯結構之化合物,能夠參閱日本特開2013-253224號公報的0042~0045段的記載,該內容被編入本說明書中。關於具有己內酯結構之化合物,例如,可以列舉由Nippon Kayaku Co.,Ltd.以KAYARAD DPCA系列市售之DPCA-20、DPCA-30、DPCA-60、DPCA-120等。As the polymerizable compound, a compound having a caprolactone structure can also be used. Regarding the compound having a caprolactone structure, please refer to the description in paragraphs 0042 to 0045 of Japanese Patent Application Laid-Open No. 2013-253224, which content is incorporated into this specification. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available as the KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
作為聚合性化合物,亦能夠使用具有伸烷氧基之聚合性化合物。具有伸烷氧基之聚合性化合物為具有乙烯氧基及/或伸丙氧基之聚合性化合物為較佳,具有乙烯氧基之聚合性化合物為更佳,具有4~20個乙烯氧基之3~6官能(甲基)丙烯酸酯化合物為進一步較佳。作為具有伸烷氧基之聚合性化合物的市售品,例如,可以列舉Sartomer Company,Inc製具有4個乙烯氧基之4官能(甲基)丙烯酸酯SR-494、Nippon Kayaku Co.,Ltd.製具有3個異丁烯氧基之3官能(甲基)丙烯酸酯KAYARAD TPA-330等。As the polymerizable compound, a polymerizable compound having an alkyloxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an vinyloxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an vinyloxy group, and a polymerizable compound having 4 to 20 vinyloxy groups. A 3- to 6-functional (meth)acrylate compound is further preferred. Examples of commercially available polymerizable compounds having an alkyleneoxy group include tetrafunctional (meth)acrylate SR-494 having four vinyloxy groups manufactured by Sartomer Company, Inc. and Nippon Kayaku Co., Ltd. Preparation of trifunctional (meth)acrylate KAYARAD TPA-330 with 3 isobutenyloxy groups.
作為聚合性化合物,亦能夠使用具有茀骨架之聚合性化合物。作為市售品,可以列舉OGSOL EA-0200、EA-0300(Osaka Gas Chemicals Co.,Ltd.製造,具有茀骨架之(甲基)丙烯酸酯單體)等。As the polymerizable compound, a polymerizable compound having a fluorine skeleton can also be used. Examples of commercially available products include OGSOL EA-0200 and EA-0300 ((meth)acrylate monomer having a fluorine skeleton, manufactured by Osaka Gas Chemicals Co., Ltd.).
作為聚合性化合物,使用實質上不含甲苯等環境管制物質之化合物亦較佳。作為此種化合物的市售品,可以列舉KAYARAD DPHA LT、KAYARAD DPEA-12 LT(Nippon Kayaku Co.,Ltd.製造)等。As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmentally controlled substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.
作為聚合性化合物,如日本特公昭48-041708號公報、日本特開昭51-037193號公報、日本特公平02-032293號公報、日本特公平02-016765號公報中記載之胺基甲酸酯丙烯酸酯類或日本特公昭58-049860號公報、日本特公昭56-017654號公報、日本特公昭62-039417號公報、日本特公昭62-039418號公報中記載之具有環氧乙烷系骨架之胺基甲酸酯化合物亦較佳。又,使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平01-105238號公報中記載之在分子內具有胺基結構或硫化物結構之聚合性化合物亦較佳。又,聚合性化合物亦能夠使用UA-7200(SHIN-NAKAMURA CHEMICAL Co.,Ltd.製造)、DPHA-40H(Nippon Kayaku Co.,Ltd.製造)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600、LINC-202UA(KYOEISHA CHEMICAL Co.,LTD.製造)等市售品。Examples of polymerizable compounds include urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Acrylates or those having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Urethane compounds are also preferred. In addition, polymerizable compounds having an amino group structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 01-105238 may also be used. Better. In addition, as the polymerizable compound, UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, Commercially available products such as AH-600, T-600, AI-600, LINC-202UA (manufactured by KYOEISHA CHEMICAL Co., LTD.).
樹脂組成物的總固體成分中的聚合性化合物的含量為1~35質量%為較佳。上限為30質量%以下為較佳,25質量%以下為更佳,20質量%以下為進一步較佳,10質量%以下為尤佳。下限為2質量%以上為較佳,5質量%以上為更佳。本發明的樹脂組成物可以僅含有1種聚合性化合物,亦可以含有2種以上的聚合性化合物。當含有2種以上的聚合性化合物時,該等的總量在上述範圍內為較佳。The content of the polymerizable compound in the total solid content of the resin composition is preferably 1 to 35% by mass. The upper limit is preferably 30 mass% or less, more preferably 25 mass% or less, still more preferably 20 mass% or less, and particularly preferably 10 mass% or less. The lower limit is preferably 2 mass% or more, and more preferably 5 mass% or more. The resin composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types of polymerizable compounds. When two or more types of polymerizable compounds are contained, the total amount is preferably within the above range.
<<光聚合起始劑>> 本發明的樹脂組成物含有光聚合起始劑為較佳。作為光聚合起始劑,並無特別限制,能夠從公知的光聚合起始劑中適當地選擇。例如,對從紫外線區域至可見區域的光線具有感光性之化合物為較佳。光聚合起始劑係光自由基聚合起始劑為較佳。 <<Photopolymerization initiator>> The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light from the ultraviolet region to the visible region are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.
作為光聚合起始劑,可以列舉鹵化烴衍生物(例如,具有三𠯤骨架之化合物、具有黃二唑骨架之化合物等)、醯基膦化合物、六芳基雙咪唑化合物、肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、α-羥基酮化合物、α-胺基酮化合物等。從曝光靈敏度的觀點而言,光聚合起始劑為三鹵甲基三𠯤化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、六芳基雙咪唑化合物、鎓化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物、環戊二烯-苯-鐵錯合物、鹵甲基黃二唑化合物及3-芳基取代香豆素化合物為較佳,選自肟化合物、α-羥基酮化合物、α-胺基酮化合物及醯基膦化合物中之化合物為更佳,肟化合物為進一步較佳。又,作為光聚合起始劑,可以列舉日本特開2014-130173號公報的0065~0111段中記載之化合物、日本專利第6301489號公報中記載之化合物、MATERIAL STAGE 37~60p,vol.19,No.3,2019中記載之過氧化物系光聚合起始劑、國際公開第2018/221177號中記載之光聚合起始劑、國際公開第2018/110179號中記載之光聚合起始劑、日本特開2019-043864號公報中記載之光聚合起始劑、日本特開2019-044030號公報中記載之光聚合起始劑、日本特開2019-167313號公報中記載之過氧化物系起始劑、日本特開2020-055992號公報中記載之具有黃唑啶基之胺基苯乙酮系起始劑、日本特開2013-190459號公報中記載之肟系光聚合起始劑、日本特開2020-172619號公報中記載之聚合物、國際公開第2020/152120號中記載之由式1表示之化合物、日本特開2021-181406號公報中記載之化合物、日本特開2022-013379號公報中記載之光聚合起始劑、日本特開2022-015747號公報中記載之由式(1)表示之化合物、日本特表2021-507058號公報中記載之含氟茀肟酯系光起始劑等。Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a trioxadiazole skeleton, compounds having a yellow diazole skeleton, etc.), acylphosphine compounds, hexaarylbisimidazole compounds, oxime compounds, and organic polymers. Oxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the perspective of exposure sensitivity, photopolymerization initiators include trihalomethyltrifluoroethylene compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, and oxidation compounds. Phosphine compounds, metallocene compounds, oxime compounds, hexaarylbisimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethane compounds The oxadiazole compound and the 3-aryl substituted coumarin compound are preferred, and the compound selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds and acylphosphine compounds is more preferred. The oxime compound For further improvement. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, The peroxide-based photopolymerization initiator described in No. 3, 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, The photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030, and the peroxide system described in Japanese Patent Application Publication No. 2019-167313 Initiator, aminoacetophenone-based initiator having a xanthozolinyl group described in Japanese Patent Application Laid-Open No. 2020-055992, oxime-based photopolymerization initiator described in Japanese Patent Application Publication No. 2013-190459, Japan The polymer described in Japanese Patent Application Publication No. 2020-172619, the compound represented by Formula 1 described in International Publication No. 2020/152120, the compound described in Japanese Patent Application Publication No. 2021-181406, Japanese Patent Application Publication No. 2022-013379 Photopolymerization initiator described in the publication, compound represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, fluorine-containing fluorine-containing oxime ester photoinitiator described in Japanese Patent Application Publication No. 2021-507058 Agents, etc.
作為六芳基雙咪唑化合物的具體例,可以列舉2,2',4-三(2-氯苯基)-5-(3,4-二甲氧基苯基)-4,5-二苯基-1,1'-雙咪唑等。Specific examples of hexaarylbisimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl Base-1,1'-bisimidazole, etc.
作為α-羥基酮化合物的市售品,可以列舉Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127(以上為IGM Resins B.V.公司製造)、Irgacure 184、Irgacure 1173、Irgacure 2959、Irgacure 127(以上為BASF公司製造)等。作為α-胺基酮化合物的市售品,可以列舉Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG(以上為IGM Resins B.V.公司製造)、Irgacure 907、Irgacure 369、Irgacure 369E、Irgacure 379EG(以上為BASF公司製造)等。作為醯基膦化合物的市售品,可以列舉Omnirad 819、Omnirad TPO(以上為IGM Resins B.V.公司製造)、Irgacure 819、Irgacure TPO(以上為BASF公司製造)等。Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (the above are manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (the above are manufactured by BASF). manufacturing), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (the above are manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (the above are manufactured by BASF). manufactured by the company), etc. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (the above manufactured by IGM Resins B.V.), Irgacure 819, and Irgacure TPO (the above manufactured by BASF), and the like.
作為肟化合物,可以列舉國際公開第2022/085485號的0142段中記載之化合物、日本專利第5430746號中記載之化合物、日本專利第5647738號中記載之化合物、日本特開2021-173858號公報的由通式(1)表示之化合物或0022至0024段中記載之化合物、日本特開2021-170089號公報的由通式(1)表示之化合物或0117至0120段中記載之化合物等。作為肟化合物的具體例,可以列舉3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁烷-2-酮、2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮、1-[4-(苯硫基)苯基]-3-環己基-丙烷-1,2-二酮-2-(O-乙醯肟)等。作為市售品,可以列舉Irgacure-OXE01、Irgacure-OXE02、Irgacure-OXE03、Irgacure-OXE04(以上為BASF公司製造)、TR-PBG-301、TR-PBG-304、TR-PBG-327(TRONLY公司製造)、Adeka Optomer N-1919(ADEKA CORPORATION製造,日本特開2012-014052號公報中記載之光聚合起始劑2)。又,作為肟化合物,使用無著色性之化合物或透明性高且不易變色之化合物亦較佳。作為市售品,可以列舉ADEKA ARKLS NCI-730、NCI-831、NCI-930(以上為ADEKA CORPORATION製造)等。Examples of the oxime compound include the compounds described in paragraph 0142 of International Publication No. 2022/085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, and the compounds described in Japanese Patent Application Laid-Open No. 2021-173858. A compound represented by general formula (1) or a compound described in paragraphs 0022 to 0024, a compound represented by general formula (1) or a compound described in paragraphs 0117 to 0120 of Japanese Patent Application Laid-Open No. 2021-170089, etc. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, and 3-propionyloxyimine. Butan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyiminopentan-1-one, 2-benzoyloxy Imino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-one Phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyl oxime), etc. Examples of commercially available products include Irgacure-OXE01, Irgacure-OXE02, Irgacure-OXE03, Irgacure-OXE04 (the above are manufactured by BASF), TR-PBG-301, TR-PBG-304, and TR-PBG-327 (TRONLY). (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052). In addition, as the oxime compound, it is also preferable to use a non-coloring compound or a compound with high transparency and resistance to discoloration. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831, NCI-930 (the above are manufactured by ADEKA CORPORATION), and the like.
作為光聚合起始劑,亦能夠使用具有茀環之肟化合物、具有咔唑環中的至少1個苯環成為萘環之骨架之肟化合物、具有氟原子之肟化合物、具有硝基之肟化合物、具有苯并呋喃骨架之肟化合物、在咔唑骨架上鍵結有具有羥基之取代基之肟化合物、國際公開第2022/085485號的0143~0149段中記載之化合物。As the photopolymerization initiator, an oxime compound having a fluorine atom, an oxime compound having a skeleton in which at least one benzene ring in the carbazole ring serves as a naphthalene ring, an oxime compound having a nitro group can also be used. , an oxime compound having a benzofuran skeleton, an oxime compound having a substituent having a hydroxyl group bonded to a carbazole skeleton, and a compound described in paragraphs 0143 to 0149 of International Publication No. 2022/085485.
以下示出可較佳地用於本發明之肟化合物的具體例,但本發明並不限定於該等。Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these.
[化學式17] [化學式18] [化學式19] [Chemical formula 17] [Chemical formula 18] [Chemical formula 19]
肟化合物為在波長350~500nm的範圍內具有極大吸收波長之化合物為較佳,在波長360~480nm的範圍內具有極大吸收波長之化合物為更佳。又,從靈敏度的觀點而言,肟化合物在波長365nm或波長405nm處的莫耳吸光係數高為較佳,1000~300000為更佳,2000~300000為進一步較佳,5000~200000為尤佳。化合物的莫耳吸光係數能夠使用公知的方法測定。例如,藉由分光光度計(Varian公司製Cary-5分光光度計(spectrophotometer)),使用乙酸乙酯溶劑,以0.01g/L的濃度進行測定為較佳。The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the oxime compound preferably has a high Mohr absorption coefficient at a wavelength of 365 nm or a wavelength of 405 nm, more preferably 1,000 to 300,000, further preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
作為光聚合起始劑,組合使用Irgacure OXE01(BASF公司製造)及/或Irgacure OXE02(BASF公司製造)和Omnirad 2959(IGM Resins B.V.公司製造)亦較佳。As a photopolymerization initiator, it is also preferable to use Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.) in combination.
作為光聚合起始劑,可以使用2官能或3官能以上的光自由基聚合起始劑。藉由使用此類光自由基聚合起始劑,從光自由基聚合起始劑的1分子產生2個以上的自由基,因此可獲得良好的靈敏度。又,在使用了非對稱結構的化合物的情況下,結晶性下降而在溶劑等中的溶解性得以提高,隨時間變得難以析出,藉此能夠提高樹脂組成物的經時穩定性。作為2官能或3官能以上的光自由基聚合起始劑的具體例,可以列舉日本特表2010-527339號公報、日本特表2011-524436號公報、國際公開第2015/004565號、日本特表2016-532675號公報的0407~0412段、國際公開第2017/033680號的0039~0055段中記載之肟化合物的二聚體、日本特表2013-522445號公報中記載之化合物(E)及化合物(G)、國際公開第2016/034963號中記載之Cmpd1~7、日本特表2017-523465號公報的0007段中記載之肟酯類光起始劑、日本特開2017-167399號公報的0020~0033段中記載之光起始劑、日本特開2017-151342號公報的0017~0026段中記載之光聚合起始劑(A)、日本專利第6469669號公報中記載之肟酯光起始劑等。As the photopolymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent or the like increases, making it difficult to precipitate over time, thereby improving the temporal stability of the resin composition. Specific examples of the bifunctional or trifunctional or more functional photoradical polymerization initiator include Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2015/004565. The dimer of the oxime compound described in paragraphs 0407 to 0412 of Publication No. 2016-532675, the dimer of the oxime compound described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, the compound (E) and the compound described in Japanese Patent Publication No. 2013-522445 (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, and 0020 of Japanese Patent Publication No. 2017-167399 The photoinitiator described in paragraphs 0033 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669 Agents, etc.
樹脂組成物的總固體成分中的光聚合起始劑的含量為0.1~30質量%為較佳。下限為0.5質量%以上為較佳,1質量%以上為更佳。上限為20質量%以下為較佳,15質量%以下為更佳。本發明的樹脂組成物可以僅含有1種光聚合起始劑,亦可以含有2種以上的光聚合起始劑。當含有2種以上的光聚合起始劑時,該等的總量在上述範圍內為較佳。The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20 mass% or less, and more preferably 15 mass% or less. The resin composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range.
<<具有環狀醚基之化合物>> 本發明的樹脂組成物能夠含有具有環狀醚基之化合物。作為環狀醚基,可以列舉環氧基、氧雜環丁烷基等。具有環狀醚基之化合物為具有環氧基之化合物(以下,亦稱為環氧化合物)為較佳。作為環氧化合物,可以列舉在1分子內具有1個以上的環氧基之化合物,具有2個以上的環氧基之化合物為較佳。環氧化合物為在1分子內具有1~100個環氧基之化合物為較佳。環氧化合物中所含之環氧基的上限例如能夠設為10個以下,亦能夠設為5個以下。環氧化合物中所含之環氧基的下限為2個以上為較佳。作為環氧化合物,亦能夠使用日本特開2013-011869號公報的0034~0036段、日本特開2014-043556號公報的0147~0156段、日本特開2014-089408號公報的0085~0092段中記載之化合物、日本特開2017-179172號公報中記載之化合物、日本特開2021-195421號公報中記載之口山口星型環氧樹脂、日本特開2021-195422號公報中記載之口山口星型環氧樹脂。 <<Compounds with cyclic ether groups>> The resin composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group, an oxetanyl group, and the like. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups per molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more. As the epoxy compound, Paragraphs 0034 to 0036 of Japanese Patent Application Laid-Open No. 2013-011869, Paragraphs 0147 to 0156 of Japanese Patent Application Laid-Open No. 2014-043556, and Paragraphs 0085 to 0092 of Japanese Patent Application Laid-Open No. 2014-089408 can also be used. Compounds described, compounds described in Japanese Patent Application Laid-Open No. 2017-179172, Kuchiyamaguchi star-shaped epoxy resin described in Japanese Patent Application Laid-Open No. 2021-195421, Kuchiyamaguchi star described in Japanese Patent Application Laid-Open No. 2021-195422 type epoxy resin.
環氧化合物可以為低分子化合物(例如,分子量未達2000,進而分子量未達1000),亦可以為高分子化合物(macromolecule)(例如,分子量為1000以上,其為聚合物時,重量平均分子量為1000以上)。具有環氧基之化合物的重量平均分子量為200~100000為較佳,500~50000為更佳。重量平均分子量的上限為10000以下為進一步較佳,5000以下為尤佳,3000以下為更進一步較佳。The epoxy compound can be a low molecular compound (for example, the molecular weight is less than 2000, and then the molecular weight is less than 1000), or it can be a macromolecule compound (for example, the molecular weight is more than 1000, and when it is a polymer, the weight average molecular weight is 1000 and above). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and still more preferably 3,000 or less.
作為具有環狀醚基之化合物的市售品,例如,可以列舉EHPE3150(Daicel Corporation製造)、EPICLON N-695(DIC Corporation製造)、Marproof G-0150M、G-0105SA、G-0130SP、G-0250SP、G-1005S、G-1005SA、G-1010S、G-2050M、G-01100、G-01758(以上為NOF CORPORATION.製造,含有環氧基之聚合物)等。Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, and G-0250SP. , G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (the above are manufactured by NOF CORPORATION., polymers containing epoxy groups), etc.
樹脂組成物的總固體成分中的具有環狀醚基之化合物的含量為0.1~20質量%為較佳。下限為例如0.5質量%以上為更佳,1質量%以上為進一步較佳。上限為例如15質量%以下為更佳,10質量%以下為進一步較佳。具有環狀醚基之化合物可以僅使用1種,亦可以使用2種以上。當使用2種以上時,該等的總量在上述範圍內為較佳。The content of the compound having a cyclic ether group in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, and still more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
<<硬化促進劑>> 本發明的樹脂組成物能夠含有硬化促進劑。作為硬化促進劑,可以列舉硫醇化合物、羥甲基化合物、胺化合物、鏻鹽化合物、脒鹽化合物、醯胺化合物、鹼產生劑、異氰酸酯化合物、烷氧基矽烷化合物、鎓鹽化合物等。作為硬化促進劑的具體例,可以列舉國際公開第2022/085485號的0164段中記載之化合物、日本特開2021-181406號公報中記載之化合物等。樹脂組成物的總固體成分中的硬化促進劑的含量為0.3~8.9質量%為較佳,0.8~6.4質量%為更佳。 <<Harding accelerator>> The resin composition of the present invention can contain a hardening accelerator. Examples of the hardening accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like. Specific examples of the hardening accelerator include the compounds described in paragraph 0164 of International Publication No. 2022/085485, the compounds described in Japanese Patent Application Laid-Open No. 2021-181406, and the like. The content of the hardening accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass.
<<紫外線吸收劑>> 本發明的樹脂組成物能夠含有紫外線吸收劑。作為紫外線吸收劑,可以列舉共軛二烯化合物、胺基二烯化合物、水楊酸酯化合物、二苯甲酮化合物、苯并三唑化合物、丙烯腈化合物、羥苯基三𠯤化合物、吲哚化合物、三𠯤化合物、二苯甲醯化合物等。作為紫外線吸收劑的具體例,亦能夠使用國際公開第2022/085485號的0179段中記載之化合物、日本特開2021-178918號公報中記載之反應性三𠯤紫外線吸收劑、日本特開2022-007884號公報中記載之紫外線吸收劑。 <<UV absorber>> The resin composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl trisulfonate compounds, and indole compounds. Compounds, tribenzoyl compounds, benzoyl compounds, etc. As specific examples of the ultraviolet absorber, the compound described in paragraph 0179 of International Publication No. 2022/085485, the reactive trifluoroethylene ultraviolet absorber described in Japanese Patent Application Laid-Open No. 2021-178918, and Japanese Patent Application Laid-Open No. 2022- can also be used. Ultraviolet absorbers described in Public Gazette No. 007884.
樹脂組成物的總固體成分中的紫外線吸收劑的含量為0.01~10質量%為較佳,0.01~5質量%為更佳。本發明的樹脂組成物可以僅含有1種紫外線吸收劑,亦可以含有2種以上的紫外線吸收劑。當含有2種以上的紫外線吸收劑時,該等的總量在上述範圍內為較佳。The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. The resin composition of the present invention may contain only one type of ultraviolet absorber, or may contain two or more types of ultraviolet absorber. When two or more types of ultraviolet absorbers are contained, the total amount is preferably within the above range.
<<聚合抑制劑>> 本發明的樹脂組成物能夠含有聚合抑制劑。作為聚合抑制劑,可以列舉氫醌、對甲氧基苯酚、二-三級丁基-對甲酚、五倍子酚、三級丁基鄰苯二酚、苯醌、4,4'-硫代雙(3-甲基-6-三級丁基苯酚)、2,2'-亞甲基雙(4-甲基-6-三級丁基苯酚)、N-亞硝基苯基羥胺鹽(銨鹽、第一鈰鹽等)。其中,對甲氧基苯酚為較佳。樹脂組成物的總固體成分中的聚合抑制劑的含量為0.0001~5質量%為較佳。本發明的樹脂組成物可以僅含有1種聚合抑制劑,亦可以含有2種以上的聚合抑制劑。當含有2種以上的聚合抑制劑時,該等的總量在上述範圍內為較佳。 <<Polymerization inhibitor>> The resin composition of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic acid, tertiary butylcatechol, benzoquinone, and 4,4'-thiobis. (3-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine salt (ammonium salt, first cerium salt, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass. The resin composition of the present invention may contain only one polymerization inhibitor, or may contain two or more polymerization inhibitors. When two or more types of polymerization inhibitors are contained, the total amount is preferably within the above range.
<<矽烷偶合劑>> 本發明的樹脂組成物能夠含有矽烷偶合劑。在本說明書中,矽烷偶合劑係指具有水解性基和除其以外的官能基之矽烷化合物。又,水解性基係指與矽原子直接鍵結,並能夠藉由水解反應及縮合反應中的至少任一種而產生矽氧烷鍵之取代基。作為水解性基,例如可以列舉鹵素原子、烷氧基、醯氧基等,烷氧基為較佳。亦即,矽烷偶合劑為具有烷氧基矽基之化合物為較佳。又,作為水解性基以外的官能基,例如,可以列舉乙烯基、(甲基)烯丙基、(甲基)丙烯醯基、巰基、環氧基、氧雜環丁烷基、胺基、脲基、硫醚基、異氰酸酯基、苯基等,胺基、(甲基)丙烯醯基及環氧基為較佳。作為矽烷偶合劑的具體例,可以列舉國際公開第2022/085485號的0177段中記載之化合物。樹脂組成物的總固體成分中的矽烷偶合劑的含量為0.01~15質量%為較佳,0.05~10質量%為更佳。本發明的樹脂組成物可以僅含有1種矽烷偶合劑,亦可以含有2種以上的矽烷偶合劑。當含有2種以上的矽烷偶合劑時,該等的總量在上述範圍內為較佳。 <<Silane Coupling Agent>> The resin composition of the present invention can contain a silane coupling agent. In this specification, a silane coupling agent refers to a silane compound having a hydrolyzable group and functional groups other than the hydrolyzable group. In addition, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a hydroxyl group, and the like, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acrylyl groups, mercapto groups, epoxy groups, oxetanyl groups, and amino groups. Urea group, thioether group, isocyanate group, phenyl group, etc. are preferred, and amino group, (meth)acrylyl group and epoxy group are preferred. Specific examples of the silane coupling agent include compounds described in paragraph 0177 of International Publication No. 2022/085485. The content of the silane coupling agent in the total solid content of the resin composition is preferably 0.01 to 15% by mass, and more preferably 0.05 to 10% by mass. The resin composition of the present invention may contain only one silane coupling agent, or may contain two or more silane coupling agents. When two or more silane coupling agents are contained, the total amount is preferably within the above range.
<<界面活性劑>> 本發明的樹脂組成物能夠含有界面活性劑。作為界面活性劑,能夠使用氟系界面活性劑、非離子性界面活性劑、陽離子性界面活性劑、陰離子性界面活性劑、聚矽氧系界面活性劑等各種界面活性劑。界面活性劑為聚矽氧系界面活性劑或氟系界面活性劑為較佳。關於界面活性劑,能夠參閱國際公開第2015/166779號的0238~0245段中記載之界面活性劑,該內容被編入本說明書中。 <<Surfactant>> The resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane-based surfactants can be used. The surfactant is preferably a polysiloxane-based surfactant or a fluorine-based surfactant. Regarding surfactants, please refer to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015/166779, and this content is incorporated into this specification.
作為氟系界面活性劑,能夠使用國際公開第2022/085485號的0167~0173段中記載之化合物。As the fluorine-based surfactant, compounds described in paragraphs 0167 to 0173 of International Publication No. 2022/085485 can be used.
作為非離子性界面活性劑,可以列舉國際公開第2022/085485號的0174段中記載之化合物。Examples of the nonionic surfactant include compounds described in Paragraph 0174 of International Publication No. 2022/085485.
作為聚矽氧系界面活性劑,可以列舉DOWSIL SH8400、SH8400 FLUID、FZ-2122、67 Additive、74 Additive、M Additive、SF 8419 OIL(以上為Dow Corning Toray Co.,Ltd.製造)、TSF-4300、TSF-4445、TSF-4460、TSF-4452(以上為Momentive Performance Materials Inc.製造)、KP-341、KF-6000、KF-6001、KF-6002、KF-6003(以上為Shin-Etsu Chemical Co.,Ltd.製造)、BYK-307、BYK-322、BYK-323、BYK-330、BYK-333、BYK-3760、BYK-UV3510(以上為BYK-Chemie GmbH製造)等。Examples of polysilicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (the above are manufactured by Dow Corning Toray Co., Ltd.), and TSF-4300 , TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (the above are manufactured by Shin-Etsu Chemical Co. ., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (the above are manufactured by BYK-Chemie GmbH), etc.
又,聚矽氧系界面活性劑亦能夠使用下述結構的化合物。 [化學式20] Moreover, the compound of the following structure can also be used as a polysiloxane surfactant. [Chemical formula 20]
樹脂組成物的總固體成分中的界面活性劑的含量為0.001質量%~5.0質量%為較佳,0.005~3.0質量%為更佳。本發明的樹脂組成物可以僅含有1種界面活性劑,亦可以含有2種以上的界面活性劑。當含有2種以上的界面活性劑時,該等的總量在上述範圍內為較佳。The content of the surfactant in the total solid content of the resin composition is preferably 0.001 mass% to 5.0 mass%, and more preferably 0.005 to 3.0 mass%. The resin composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more surfactants are contained, the total amount is preferably within the above range.
<<抗氧化劑>> 本發明的樹脂組成物能夠含有抗氧化劑。作為抗氧化劑,可以列舉酚系抗氧化劑、胺系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等。作為酚系抗氧化劑,可以列舉受阻酚化合物。酚系抗氧化劑為在與酚性羥基相鄰之部位(鄰位)具有取代基之化合物為較佳。作為前述取代基,碳數1~22的經取代或未經取代之烷基為較佳。又,抗氧化劑為在同一分子內具有酚基和亞磷酸酯基之化合物亦較佳。又,抗氧化劑亦能夠較佳地使用磷系抗氧化劑。作為磷系抗氧化劑,可以列舉三[2-[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-6-基]氧基]乙基]胺、三[2-[(4,6,9,11-四-三級丁基二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-2-基)氧基]乙基]胺、亞磷酸乙基雙(2,4-二-三級丁基-6-甲基苯基)等。作為抗氧化劑的市售品,例如,可以列舉ADEKA STAB AO-20、ADEKA STAB AO-30、ADEKA STAB AO-40、ADEKA STAB AO-50、ADEKA STAB AO-50F、ADEKA STAB AO-60、ADEKA STAB AO-60G、ADEKA STAB AO-80、ADEKA STAB AO-330(以上為ADEKA CORPORATION製造)等。又,抗氧化劑亦能夠使用日本專利第6268967號公報的0023~0048段中記載之化合物、國際公開第2017/006600號中記載之化合物、國際公開第2017/164024號中記載之化合物、韓國公開專利第10-2019-0059371號公報中記載之化合物。樹脂組成物的總固體成分中的抗氧化劑的含量為0.01~20質量%為較佳,0.3~15質量%為更佳。本發明的樹脂組成物可以僅含有1種抗氧化劑,亦可以含有2種以上的抗氧化劑。當含有2種以上的抗氧化劑時,該等的總量在上述範圍內為較佳。 <<Antioxidants>> The resin composition of the present invention can contain antioxidants. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Examples of phenolic antioxidants include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at the position adjacent to the phenolic hydroxyl group (ortho position). As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. Moreover, as an antioxidant, a phosphorus-type antioxidant can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]di Oxaphosphineheterocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f][ 1,3,2]dioxaphosphineheterocycloheptadien-2-yl)oxy]ethyl]amine, ethylbis(2,4-di-tertiary butyl-6-methylbenzene phosphite) base) etc. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, and ADEKA STAB. AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. Moreover, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, and Korean Patent Publication can also be used as antioxidants. Compounds described in Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The resin composition of the present invention may contain only one type of antioxidant, or may contain two or more types of antioxidants. When two or more antioxidants are contained, the total amount is preferably within the above range.
<<其他成分>> 本發明的樹脂組成物可以視需要含有增感劑、硬化促進劑、填料、熱硬化促進劑、可塑劑及其他助劑類(例如,導電性粒子、消泡劑、阻燃劑、調平劑、剝離促進劑、香料、表面張力調節劑、鏈轉移劑等)。藉由適當地含有該等成分,能夠調節膜物理性質等性質。作為該等成分,可以列舉國際公開第2022/085485號的0182段中記載之化合物。 <<Other ingredients>> The resin composition of the present invention may optionally contain sensitizers, hardening accelerators, fillers, thermal hardening accelerators, plasticizers and other auxiliaries (for example, conductive particles, defoaming agents, flame retardants, leveling agents , peeling accelerators, spices, surface tension regulators, chain transfer agents, etc.). By appropriately containing these components, film physical properties and other properties can be adjusted. Examples of these components include compounds described in paragraph 0182 of International Publication No. 2022/085485.
本發明的樹脂組成物可以含有耐光性改良劑。作為耐光性改良劑,可以列舉國際公開第2022/085485號的0183段中記載之化合物。The resin composition of the present invention may contain a light resistance improving agent. Examples of the light resistance improving agent include compounds described in paragraph 0183 of International Publication No. 2022/085485.
本發明的樹脂組成物實質上不含對苯二甲酸酯亦較佳。在此,“實質上不含”係指對苯二甲酸酯的含量在樹脂組成物的總量中為1000質量ppb以下,100質量ppb以下為更佳,0為尤佳。 本發明的樹脂組成物的游離金屬含量為100ppm以下為較佳,50ppm以下為更佳。又,游離鹵素含量為100ppm以下為較佳,50ppm以下為更佳。作為減少樹脂組成物中的游離金屬或鹵素的方法,可以列舉利用離子交換水之洗淨、過濾、超濾、利用離子交換樹脂之精製等方法。 It is also preferred that the resin composition of the present invention contains substantially no terephthalate ester. Here, "substantially free" means that the content of terephthalate ester in the total amount of the resin composition is 1000 mass ppb or less, more preferably 100 mass ppb or less, and 0 is particularly preferably 0. The free metal content of the resin composition of the present invention is preferably 100 ppm or less, and more preferably 50 ppm or less. Moreover, the free halogen content is preferably 100 ppm or less, and more preferably 50 ppm or less. Examples of methods for reducing free metals or halogens in the resin composition include washing with ion-exchange water, filtration, ultrafiltration, and purification with ion-exchange resin.
從環境管制的觀點而言,有時全氟烷基磺酸及其鹽、以及全氟烷基羧酸及其鹽的使用受到管制。在本發明的樹脂組成物中,當降低上述之化合物的含有率時,相對於著色組成物的總固體成分,全氟烷基磺酸(尤其全氟烷基的碳數為6~8的全氟烷基磺酸)及其鹽、以及全氟烷基羧酸(尤其全氟烷基的碳數為6~8的全氟烷基羧酸)及其鹽的含有率為0.01ppb~1,000ppb的範圍為較佳,0.05ppb~500ppb的範圍為更佳,0.1ppb~300ppb的範圍為進一步較佳。本發明的樹脂組成物可以實質上不含全氟烷基磺酸及其鹽以及全氟烷基羧酸及其鹽。例如,藉由使用能夠代替全氟烷基磺酸及其鹽之化合物、以及能夠代替全氟烷基羧酸及其鹽之化合物,可以選擇實質上不含全氟烷基磺酸及其鹽以及全氟烷基羧酸及其鹽之樹脂組成物。作為能夠代替管制化合物之化合物,例如,可以列舉由於全氟烷基的碳數的不同而從管制對象排除之化合物。然而,上述之內容並不妨礙全氟烷基磺酸及其鹽以及全氟烷基羧酸及其鹽的使用。本發明的樹脂組成物可以在所容許之最大範圍內包含全氟烷基磺酸及其鹽以及全氟烷基羧酸及其鹽。From the viewpoint of environmental regulation, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts is sometimes regulated. In the resin composition of the present invention, when the content rate of the above-mentioned compounds is reduced, perfluoroalkyl sulfonic acid (especially perfluoroalkyl group having a carbon number of 6 to 8) is increased relative to the total solid content of the coloring composition. Fluoroalkylsulfonic acid) and its salts, and perfluoroalkylcarboxylic acids (especially perfluoroalkylcarboxylic acids with a perfluoroalkyl group having 6 to 8 carbon atoms) and their salts are contained in a ratio of 0.01 ppb to 1,000 ppb The range of is preferred, the range of 0.05ppb to 500ppb is more preferred, and the range of 0.1ppb to 300ppb is further preferred. The resin composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts. For example, by using compounds that can replace perfluoroalkyl sulfonic acid and its salts, and compounds that can replace perfluoroalkyl carboxylic acids and its salts, you can choose to be substantially free of perfluoroalkyl sulfonic acid and its salts, and Resin compositions of perfluoroalkylcarboxylic acids and their salts. Examples of compounds that can replace the regulated compounds include compounds that are excluded from the subject of regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acids and its salts. The resin composition of the present invention may contain perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts within the maximum allowable range.
<<收容容器>> 作為樹脂組成物的收容容器,並無特別限制,能夠使用公知的收容容器。又,作為收容容器,能夠使用國際公開第2022/085485號的0187段中記載之容器。 <<Container>> There is no particular limitation on the container for storing the resin composition, and a known container can be used. In addition, as the storage container, the container described in paragraph 0187 of International Publication No. 2022/085485 can be used.
<樹脂組成物的製造方法> 本發明的樹脂組成物的製造方法的特徵為,包括:在溶劑中分散顏料、基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物及樹脂之步驟。 <Method for producing a resin composition> The method for producing a resin composition of the present invention is characterized by dispersing a pigment in a solvent, a pigment derivative with a BET specific surface area of 2 to 300 m 2 /g based on the nitrogen adsorption method, and a resin. steps.
作為溶劑、顏料及樹脂,可以列舉作為上述之樹脂組成物中所含者進行說明之溶劑、顏料及樹脂。樹脂包含作為分散劑的樹脂為較佳。Examples of the solvent, pigment, and resin include the solvents, pigments, and resins described as contained in the above-mentioned resin composition. The resin preferably contains a resin as a dispersant.
作為顏料衍生物的化學結構的較佳態樣,與上述之樹脂組成物中所含之特定粒子的項中進行說明之內容相同。A preferred aspect of the chemical structure of the pigment derivative is the same as that described in the section regarding the specific particles contained in the above-mentioned resin composition.
顏料衍生物的基於氮氣吸附法之BET比表面積為2~300m 2/g。顏料衍生物的BET比表面積的下限為3m 2/g以上為較佳,5m 2/g以上為更佳。顏料衍生物的BET比表面積的上限為250m 2/g以下為較佳,200m 2/g以下為更佳,150m 2/g以下為進一步較佳,100m 2/g以下為更進一步較佳。若顏料衍生物的基於氮氣吸附法之BET比表面積在上述範圍內,則能夠製造顏料的分散穩定性優異的樹脂組成物。 The BET specific surface area of the pigment derivative based on the nitrogen adsorption method is 2 to 300 m 2 /g. The lower limit of the BET specific surface area of the pigment derivative is preferably 3 m 2 /g or more, and more preferably 5 m 2 /g or more. The upper limit of the BET specific surface area of the pigment derivative is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less, further preferably 150 m 2 /g or less, and still more preferably 100 m 2 /g or less. If the BET specific surface area of the pigment derivative based on the nitrogen adsorption method is within the above range, a resin composition having excellent pigment dispersion stability can be produced.
顏料衍生物的平均一次粒徑為5~200nm為較佳。上限為150nm以下為較佳,100nm以下為更佳。下限為10nm以上為較佳,20nm以上為更佳。The average primary particle diameter of the pigment derivative is preferably 5 to 200 nm. The upper limit is preferably 150 nm or less, and more preferably 100 nm or less. The lower limit is preferably 10 nm or more, and more preferably 20 nm or more.
顏料的平均一次粒徑為1~200nm為較佳。下限為5nm以上為較佳,10nm以上為更佳,20nm以上為進一步較佳,30nm以上為更進一步較佳。上限為180nm以下為較佳,150nm以下為更佳,100nm以下為進一步較佳,90nm以下為更進一步較佳,80nm以下為尤佳。The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, and still further preferably 30 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, still more preferably 90 nm or less, and particularly preferably 80 nm or less.
顏料衍生物的平均一次粒徑與顏料的平均一次粒徑之差為0~100nm為較佳。上限為50nm以下為較佳,30nm以下為更佳。下限為2nm以上為較佳,5nm以上為更佳。The difference between the average primary particle diameter of the pigment derivative and the average primary particle diameter of the pigment is preferably 0 to 100 nm. The upper limit is preferably 50 nm or less, and more preferably 30 nm or less. The lower limit is preferably 2 nm or more, and more preferably 5 nm or more.
本發明的樹脂組成物的製造方法在上述步驟(在溶劑中分散顏料、基於氮氣吸附法之BET比表面積為2~300m 2/g的顏料衍生物及樹脂之步驟)中製造分散液之後,可以進一步包括將所獲得之分散液與聚合性化合物、光聚合起始劑、樹脂、溶劑等其他材料混合之步驟。其他材料能夠依據樹脂組成物的用途適當選擇。例如,當製造光微影用樹脂組成物時,作為其他材料,選擇含有聚合性化合物和光聚合起始劑者為較佳。又,作為其他材料,可以進一步添加樹脂、溶劑、界面活性劑、矽烷偶合劑、聚合抑制劑、紫外線吸收劑等在上述之樹脂組成物的項中進行說明之材料。 In the method for producing the resin composition of the present invention, after the dispersion liquid is produced in the above steps (the step of dispersing a pigment, a pigment derivative with a BET specific surface area of 2 to 300 m 2 /g based on the nitrogen adsorption method, and a resin in a solvent), the dispersion liquid can be It further includes the step of mixing the obtained dispersion with other materials such as polymerizable compounds, photopolymerization initiators, resins, and solvents. Other materials can be appropriately selected depending on the use of the resin composition. For example, when manufacturing a resin composition for photolithography, it is preferable to select one containing a polymerizable compound and a photopolymerization initiator as other materials. In addition, as other materials, materials such as resin, solvent, surfactant, silane coupling agent, polymerization inhibitor, ultraviolet absorber, etc. described in the above-mentioned section of the resin composition may be further added.
製造樹脂組成物時,以去除雜質、減少缺陷等為目的,用過濾器過濾樹脂組成物為較佳。作為用於過濾之過濾器的種類及過濾方法,可以列舉國際公開第2022/085485號的0196~0199段中記載之過濾器及過濾方法。When manufacturing a resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing impurities, reducing defects, etc. Examples of types of filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of International Publication No. 2022/085485.
<顏料衍生物> 本發明的顏料衍生物的特徵為,其為具有選自由色素結構及三𠯤結構組成之群組中之至少1種結構和酸基或鹼基之化合物的粒子,其中,上述粒子的基於氮氣吸附法之BET比表面積為2~300m 2/g。 <Pigment Derivative> The pigment derivative of the present invention is characterized in that it is a particle having a compound having at least one structure selected from the group consisting of a pigment structure and a trivalent structure and an acid group or a base, wherein the above-mentioned The BET specific surface area of the particles based on the nitrogen adsorption method is 2 to 300 m 2 /g.
顏料衍生物的BET比表面積的下限為3m 2/g以上為較佳,5m 2/g以上為更佳。顏料衍生物的BET比表面積的上限為250m 2/g以下為較佳,200m 2/g以下為更佳,150m 2/g以下為進一步較佳,100m 2/g以下為更進一步較佳。 The lower limit of the BET specific surface area of the pigment derivative is preferably 3 m 2 /g or more, and more preferably 5 m 2 /g or more. The upper limit of the BET specific surface area of the pigment derivative is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less, further preferably 150 m 2 /g or less, and still more preferably 100 m 2 /g or less.
顏料衍生物的平均一次粒徑為5~200nm為較佳。上限為150nm以下為較佳,100nm以下為更佳。下限為10nm以上為較佳,20nm以上為更佳。The average primary particle diameter of the pigment derivative is preferably 5 to 200 nm. The upper limit is preferably 150 nm or less, and more preferably 100 nm or less. The lower limit is preferably 10 nm or more, and more preferably 20 nm or more.
作為顏料衍生物的化學結構的較佳態樣,與上述之樹脂組成物中所含之特定粒子的項中進行說明之內容相同。A preferred aspect of the chemical structure of the pigment derivative is the same as that described in the section regarding the specific particles contained in the above-mentioned resin composition.
本發明的顏料衍生物為分散助劑為較佳。The pigment derivative of the present invention is preferably a dispersion aid.
<膜> 本發明的膜為由上述之本發明的樹脂組成物獲得之膜。本發明的膜的膜厚能夠依據目的適當調整。例如,膜厚為20μm以下為較佳,10μm以下為更佳,5μm以下為進一步較佳。膜厚的下限為0.1μm以上為較佳,0.2μm以上為更佳,0.3μm以上為進一步較佳。 <Membrane> The film of the present invention is a film obtained from the above-mentioned resin composition of the present invention. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.
本發明的膜能夠用於濾色器、近紅外線透射濾波器、近紅外線截止濾波器、黑矩陣、遮光膜等中。本發明的膜能夠較佳地用作濾色器的著色像素。作為著色像素,可以列舉紅色像素、綠色像素、藍色像素、品紅色像素、青色像素、黃色像素等。The film of the present invention can be used in color filters, near-infrared transmission filters, near-infrared cutoff filters, black matrices, light-shielding films, and the like. The film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, and the like.
當將本發明的膜用作近紅外線截止濾波器時,本發明的膜的極大吸收波長存在於波長700~1800nm的範圍內為較佳,存在於波長700~1400nm的範圍內為更佳,存在於波長700~1200nm的範圍內為進一步較佳。又,在膜的波長400~650nm的所有範圍內的透射率為70%以上為較佳,80%以上為更佳,90%以上為進一步較佳。又,在膜的波長700~1800nm的範圍內的至少1處的透射率為20%以下為較佳。又,極大吸收波長下的吸光度Amax與波長550nm下的吸光度A550之比(吸光度Amax/吸光度A550)為20~500為較佳,50~500為更佳,70~450為進一步較佳,100~400為尤佳。When the film of the present invention is used as a near-infrared cutoff filter, it is preferable that the maximum absorption wavelength of the film of the present invention exists in the range of wavelength 700 to 1800 nm, and it is more preferable that it exists in the range of wavelength 700 to 1400 nm. It is more preferable to have a wavelength in the range of 700 to 1200 nm. In addition, the transmittance of the film in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Moreover, it is preferable that the transmittance of at least one place within the wavelength range of 700 to 1800 nm of the film is 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength and the absorbance A550 at the wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500, further preferably 70 to 450, and 100 to 400 is especially good.
當將本發明的膜用作近紅外線透射濾波器時,本發明的膜具有以下(i1)~(i5)中的任一種分光特性為較佳。 (i1):在波長400~640nm的範圍內之透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長800~1500nm的範圍內之透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之膜。具有此種分光特性之膜能夠遮蔽波長400~640nm的範圍內的光,而能夠使波長超過750nm的光透射。 (i2):在波長400~750nm的範圍內之透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長900~1500nm的範圍內之透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之膜。具有此種分光特性之膜能夠遮蔽波長400~750nm的範圍內的光,而能夠使波長超過850nm的光透射。 (i3):在波長400~830nm的範圍內之透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1000~1500nm的範圍內之透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之膜。具有此種分光特性之膜能夠遮蔽波長400~830nm的範圍內的光,而能夠使波長超過950nm的光透射。 (i4):在波長400~950nm的範圍內之透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1100~1500nm的範圍內之透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之膜。具有此種分光特性之膜能夠遮蔽波長400~950nm的範圍內的光,而能夠使波長超過1050nm的光透射。 (i5):在波長400~1050nm的範圍內之透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1200~1500nm的範圍內之透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之膜。具有此種分光特性之膜能夠遮蔽波長400~1050nm的範圍內的光,而能夠使波長超過1150nm的光透射。 When the film of the present invention is used as a near-infrared transmission filter, it is preferable that the film of the present invention has any one of the following spectral characteristics (i1) to (i5). (i1): The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 800 to 1500 nm The minimum value is a film of more than 70% (preferably more than 75%, more preferably more than 80%). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 640 nm, and can transmit light with a wavelength exceeding 750 nm. (i2): The maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 900 to 1500 nm The minimum value is a film of more than 70% (preferably more than 75%, more preferably more than 80%). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 750 nm, and can transmit light with a wavelength exceeding 850 nm. (i3): The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1000 to 1500 nm The minimum value is a film of more than 70% (preferably more than 75%, more preferably more than 80%). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 830 nm, and can transmit light with a wavelength exceeding 950 nm. (i4): The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1100 to 1500 nm The minimum value is a film of more than 70% (preferably more than 75%, more preferably more than 80%). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 950 nm, and can transmit light with a wavelength exceeding 1050 nm. (i5): The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1200 to 1500 nm The minimum value is a film of more than 70% (preferably more than 75%, more preferably more than 80%). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 1050 nm, and can transmit light with a wavelength exceeding 1150 nm.
<膜的製造方法> 接著,對本發明的膜的製造方法進行說明。本發明的膜能夠經過塗布本發明的樹脂組成物之步驟來製造。在膜的製造方法中,進一步包括形成圖案(像素)之步驟為較佳。作為圖案(像素)的形成方法,可以列舉光微影法、乾式蝕刻法,光微影法為較佳。 <Membrane manufacturing method> Next, the manufacturing method of the film of this invention is demonstrated. The film of the present invention can be produced by applying the resin composition of the present invention. It is preferable that the film manufacturing method further includes a step of forming a pattern (pixel). Examples of methods for forming patterns (pixels) include photolithography and dry etching, with photolithography being preferred.
利用光微影法之圖案形成包括以下步驟為較佳:使用本發明的樹脂組成物在支撐體上形成樹脂組成物層之步驟;將樹脂組成物層以圖案狀進行曝光之步驟;及顯影去除樹脂組成物層的未曝光部以形成圖案(像素)之步驟。視需要,可以設置烘烤樹脂組成物層之步驟(預烘烤步驟)及烘烤經顯影之圖案(像素)之步驟(後烘烤步驟)。Pattern formation using photolithography preferably includes the following steps: forming a resin composition layer on a support using the resin composition of the present invention; exposing the resin composition layer in a pattern; and developing and removing it. The step of forming patterns (pixels) on the unexposed portions of the resin composition layer. If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may be provided.
在形成樹脂組成物層之步驟中,使用本發明的樹脂組成物在支撐體上形成樹脂組成物層。作為支撐體,並無特別限定,能夠依據用途適當地選擇。例如,可以列舉玻璃基板、矽基板等,矽基板為較佳。又,在矽基板上,亦可以形成有電荷耦合元件(CCD)、互補金屬氧化膜半導體(CMOS)、透明導電膜等。又,在矽基板上,有時亦會形成有隔離各像素之黑矩陣。又,在矽基板上,亦可以設置有用於改善與上部層的密接性、防止物質的擴散或者使基板表面的平坦化之基底層。關於基底層的表面接觸角,用二碘甲烷測定時,20~70°為較佳。又,用水測定時,30~80°為較佳。In the step of forming the resin composition layer, the resin composition layer of the present invention is used to form the resin composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the use. For example, a glass substrate, a silicon substrate, etc. are mentioned, and a silicon substrate is preferable. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may also be formed on the silicon substrate. In addition, a black matrix is sometimes formed on the silicon substrate to isolate each pixel. Furthermore, the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. In addition, when measuring with water, 30 to 80° is preferred.
作為樹脂組成物的塗布方法,能夠使用公知的方法。例如,能夠使用國際公開第2022/085485號的0207段中記載之塗布方法。As a coating method of the resin composition, a known method can be used. For example, the coating method described in paragraph 0207 of International Publication No. 2022/085485 can be used.
可以對形成於支撐體上之樹脂組成物層進行乾燥(預烘烤)。藉由低溫製程製造膜時,可以不進行預烘烤。進行預烘烤時,預烘烤溫度為150℃以下為較佳,120℃以下為更佳,110℃以下為進一步較佳。下限例如能夠設為50℃以上,亦能夠設為80℃以上。預烘烤時間為10~300秒為較佳,40~250秒為更佳,80~220秒為進一步較佳。預烘烤能夠利用加熱板、烘箱等來進行。The resin composition layer formed on the support may be dried (prebaked). When the film is manufactured by a low-temperature process, pre-baking is not required. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and further preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed using a heating plate, oven, etc.
接著,將樹脂組成物層以圖案狀進行曝光(曝光步驟)。例如,使用步進曝光機、掃描曝光機等,隔著具有規定遮罩圖案之遮罩,對樹脂組成物層進行曝光,藉此能夠以圖案狀進行曝光。藉此,能夠硬化曝光部分。Next, the resin composition layer is exposed in a pattern (exposure step). For example, the resin composition layer can be exposed in a pattern by using a stepper exposure machine, a scanning exposure machine, etc. through a mask having a predetermined mask pattern. Thereby, the exposed portion can be hardened.
作為能夠在曝光時使用之放射線(光),可以列舉g射線、i射線等。又,亦能夠使用波長300nm以下的光(較佳為波長180~300nm的光)。作為波長300nm以下的光,可以列舉KrF射線(波長248nm)、ArF射線(波長193nm)等,KrF射線(波長248nm)為較佳。又,亦能夠利用300nm以上的長波長的光源。作為光源,能夠使用無電極紫外線燈系統、紫外線和紅外線的混合硬化。Examples of radiation (light) that can be used during exposure include g-rays, i-rays, and the like. In addition, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), and KrF rays (wavelength: 248 nm) are preferred. In addition, a long-wavelength light source of 300 nm or more can also be used. As a light source, it is possible to use electrodeless UV lamp systems, mixed curing of UV and infrared rays.
又,在曝光時,可以連續照射光而進行曝光,亦可以實施脈衝式照射而進行曝光(脈衝曝光)。另外,脈衝曝光係指以短時間(例如,毫秒級以下)為週期,反覆進行光的照射和暫停而進行曝光之方式的曝光方法。In addition, during exposure, light may be continuously irradiated for exposure, or pulse irradiation may be performed for exposure (pulse exposure). In addition, pulse exposure refers to an exposure method in which light is irradiated and paused repeatedly to perform exposure in a short period of time (for example, milliseconds or less).
例如,照射量(曝光量)為0.03~2.5J/cm 2為較佳,0.05~1.0J/cm 2為更佳。曝光時的氧濃度能夠適當地選擇,除了在大氣下進行以外,例如,亦可以在氧濃度為19體積%以下的低氧環境下(例如,15體積%、5體積%或實質上無氧)進行曝光,亦可以在氧濃度超過21體積%之高氧環境下(例如,22體積%、30體積%或50體積%)進行曝光。又,曝光照度能夠適當地設定,通常能夠選自1000W/m 2~100000W/m 2(例如,5000W/m 2、15000W/m 2或35000W/m 2)的範圍。氧濃度和曝光照度的條件可以適當地組合,例如能夠設為氧濃度為10體積%且照度為10000W/m 2、氧濃度為35體積%且照度為20000W/m 2等。 For example, the irradiation amount (exposure amount) is preferably 0.03 to 2.5 J/cm 2 , and more preferably 0.05 to 1.0 J/cm 2 . The oxygen concentration during exposure can be appropriately selected. In addition to performing it in the atmosphere, for example, it can also be performed in a low-oxygen environment with an oxygen concentration of 19 volume % or less (for example, 15 volume %, 5 volume %, or substantially no oxygen). Exposure can also be carried out in a high oxygen environment with an oxygen concentration exceeding 21 volume % (for example, 22 volume %, 30 volume % or 50 volume %). In addition, the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 or 35000W/m 2 ). The conditions of oxygen concentration and exposure illuminance can be combined appropriately. For example, the oxygen concentration can be 10 volume % and the illuminance is 10000 W/m 2 , the oxygen concentration can be 35 volume % and the illuminance is 20000 W/m 2 , etc.
接著,顯影去除樹脂組成物層的未曝光部以形成圖案(像素)。能夠使用顯影液進行樹脂組成物層的未曝光部的顯影去除。藉此,曝光步驟中的未曝光部的樹脂組成物層溶出至顯影液中,僅殘留已光硬化之部分。例如,顯影液的溫度為20~30℃為較佳。顯影時間為20~180秒為較佳。又,為了提高殘渣去除性,可以反覆進行複數次每隔60秒甩掉顯影液,進而供給新的顯影液之步驟。Next, the unexposed portion of the resin composition layer is removed by development to form a pattern (pixel). The unexposed portion of the resin composition layer can be removed by development using a developing solution. Thereby, the resin composition layer in the unexposed portion in the exposure step is dissolved into the developer, leaving only the photohardened portion. For example, the temperature of the developer is preferably 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal performance, the step of shaking off the developer every 60 seconds and supplying new developer may be repeated several times.
顯影液可以列舉有機溶劑、鹼顯影液等,可較佳地使用鹼顯影液。關於顯影液及顯影後的洗淨(沖洗)方法,能夠使用國際公開第2022/085485號的0214段中記載之顯影液或洗淨方法。Examples of the developer include organic solvents, alkali developers, and the like, and an alkali developer is preferably used. Regarding the developer and the cleaning (rinsing) method after development, the developer or the cleaning method described in paragraph 0214 of International Publication No. 2022/085485 can be used.
顯影之後,在實施乾燥之後進行追加曝光處理、加熱處理(後烘烤)為較佳。追加曝光處理、後烘烤為用於使其完全硬化之顯影後的硬化處理。後烘烤中的加熱溫度例如100~240℃為較佳,200~240℃為更佳。為了達到上述條件,能夠使用加熱板或對流烘箱(熱風循環式乾燥機)、高頻加熱機等加熱機構,以連續式或間歇式,對顯影後的膜進行後烘烤。進行追加曝光處理時,用於曝光之光為波長400nm以下的光為較佳。又,追加曝光處理可以藉由韓國公開專利第10-2017-0122130號公報中記載之方法進行。After development, it is preferable to perform additional exposure processing and heat processing (post-baking) after drying. The additional exposure process and post-baking are hardening processes after development for complete hardening. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. In order to achieve the above conditions, heating mechanisms such as heating plates, convection ovens (hot air circulation dryers), and high-frequency heating machines can be used to post-bake the developed film in a continuous or intermittent manner. When performing additional exposure processing, it is preferable that the light used for exposure is light with a wavelength of 400 nm or less. In addition, the additional exposure process can be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
藉由乾式蝕刻法的圖案形成包括以下步驟為較佳:使用本發明的樹脂組成物在支撐體上形成樹脂組成物層,並使該樹脂組成物層整體硬化以形成硬化物層之步驟;在該硬化物層上形成光阻層之步驟;將光阻層以圖案狀進行曝光之後進行顯影以形成抗蝕劑圖案之步驟;及將該抗蝕劑圖案作為遮罩,使用蝕刻氣體對硬化物層進行乾式蝕刻之步驟。形成光阻層時,進一步實施預烘烤處理為較佳。尤其,作為光阻層的形成製程,期望實施曝光後的加熱處理、顯影後的加熱處理(後烘烤處理)之形態。關於藉由乾式蝕刻法形成圖案的內容,能夠參閱日本特開2013-064993號公報的0010~0067段的記載,該內容被編入本說明書中。Pattern formation by dry etching preferably includes the following steps: forming a resin composition layer on a support using the resin composition of the present invention, and solidifying the entire resin composition layer to form a hardened material layer; The steps of forming a photoresist layer on the hardened material layer; the steps of exposing the photoresist layer in a pattern and then developing it to form a resist pattern; and using the resist pattern as a mask to use etching gas to etch the hardened material. The step of dry etching the layer. When forming the photoresist layer, it is better to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, it is desirable to perform heat treatment after exposure and heat treatment after development (post-baking treatment). Regarding the formation of patterns by dry etching, please refer to paragraphs 0010 to 0067 of Japanese Patent Application Laid-Open No. 2013-064993, which content is incorporated into this specification.
<濾光器> 本發明的濾光器具有上述之本發明的膜。作為濾光器的種類,可以列舉濾色器、近紅外線截止濾波器及近紅外線透射濾波器等,濾色器為較佳。濾色器具有本發明的膜作為其像素為較佳,具有本發明的膜作為著色像素為更佳。 <Optical filter> The optical filter of the present invention has the above-mentioned film of the present invention. Examples of types of optical filters include color filters, near-infrared cutoff filters, near-infrared transmission filters, and the like, with color filters being preferred. It is preferable that the color filter has the film of the present invention as its pixel, and it is more preferable that it has the film of the present invention as the colored pixel.
在濾光器中,本發明的膜的膜厚能夠依據目的適當地調整。膜厚為20μm以下為較佳,10μm以下為更佳,5μm以下為進一步較佳。膜厚的下限為0.1μm以上為較佳,0.2μm以上為更佳,0.3μm以上為進一步較佳。In the optical filter, the film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.
濾光器中所含之像素的寬度為0.4~10.0μm為較佳。下限為0.4μm以上為較佳,0.5μm以上為更佳,0.6μm以上為進一步較佳。上限為5.0μm以下為較佳,2.0μm以下為更佳,1.0μm以下為進一步較佳,0.8μm為更進一步較佳。又,像素的楊氏模量為0.5~20GPa為較佳,2.5~15GPa為更佳。The width of the pixels included in the filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and still more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, further preferably 1.0 μm or less, and still more preferably 0.8 μm. In addition, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.
濾光器中所含之各像素具有高平坦性為較佳。具體而言,像素的表面粗糙度Ra為100nm以下為較佳,40nm以下為更佳,15nm以下為進一步較佳。下限並無規定,但例如0.1nm以上為較佳。像素的表面粗糙度例如能夠使用Veeco Instruments Inc. 製AFM(原子力顯微鏡)Dimension3100來測定。又,像素上的水的接觸角能夠適當地設定為較佳值,但典型地為50~110°的範圍。接觸角例如能夠使用接觸角計CV-DT・A型(Kyowa Interface Science Co., Ltd製造)來測定。又,像素的體積電阻值為高為較佳。具體而言,像素的體積電阻值為10 9Ω・cm以上為較佳,10 11Ω・cm以上為更佳。上限並無規定,但例如10 14Ω・cm以下為較佳。像素的體積電阻值能夠使用超高電阻計5410(Advantest Corporation製造)來測定。 It is preferred that each pixel included in the filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. There is no lower limit, but for example, 0.1 nm or more is preferred. The surface roughness of a pixel can be measured using AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco Instruments Inc., for example. In addition, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured, for example, using a contact angle meter CV-DT・A type (manufactured by Kyowa Interface Science Co., Ltd.). In addition, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, and more preferably 10 11 Ω·cm or more. There is no upper limit, but for example, it is preferably 10 14 Ω·cm or less. The volume resistance value of the pixel can be measured using ultra-high resistance meter 5410 (manufactured by Advantest Corporation).
在濾光器中,可以在本發明的膜的表面設置保護層。藉由設置保護層,能夠賦予阻隔氧氣化、低反射化、親疏水化、遮蔽特定波長的光(紫外線、近紅外線等)等各種功能。作為保護層的厚度,0.01~10μm為較佳,0.1~5μm為更佳。作為保護層的形成方法,可以列舉塗布保護層形成用組成物而形成之方法、化學氣相沉積法、用接著劑貼附已成型之樹脂之方法等。作為構成保護層之成分,可以列舉(甲基)丙烯酸樹脂、烯-硫醇樹脂、聚碳酸酯樹脂、聚醚樹脂、聚芳酯樹脂、聚碸樹脂、聚醚碸樹脂、聚苯樹脂、聚伸芳基醚氧化膦樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚烯烴樹脂、環狀烯烴樹脂、聚酯樹脂、苯乙烯樹脂、多元醇樹脂、聚偏二氯乙烯樹脂、三聚氰胺樹脂、胺酯樹脂、 聚芳醯胺樹脂、聚醯胺樹脂、醇酸樹脂、環氧樹脂、改質聚矽氧樹脂、氟樹脂、聚丙烯腈樹脂、纖維素樹脂、Si、C、W、Al 2O 3、Mo、SiO 2、Si 2N 4等,可以含有二種以上的該等成分。例如,在以阻隔氧氣化為目的的保護層的情況下,保護層含有多元醇樹脂、SiO 2及Si 2N 4為較佳。又,在以低反射化為目的的保護層的情況下,保護層含有(甲基)丙烯酸樹脂和氟樹脂為較佳。 In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions can be provided, such as blocking oxygen oxidation, making it low-reflective, making it hydrophilic and hydrophobic, and blocking light of specific wavelengths (ultraviolet, near-infrared, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Examples of methods for forming the protective layer include a method of applying a protective layer-forming composition, a chemical vapor deposition method, a method of attaching a molded resin with an adhesive, and the like. Examples of components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polystyrene resin, polyetherstyrene resin, polyphenylene resin, polystyrene resin, Aryl ether phosphine oxide resin, polyimide resin, polyamide imine resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, Melamine resin, urethane resin, polyarylamine resin, polyamide resin, alkyd resin, epoxy resin, modified polysiloxane resin, fluorine resin, polyacrylonitrile resin, cellulose resin, Si, C, W , Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 , etc., and may contain two or more of these components. For example, in the case of a protective layer with the purpose of blocking oxygen oxidation, it is preferable that the protective layer contains polyol resin, SiO 2 and Si 2 N 4 . Moreover, in the case of a protective layer for the purpose of low reflection, it is preferable that the protective layer contains (meth)acrylic resin and fluororesin.
視需要,保護層可以含有有機/無機微粒、特定波長的光(例如,紫外線、近紅外線等)的吸收劑、折射率調節劑、抗氧化劑、黏附劑、界面活性劑等添加劑。作為有機/無機微粒的例子,例如,可以列舉高分子微粒(例如,聚矽氧樹脂微粒、聚苯乙烯微粒、三聚氰胺樹脂微粒)、氧化鈦、氧化鋅、氧化鋯、氧化銦、氧化鋁、氮化鈦、氮氧化鈦、氟化鎂、中空二氧化矽、二氧化矽、碳酸鈣、硫酸鋇等。特定波長的光的吸收劑能夠使用公知的吸收劑。該等添加劑的含量能夠適當地調整,但相對於保護層的總質量,0.1~70質量%為較佳,1~60質量%為進一步較佳。If necessary, the protective layer may contain organic/inorganic particles, absorbers for specific wavelengths of light (for example, ultraviolet, near-infrared, etc.), refractive index adjusters, antioxidants, adhesives, surfactants and other additives. Examples of organic/inorganic fine particles include polymer fine particles (for example, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, nitrogen Titanium oxide, titanium oxynitride, magnesium fluoride, hollow silicon dioxide, silicon dioxide, calcium carbonate, barium sulfate, etc. As an absorber for light of a specific wavelength, a known absorber can be used. The content of these additives can be appropriately adjusted, but relative to the total mass of the protective layer, 0.1 to 70 mass % is more preferred, and 1 to 60 mass % is further more preferred.
作為保護層,亦能夠使用日本特開2017-151176號公報的0073~0092段中記載之保護層。As the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 can also be used.
濾光器亦可以具有如下結構:在藉由隔壁分隔成例如方格狀之空間嵌入有各像素。The optical filter may have a structure in which each pixel is embedded in a space divided by partition walls into, for example, a grid shape.
<固體攝像元件> 本發明的固體攝像元件具有上述之本發明的膜。作為固體攝像元件的結構,只要為作為固體攝像元件發揮作用之結構,則並無特別限定,例如,可以列舉以下結構。 <Solid-state imaging device> The solid-state imaging element of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging element is not particularly limited as long as it functions as a solid-state imaging element. For example, the following structures can be cited.
固體攝像元件為如下結構:在基板上具有由構成固體攝像元件(CCD(電荷耦合元件)影像感測器、CMOS(互補金屬氧化膜半導體)影像感測器等)的受光區域之複數個光二極體及聚矽等構成之傳輸電極,在光二極體及傳輸電極上具有僅光二極體的受光部開口之遮光膜,在遮光膜上具有以覆蓋遮光膜整體及光二極體受光部之方式形成之由氮化矽等構成之元件保護膜,在元件保護膜上具有濾色器。進而,亦可以為在元件保護膜上且在濾色器的下方(靠近基板側)具有聚光機構(例如,微透鏡等。以下相同)之結構或在濾色器上具有聚光機構之結構等。又,濾色器亦可以具有如下結構:在藉由隔壁分隔成例如方格狀之空間嵌入有各像素。此時的隔壁的折射率比各著色像素低為較佳。作為具有此種結構之攝像裝置的例子,可以列舉日本特開2012-227478號公報、日本特開2014-179577號公報、國際公開第2018/043654號中記載之裝置。又,如日本特開2019-211559號公報中所示,可以在固體攝像元件的結構內設置紫外線吸收層以改善耐光性。具備本發明的固體攝像元件之攝像裝置,除了能夠用於數位相機或具有攝像功能之電子設備(移動電話等)以外,亦能夠用作行車紀錄器或監視攝影機用。A solid-state imaging device has a structure in which a plurality of photodiodes constituting the light-receiving area of a solid-state imaging device (CCD (Charge Coupled Device) image sensor, CMOS (Complementary Metal Oxide Semiconductor) image sensor, etc.) are provided on a substrate. The transmission electrode is composed of silicon and polysilicon, and has a light-shielding film on the photodiode and the transmission electrode with only the light-receiving part of the photodiode opening. The light-shielding film has a light-shielding film formed in such a manner as to cover the entire light-shielding film and the light-receiving part of the photodiode. The element protective film composed of silicon nitride, etc. has a color filter on the element protective film. Furthermore, a structure in which a light condensing mechanism (for example, a microlens, etc.; the same applies to the following) is provided on the element protective film and below the color filter (closer to the substrate side) or a structure in which a light condensing mechanism is provided on the color filter may be used. wait. Furthermore, the color filter may have a structure in which each pixel is embedded in a space divided by partition walls into, for example, a grid shape. At this time, it is preferable that the refractive index of the partition wall is lower than that of each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Laid-Open No. 2012-227478, Japanese Patent Application Laid-Open No. 2014-179577, and International Publication No. 2018/043654. Furthermore, as shown in Japanese Patent Application Publication No. 2019-211559, an ultraviolet absorbing layer can be provided in the structure of the solid-state imaging element to improve light resistance. The imaging device equipped with the solid-state imaging element of the present invention can be used not only as a digital camera or an electronic device (mobile phone, etc.) with imaging functions, but also as a driving recorder or a surveillance camera.
<圖像顯示裝置> 本發明的圖像顯示裝置具有上述之本發明的膜。作為圖像顯示裝置,可以列舉液晶顯示裝置、有機電致發光顯示裝置等。關於圖像顯示裝置的定義、各圖像顯示裝置的詳細內容,例如記載於“電子顯示裝置(佐佐木昭夫著,Kogyo Chosakai Publishing Co.,Ltd.,1990年發行)”、“顯示裝置(伊吹順章著,Sangyo Tosho Publishing Co.,Ltd.,1989年發行)”等。又,關於液晶顯示裝置,例如記載於“下一代液晶顯示技術(內田龍男編輯,Kogyo Chosakai Publishing Co.,Ltd.,1994年發行)”。能夠應用本發明之液晶顯示裝置並無特別限制,例如能夠應用於上述“下一代液晶顯示技術”中記載之各種方式的液晶顯示裝置。 [實施例] <Image display device> The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices, organic electroluminescence display devices, and the like. The definition of an image display device and the details of each image display device are described in, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd., 1990)" and "Display Devices (Jun Ibuki)" Chapter book, Sangyo Tosho Publishing Co., Ltd., released in 1989)" and so on. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". [Example]
以下,列舉實施例對本發明更具體地進行說明。以下實施例所示之材料、使用量、比例、處理內容、處理順序等,只要不脫離本發明的主旨,則能夠適當地變更。因此,本發明的範圍並不限定於以下所示之具體例。又,以下所示之結構式中,Me為甲基,Et為乙基,Ph為苯基。Hereinafter, an Example is given and this invention is demonstrated more concretely. The materials, usage amounts, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Moreover, in the structural formula shown below, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group.
<利用凝膠滲透層析法的重量平均分子量及數平均分子量的測定條件> 管柱的種類:將TOSOH TSKgel Super HZM-H、TOSOH TSKgel Super HZ4000及TOSOH TSKgel Super HZ2000連結而成之管柱 展開溶劑:四氫呋喃 管柱溫度:40℃ 流量(樣品注入量):1.0μL(樣品濃度:0.1質量%) 裝置名:Tosoh Corporation製造 HLC-8220GPC 檢測器:RI(折射率)檢測器 校準曲線基本樹脂:聚苯乙烯樹脂 <Measurement conditions of weight average molecular weight and number average molecular weight using gel permeation chromatography> Type of column: Column formed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 Development solvent: tetrahydrofuran Tube string temperature: 40℃ Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1 mass%) Device name: HLC-8220GPC manufactured by Tosoh Corporation Detector: RI (Refractive Index) Detector Calibration Curve Basic Resin: Polystyrene Resin
<顏料及顏料衍生物的平均一次粒徑的測定方法> 從使用穿透式電子顯微鏡(TEM:Transmission Electron Microscope)拍攝之照片直接測定了顏料的一次粒子的大小。具體而言,計測了各個顏料的一次粒子的短軸徑和長軸徑,並將其平均作為該顏料的一次粒徑。接著,對於100個顏料的一次粒子,以近似於一次粒子的粒徑的立方體的方式求出各個一次粒子的體積,並將其體積平均粒徑作為顏料的平均一次粒徑。對於顏料衍生物,亦以相同的方法測定了平均一次粒徑。 <Measurement method of average primary particle size of pigments and pigment derivatives> The size of the primary particles of the pigment is directly measured from photos taken using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was used as the primary particle diameter of the pigment. Next, for 100 primary particles of the pigment, the volume of each primary particle was determined in a manner similar to a cube with the particle diameter of the primary particle, and the volume average particle diameter was used as the average primary particle diameter of the pigment. Regarding the pigment derivative, the average primary particle size was measured in the same manner.
<分散液(樹脂組成物)的製造> (配方1) 使用珠磨機(直徑為0.1mm的二氧化鋯珠),將合計15.6質量份的顏料和顏料衍生物、3.9質量份的樹脂、80.5質量份的溶劑的混合液,混合及分散了3小時。接著,使用附減壓機構之高壓分散機NANO-3000-10(Nippon BEE Co.,Ltd.製造),在壓力為2000kg/cm 2及流量為500g/分鐘的條件下進行了分散處理。反覆該分散處理至共10次,以獲得了分散液。再者,顏料、顏料衍生物、樹脂及溶劑分別使用了下述表中所示之材料。又,下述表中的顏料的混合比率為固體成分換算值,並且顏料衍生物的BET比表面積為使用自動蒸氣吸附量測定裝置(MicrotracBEL Corp.製“BELSORP18”)並依據基於氮氣吸附法之BET法來測定之值。 <Preparation of dispersion (resin composition)> (Recipe 1) Using a bead mill (zirconia beads with a diameter of 0.1 mm), a total of 15.6 parts by mass of pigments and pigment derivatives, 3.9 parts by mass of resin, and 80.5 The mixture of parts by mass of the solvent was mixed and dispersed for 3 hours. Next, a high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion processing at a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersion process was repeated a total of 10 times to obtain a dispersion liquid. In addition, the pigments, pigment derivatives, resins, and solvents were each used as shown in the following table. In addition, the mixing ratio of the pigment in the following table is a solid content conversion value, and the BET specific surface area of the pigment derivative is based on the BET based on the nitrogen adsorption method using an automatic vapor adsorption capacity measuring device ("BELSORP18" manufactured by MicrotracBEL Corp.). method to measure the value.
(配方2) 將合計13質量份的顏料和顏料衍生物、7.8質量份的樹脂、150質量份的溶劑的混合液與珠子(直徑為0.3mm的二氧化鋯珠)混合,並使用塗料攪拌器分散了5小時。之後,用過濾器分離珠以獲得了分散液。再者,顏料、顏料衍生物、樹脂及溶劑分別使用了下述表中所示之材料。又,下述表中的顏料的混合比率為固體成分換算值,並且顏料衍生物的BET比表面積為使用自動蒸氣吸附量測定裝置(MicrotracBEL Corp.製“BELSORP18”)並依據基於氮氣吸附法之BET法來測定之值。 (Recipe 2) A mixture of a total of 13 parts by mass of pigments and pigment derivatives, 7.8 parts by mass of resin, and 150 parts by mass of solvent was mixed with beads (zirconium dioxide beads with a diameter of 0.3 mm) and dispersed for 5 hours using a paint stirrer. . After that, the beads were separated with a filter to obtain a dispersion. In addition, the pigments, pigment derivatives, resins, and solvents were each used as shown in the following table. In addition, the mixing ratio of the pigment in the following table is a solid content conversion value, and the BET specific surface area of the pigment derivative is based on the BET based on the nitrogen adsorption method using an automatic vapor adsorption capacity measuring device ("BELSORP18" manufactured by MicrotracBEL Corp.). method to measure the value.
[表1]
[表2]
[表3]
[表4]
上述表中的用縮寫記載之原料的詳細內容如下。Details of the raw materials described with abbreviations in the above table are as follows.
(顏料) P.R.177:C.I.顏料紅177(紅色顏料) P.R.254:C.I.顏料紅254(紅色顏料) P.R.272:C.I.顏料紅272(紅色顏料) P.Y.117:C.I.顏料黃117(黃色顏料) P.Y.129:C.I.顏料黃129(黃色顏料) P.Y.138:C.I.顏料黃138(黃色顏料) P.Y.139:C.I.顏料黃139(黃色顏料) P.Y.185:C.I.顏料黃185(黃色顏料) P.B.15:6:C.I.顏料藍15:6(藍色顏料) P.V.19:C.I.顏料紫19(紫色顏料) P.V.23:C.I.顏料紫23(紫色顏料) PP-Pig-1~PP-Pig-22:下述結構的化合物(近紅外線吸收顏料) [化學式21] [化學式22] [化學式23] [化學式24] [化學式25] [化學式26] [化學式27] (Pigment) PR177: CI Pigment Red 177 (red pigment) PR254: CI Pigment Red 254 (red pigment) PR272: CI Pigment Red 272 (red pigment) PY117: CI Pigment Yellow 117 (yellow pigment) PY129: CI Pigment Yellow 129 ( Yellow pigment) PY138: CI Pigment Yellow 138 (yellow pigment) PY139: CI Pigment Yellow 139 (yellow pigment) PY185: CI Pigment Yellow 185 (yellow pigment) PB15:6: CI Pigment Blue 15:6 (blue pigment) PV19: CI Pigment Violet 19 (purple pigment) PV23: CI Pigment Violet 23 (purple pigment) PP-Pig-1 to PP-Pig-22: Compounds with the following structures (near-infrared absorbing pigments) [Chemical Formula 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] [Chemical formula 25] [Chemical formula 26] [Chemical formula 27]
(顏料衍生物) DPP-1~DPP-30:下述結構的化合物(具有二酮吡咯并吡咯結構之顏料衍生物) [化學式28] [化學式29] [化學式30] [化學式31] (Pigment derivatives) DPP-1 to DPP-30: Compounds with the following structure (pigment derivatives having a diketopyrrolopyrrole structure) [Chemical Formula 28] [Chemical formula 29] [Chemical formula 30] [Chemical Formula 31]
PP-1~PP-29:下述結構的化合物(具有吡咯并吡咯結構之顏料衍生物) [化學式32] [化學式33] [化學式34] [化學式35] [化學式36] PP-1 to PP-29: Compounds with the following structure (pigment derivatives having a pyrrolopyrrole structure) [Chemical Formula 32] [Chemical formula 33] [Chemical formula 34] [Chemical formula 35] [Chemical formula 36]
AZM-1~AZM-36:下述金屬與下述配位體的錯合物(具有甲亞胺結構之顏料衍生物)
[表5]
IIN-1~IIN-3:下述結構的化合物(具有異吲哚啉結構之顏料衍生物) [化學式40] IIN-1~IIN-3: Compounds with the following structure (pigment derivatives with isoindoline structure) [Chemical Formula 40]
QP-1:下述結構的化合物(具有喹啉黃結構之顏料衍生物) [化學式41] QP-1: Compound with the following structure (pigment derivative with quinoline yellow structure) [Chemical Formula 41]
AZO-1:下述結構的化合物(具有偶氮結構之顏料衍生物) [化學式42] AZO-1: Compound with the following structure (pigment derivative with azo structure) [Chemical Formula 42]
ATQ-1~ATQ-3:下述結構的化合物(具有蒽醌結構之顏料衍生物) [化學式43] ATQ-1~ATQ-3: Compounds with the following structure (pigment derivatives with anthraquinone structure) [Chemical Formula 43]
TI-1:下述結構的化合物(具有噻𠯤靛藍結構之顏料衍生物) [化學式44] TI-1: Compound with the following structure (pigment derivative with thiolindigo structure) [Chemical Formula 44]
QCD-1:下述結構的化合物(具有喹吖酮結構之顏料衍生物) [化學式45] QCD-1: Compound with the following structure (pigment derivative with quinacridone structure) [Chemical Formula 45]
BZI-1:下述結構的化合物(具有苯并吲哚結構之顏料衍生物) [化學式46] BZI-1: Compound with the following structure (pigment derivative with benzindole structure) [Chemical Formula 46]
PC-1:下述結構的化合物(具有酞菁結構之顏料衍生物) [化學式47] PC-1: Compound with the following structure (pigment derivative with phthalocyanine structure) [Chemical Formula 47]
DOZ-1:下述結構的化合物(具有二黃𠯤結構之顏料衍生物) [化學式48] DOZ-1: Compound with the following structure (pigment derivative with diyellow 𠯤 structure) [Chemical Formula 48]
TAZ-1:下述結構的化合物(具有三𠯤結構之顏料衍生物) [化學式49] TAZ-1: Compound with the following structure (pigment derivative with three 𠯤 structure) [Chemical Formula 49]
(樹脂) D-1:藉由以下方法合成之樹脂D-1 將甲基丙烯酸甲酯50質量份、甲基丙烯酸正丁酯30質量份、甲基丙烯酸三級丁酯20質量份、丙二醇單甲醚乙酸酯(PGMEA)45.4質量份裝入反應容器中,並將環境氣體取代為氮氣。將反應容器內加熱至70℃,並添加3-巰基-1,2-丙二醇6質量份,進而加入AIBN(偶氮雙異丁腈)0.12質量份,使其反應了12小時。藉由固體成分的測定來確認了已反應95%。接著,追加均苯四甲酸酐9.7質量份、PGMEA70.3質量份、作為觸媒之DBU(1,8-二氮雜雙環-[5.4.0]-7-十一碳烯)0.20質量份,並在120℃下使其反應了7小時。藉由酸值的測定來確認了98%以上的酸酐被半酯化,並結束反應,以獲得了酸值為43mgKOH/g、重量平均分子量(Mw)為9000的下述結構的樹脂D-1。 [化學式50] (Resin) D-1: Resin D-1 synthesized by the following method: 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of tertiary butyl methacrylate, propylene glycol mono 45.4 parts by mass of methyl ether acetate (PGMEA) was put into the reaction vessel, and the ambient gas was replaced with nitrogen. The inside of the reaction vessel was heated to 70° C., 6 parts by mass of 3-mercapto-1,2-propanediol was added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) was added, and the reaction was carried out for 12 hours. By measuring the solid content, it was confirmed that 95% of the reaction was completed. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added. The reaction was carried out at 120°C for 7 hours. By measuring the acid value, it was confirmed that more than 98% of the acid anhydride was half-esterified, and the reaction was completed to obtain resin D-1 of the following structure with an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9000. . [Chemical formula 50]
D-2:藉由以下方法合成之樹脂D-2 將3-巰基-1,2-丙二醇6.0質量份、均苯四甲酸酐9.5質量份、PGMEA62質量份、1,8-二氮雜雙環-[5.4.0]-7-十一碳烯0.2質量份裝入反應容器中,並將環境氣體取代為氮氣。將反應容器內加熱至100℃,使其反應了7小時。藉由酸值的測定來確認了98%以上的酸酐被半酯化之後,將系統內的溫度冷卻至70℃,並添加甲基丙烯酸甲酯65質量份、丙烯酸乙酯5.0質量份、丙烯酸三級丁酯15質量份、甲基丙烯酸5.0質量份、甲基丙烯酸羥乙酯10質量份、溶解有2,2’-偶氮雙異丁腈0.1質量份之PGMEA溶液53.5質量份,使其反應了10小時。藉由固體成分測定確認了聚合已進行95%,並結束反應,以獲得了酸值為70.5mgKOH/g、重量平均分子量(Mw)為10000的下述結構的樹脂D-2。 [化學式51] D-2: Resin D-2 synthesized by the following method: 6.0 parts by mass of 3-mercapto-1,2-propanediol, 9.5 parts by mass of pyromellitic anhydride, 62 parts by mass of PGMEA, 1,8-diazabicyclo- 0.2 mass parts of [5.4.0]-7-undecene was put into the reaction vessel, and the ambient gas was replaced with nitrogen. The inside of the reaction vessel was heated to 100°C and the reaction was carried out for 7 hours. After confirming that more than 98% of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, and 65 parts by mass of methyl methacrylate, 5.0 parts by mass of ethyl acrylate, and triacrylate were added. 15 parts by mass of grade butyl ester, 5.0 parts by mass of methacrylic acid, 10 parts by mass of hydroxyethyl methacrylate, and 53.5 parts by mass of PGMEA solution in which 0.1 part by mass of 2,2'-azobisisobutyronitrile was dissolved 10 hours. It was confirmed by solid content measurement that 95% of the polymerization had progressed, and the reaction was completed to obtain resin D-2 having the following structure with an acid value of 70.5 mgKOH/g and a weight average molecular weight (Mw) of 10,000. [Chemical formula 51]
D-3:藉由以下方法合成之樹脂D-3 在樹脂D-1的合成中,將甲基丙烯酸三級丁酯20質量份變更為甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯20質量份,除此以外,以相同的方式獲得了酸值為43mgKOH/g、重量平均分子量(Mw)為9000的下述結構的樹脂D-3。 [化學式52] D-3: Resin D-3 synthesized by the following method. In the synthesis of resin D-1, 20 parts by mass of tertiary butyl methacrylate was changed to methacrylic acid (3-ethyloxetane- Resin D-3 having the following structure with an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9000 was obtained in the same manner except that 20 parts by mass of 3-yl) methyl ester was added. [Chemical formula 52]
D-4:藉由以下方法合成之樹脂D-4 將1-硫甘油108質量份、均苯四甲酸酐174質量份、乙酸甲氧基丙酯(Methoxypropyl acetate)650質量份、作為觸媒之單丁基氧化錫(monobutyltin oxide)0.2質量份裝入反應容器中,並將環境氣體取代為氮氣之後,在120℃下使其反應了5小時(第一步驟)。藉由酸值的測定來確認了95%以上的酸酐被半酯化。接著,將在第一步驟中所獲得之化合物以固體成分換算計160質量份、甲基丙烯酸2-羥基丙酯200質量份、丙烯酸乙酯200質量份、丙烯酸三級丁酯150質量份、2-甲氧基丙烯酸乙酯200質量份、丙烯酸甲酯200質量份、甲基丙烯酸50質量份、PGMEA663質量份裝入反應容器中,並將反應容器內加熱至80℃,並且添加2,2’-偶氮雙(2,4-二甲基戊腈)1.2質量份,使其反應了12小時(第二步驟)。藉由固體成分的測定來確認了已反應95%。最後,將在第二步驟中所獲得之化合物50質量%PGMEA溶液500質量份、2-甲基丙烯醯氧基乙基異氰酸酯(methacryloyloxyethyl isocyanate)(MOI)27.0質量份、氫醌0.1質量份裝入反應容器中進行反應,直至確認基於異氰酸酯基之2270cm -1的峰消失為止(第三步驟)。確認峰消失之後,冷卻反應溶液,以獲得了酸值為68mgKOH/g、乙烯性不飽和鍵值為0.62mmol/g、重量平均分子量(Mw)為13000的下述結構的樹脂D-4。 [化學式53] D-4: Resin D-4 synthesized by the following method: 108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, and 650 parts by mass of methoxypropyl acetate as a catalyst 0.2 parts by mass of monobutyltin oxide was put into the reaction vessel, and the ambient gas was replaced with nitrogen, and then the reaction was carried out at 120° C. for 5 hours (first step). By measuring the acid value, it was confirmed that more than 95% of the acid anhydride was half-esterified. Next, 160 parts by mass of the compound obtained in the first step in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of tertiary butyl acrylate, 2 -Put 200 parts by mass of ethyl methoxyacrylate, 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA into a reaction vessel, heat the reaction vessel to 80°C, and add 2,2' - 1.2 parts by mass of azobis(2,4-dimethylvaleronitrile) and reacted for 12 hours (second step). By measuring the solid content, it was confirmed that 95% of the reaction was completed. Finally, 500 parts by mass of the 50% by mass PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part by mass of hydroquinone were loaded The reaction was carried out in the reaction vessel until it was confirmed that the peak at 2270 cm -1 based on the isocyanate group disappeared (the third step). After confirming that the peak disappeared, the reaction solution was cooled to obtain resin D-4 of the following structure with an acid value of 68 mgKOH/g, an ethylenically unsaturated bond value of 0.62 mmol/g, and a weight average molecular weight (Mw) of 13,000. [Chemical formula 53]
D-5:下述結構的樹脂(標註於主鏈之數值為莫耳比,標註於側鏈之數值為重複單元數。重量平均分子量16000、酸值67mgKOH/g) [化學式54] D-5: Resin with the following structure (the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH/g) [Chemical Formula 54]
D-6:下述結構的樹脂(標註於主鏈之數值為莫耳比,標註於側鏈之數值為重複單元數。重量平均分子量20000、酸值36mgKOH/g) [化學式55] D-6: Resin with the following structure (the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. Weight average molecular weight 20000, acid value 36 mgKOH/g) [Chemical Formula 55]
D-7:DISPERBYK-111(BYK-Chemie GmbH製造,酸性分散劑) D-8:BYK LPN-21116(BYK-Chemie GmbH製造,鹼性分散劑) D-9:Solsperse 20000(Lubrizol Japan Ltd.製造,鹼性分散劑) D-10:AJISPER PB821(Ajinomoto Fine-Techno Co.,Inc.製造,鹼性分散劑) D-7: DISPERBYK-111 (manufactured by BYK-Chemie GmbH, acidic dispersant) D-8: BYK LPN-21116 (manufactured by BYK-Chemie GmbH, alkaline dispersant) D-9: Solsperse 20000 (manufactured by Lubrizol Japan Ltd., alkaline dispersant) D-10: AJISPER PB821 (manufactured by Ajinomoto Fine-Techno Co., Inc., alkaline dispersant)
D-11:下述結構的樹脂(標註於主鏈之數值為莫耳比,標註於側鏈之數值為重複單元數。重量平均分子量18000、酸值82.1mgKOH/g) [化學式56] D-11: Resin with the following structure (the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. Weight average molecular weight 18000, acid value 82.1mgKOH/g) [Chemical Formula 56]
(溶劑) S-1:丙二醇單甲醚乙酸酯(PGMEA) (solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA)
<分散液的評價> (粗大粒子) 在玻璃基板上,使用旋塗機塗布剛製造之後的分散液及在45℃下保管72小時之後的分散液,以使加熱後的厚度成為0.25μm,並使用加熱板在85℃下加熱2分鐘以形成了膜。對於該膜,用光學顯微鏡(倍率:200倍)觀察5個視場,計數最大寬度為0.3μm以上的粗大粒子的個數,並按照下述評價基準評價了粗大粒子。 對於使用剛製造之後的分散液之情況下的評價結果,記載於初始欄中,對於使用在45℃下保管72小時之後的分散液之情況下的評價結果,記載於經時欄中。 A:粗大粒子的個數為20個以下 B:粗大粒子的個數超過20個且為40個以下 C:粗大粒子的個數超過40個且為100個以下 D:粗大粒子的個數超過100個 <Evaluation of dispersion liquid> (coarse particles) On the glass substrate, the dispersion immediately after production and the dispersion stored at 45°C for 72 hours were applied using a spin coater so that the thickness after heating would be 0.25 μm, and heated at 85°C for 2 minutes using a hot plate. to form a film. This film was observed in 5 fields of view with an optical microscope (magnification: 200 times), the number of coarse particles with a maximum width of 0.3 μm or more was counted, and the coarse particles were evaluated according to the following evaluation criteria. The evaluation results when using the dispersion liquid immediately after production are described in the initial column, and the evaluation results when using the dispersion liquid stored at 45° C. for 72 hours are described in the elapsed time column. A: The number of coarse particles is 20 or less B: The number of coarse particles exceeds 20 and is less than 40 C: The number of coarse particles exceeds 40 and is less than 100 D: The number of coarse particles exceeds 100
(經時穩定性) 用E型黏度計(Toki Sangyo Co.,Ltd製造,RE-85L)測定了剛製造之後的各分散液的黏度(mPa・s)。測定後,將各分散液在45℃、3天的條件下靜置之後,再度測定了黏度。算出靜置前後的分散液的黏度變化率,並按照下述評價基準評價了經時穩定性。可以說黏度變化率的數值愈小,經時穩定性愈良好。上述黏度測定均在將溫濕度控制在22±5℃、60±20%之實驗室中且將分散液的溫度調整在25℃之狀態下進行了測定。所有測定均進行了3次,並使用了平均值。 黏度變化率(%)=(|在45℃下靜置3天之後的分散液的黏度-剛製造之後的分散液的黏度|/剛製造之後的分散液的黏度)×100 A:黏度變化率為5%以下 B:黏度變化率超過5%且為10%以下 C:黏度變化率超過10%且為15%以下 D:黏度變化率超過15% (Stability over time) The viscosity (mPa·s) of each dispersion immediately after production was measured using an E-type viscometer (RE-85L manufactured by Toki Sangyo Co., Ltd.). After the measurement, each dispersion liquid was left to stand at 45° C. for 3 days, and then the viscosity was measured again. The viscosity change rate of the dispersion liquid before and after standing was calculated, and the stability over time was evaluated based on the following evaluation criteria. It can be said that the smaller the value of the viscosity change rate, the better the stability over time. The above viscosity measurements were all performed in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, and the temperature of the dispersion was adjusted to 25°C. All determinations were performed three times and the average value was used. Viscosity change rate (%) = (|Viscosity of the dispersion after standing at 45°C for 3 days - Viscosity of the dispersion immediately after production | / Viscosity of the dispersion immediately after production) × 100 A: The viscosity change rate is less than 5% B: The viscosity change rate exceeds 5% and is less than 10% C: The viscosity change rate exceeds 10% and is less than 15% D: The viscosity change rate exceeds 15%
[表6]
[表7]
[表8]
[表9]
[表10]
如上述表所示,實施例的分散液(樹脂組成物)的粗大粒子少,經時穩定性優異,顏料的分散穩定性優異。 再者,實施例1~181的分散液(分散液1~181)中所含之顏料衍生物的BET比表面積在2~300m 2/g的範圍內。又,實施例1~181的分散液(分散液1~181)中所含之顏料的平均一次粒徑在10~100nm的範圍內,並且顏料衍生物的平均一次粒徑在5~200nm的範圍內。 另一方面,比較例1的分散液(分散液C1)中所含之顏料衍生物的BET比表面積未達2m 2/g,並且比較例2的分散液(分散液C2)中所含之顏料衍生物的BET比表面積超過了300m 2/g。 As shown in the above table, the dispersion liquid (resin composition) of the Example has few coarse particles, has excellent stability over time, and has excellent pigment dispersion stability. Furthermore, the BET specific surface area of the pigment derivative contained in the dispersions of Examples 1 to 181 (dispersions 1 to 181) is in the range of 2 to 300 m 2 /g. Furthermore, the average primary particle diameter of the pigment contained in the dispersions of Examples 1 to 181 (dispersion 1 to 181) is in the range of 10 to 100 nm, and the average primary particle diameter of the pigment derivative is in the range of 5 to 200 nm. within. On the other hand, the BET specific surface area of the pigment derivative contained in the dispersion liquid of Comparative Example 1 (dispersion C1) is less than 2 m 2 /g, and the pigment contained in the dispersion liquid of Comparative Example 2 (dispersion C2) The BET specific surface area of the derivative exceeds 300m 2 /g.
<樹脂組成物的製造> 將各材料以以下所示之配方1~3的比例來混合,並藉由孔徑為0.45μm的尼龍製過濾器(Nihon Pall Ltd.製造)進行過濾而製造了各樹脂組成物。 <Manufacturing of resin composition> Each material was mixed at the ratio of Formulations 1 to 3 shown below and filtered through a nylon filter (manufactured by Nihon Pall Ltd.) with a pore diameter of 0.45 μm to produce each resin composition.
(配方1) 下述表中記載之分散液・・・・・・78.8質量份 下述表中記載之聚合性單體・・・・・・0.6質量份 下述表中記載之樹脂・・・・・・5.5質量份(在20質量%PGMEA溶液或20質量%環己酮溶液中的摻合量) 下述表中記載之光聚合起始劑・・・・・・0.5質量份 下述表中記載之界面活性劑・・・・・・0.0001質量份 下述表中記載之聚合抑制劑・・・・・・0.00135質量份 下述表中記載之溶劑・・・・・・14.7質量份 (Recipe 1) Dispersion liquid listed in the following table・・・・・・78.8 parts by mass Polymerizable monomers listed in the table below・・・・・・0.6 parts by mass Resin listed in the table below・・・・・・5.5 parts by mass (amount blended in 20 mass% PGMEA solution or 20 mass% cyclohexanone solution) Photopolymerization initiator listed in the following table・・・・・・0.5 parts by mass Surfactant listed in the table below・・・・・・0.0001 parts by mass Polymerization inhibitors listed in the following table・・・・・・0.00135 parts by mass Solvents listed in the table below・・・・・・14.7 parts by mass
(配方2) 下述表中記載之分散液・・・・・・55.0質量份 下述表中記載之聚合性單體・・・・・・6.4質量份 下述表中記載之樹脂・・・・・・27.5質量份(在20質量%PGMEA溶液或20質量%環己酮溶液中的摻合量) 下述表中記載之光聚合起始劑・・・・・・1.0質量份 下述表中記載之添加劑・・・・・・0.5質量份 下述表中記載之界面活性劑・・・・・・0.03質量份 下述表中記載之聚合抑制劑・・・・・・0.001質量份 下述表中記載之溶劑・・・・・・43.2質量份 (Recipe 2) Dispersion liquid listed in the following table・・・・・・55.0 parts by mass Polymerizable monomers listed in the following table・・・・・・6.4 parts by mass Resin listed in the table below・・・・・・27.5 parts by mass (blending amount in 20 mass% PGMEA solution or 20 mass% cyclohexanone solution) Photopolymerization initiator listed in the following table・・・・・・1.0 parts by mass Additives listed in the table below・・・・・・0.5 parts by mass Surfactant listed in the following table・・・・・・0.03 parts by mass Polymerization inhibitor listed in the following table・・・・・・0.001 parts by mass Solvents listed in the table below・・・・・・43.2 parts by mass
(配方3) 下述表中記載之分散液・・・・・・78.8質量份 下述表中記載之聚合性單體・・・・・・0.6質量份 下述表中記載之樹脂・・・・・・4.0質量份(在20質量%PGMEA溶液或20質量%環己酮溶液中的摻合量) 下述表中記載之光聚合起始劑・・・・・・0.5質量份 下述表中記載之添加劑・・・・・・0.3質量份 下述表中記載之界面活性劑・・・・・・0.0001質量份 下述表中記載之聚合抑制劑・・・・・・0.00135質量份 下述表中記載之溶劑・・・・・・15.9質量份 (Recipe 3) Dispersion liquid listed in the following table・・・・・・78.8 parts by mass Polymerizable monomers listed in the table below・・・・・・0.6 parts by mass Resin listed in the table below・・・・・・4.0 parts by mass (blending amount in 20 mass% PGMEA solution or 20 mass% cyclohexanone solution) Photopolymerization initiator listed in the following table・・・・・・0.5 parts by mass Additives listed in the following table・・・・・・0.3 parts by mass Surfactant listed in the table below・・・・・・0.0001 parts by mass Polymerization inhibitors listed in the following table・・・・・・0.00135 parts by mass Solvents listed in the table below・・・・・・15.9 parts by mass
[表11]
[表12]
[表13]
[表14]
[表15]
[表16]
[表17]
[表18]
[表19]
上述表中的用縮寫記載之原料的詳細內容如下。Details of the raw materials described with abbreviations in the above table are as follows.
(分散液) 分散液1~181、分散液C1、分散液C2:上述分散液1~181、分散液C1、分散液C2 (Dispersions) Dispersions 1 to 181, dispersion C1, and dispersion C2: the above dispersions 1 to 181, dispersion C1, and dispersion C2
(聚合性單體) M-1:下述結構的化合物 [化學式57] M-2:下述結構的化合物 [化學式58] M-3:KAYARAD DPHA(Nippon Kayaku Co.,Ltd.製造,二新戊四醇五丙烯酸酯與二新戊四醇六丙烯酸酯的混合物,Nippon Kayaku Co.,Ltd.製造) M-4:下述結構的化合物 [化學式59] M-5:下述結構的化合物的混合物(含有55莫耳%~63莫耳%的左側化合物) [化學式60] M-6:下述結構的化合物。 [化學式61] (Polymerizable monomer) M-1: A compound with the following structure [Chemical Formula 57] M-2: Compound with the following structure [Chemical Formula 58] M-3: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipenterythritol pentaacrylate and dipenterythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) M-4: Lower The compound with the above structure [Chemical Formula 59] M-5: A mixture of compounds with the following structure (containing 55 mol% to 63 mol% of the compound on the left) [Chemical Formula 60] M-6: Compound with the following structure. [Chemical formula 61]
(光聚合起始劑) I-1:Irgacure OXE01(BASF公司製造,肟化合物) I-2:Irgacure OXE02(BASF公司製造,肟化合物) I-3~I-8:下述結構的化合物 [化學式62] I-9:Omnirad 379(IGM Resins B.V.公司製造,α-胺基酮化合物) I-10:Omnirad 907(IGM Resins B.V.公司製造,α-胺基酮化合物) I-11~I-12:下述結構的化合物 [化學式63] (Photopolymerization initiator) I-1: Irgacure OXE01 (manufactured by BASF, oxime compound) I-2: Irgacure OXE02 (manufactured by BASF, oxime compound) I-3 to I-8: Compounds with the following structures [chemical formula 62] I-9: Omnirad 379 (IGM Resins BV, α-aminoketone compound) I-10: Omnirad 907 (IGM Resins BV, α-aminoketone compound) I-11 to I-12: The following Structure of the compound [Chemical Formula 63]
(樹脂) B-1:下述結構的樹脂(標註於主鏈之數值為莫耳比。具有酸基之樹脂,重量平均分子量11000,酸值69.2mgKOH/g)的20質量%PGMEA溶液 [化學式64] (Resin) B-1: 20 mass % PGMEA solution [Chemical formula 64]
B-2:下述結構的樹脂(標註於主鏈之數值為莫耳比。具有酸基之樹脂,重量平均分子量21000)的20質量%環己酮溶液 [化學式65] B-2: 20 mass% cyclohexanone solution [Chemical Formula 65] of a resin with the following structure (the value indicated on the main chain is molar ratio. Resin with acidic groups, weight average molecular weight 21000)
B-3:下述結構的樹脂(標註於主鏈之數值為莫耳比,標註於側鏈之數值為重複單元數。重量平均分子量16000,酸值67mgKOH/g)的20質量%PGMEA溶液 [化學式66] B-3: 20 mass% PGMEA solution of the resin with the following structure (the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. The weight average molecular weight is 16000, the acid value is 67 mgKOH/g) [ Chemical formula 66]
B-4:下述結構的樹脂(標註於主鏈之數值為莫耳比,標註於側鏈之數值為重複單元數。重量平均分子量18000,酸值82.1mgKOH/g)的20質量%PGMEA溶液 [化學式67] B-4: 20 mass% PGMEA solution of the resin with the following structure (the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. Weight average molecular weight 18000, acid value 82.1mgKOH/g) [Chemical formula 67]
B-5:下述結構的樹脂(標註於主鏈之數值為莫耳比。具有酸基之樹脂,重量平均分子量10000,酸值110mgKOH/g)的20質量%PGMEA溶液 [化學式68] B-5: 20 mass% PGMEA solution [Chemical Formula 68] of the resin with the following structure (the value marked on the main chain is molar ratio. Resin with acid group, weight average molecular weight 10000, acid value 110 mgKOH/g)
B-6:下述結構的樹脂(標註於主鏈之數值為莫耳比。具有酸基之樹脂,重量平均分子量10000,酸值110mgKOH/g)的20質量%PGMEA溶液 [化學式69] B-6: 20 mass% PGMEA solution [Chemical Formula 69] of the resin with the following structure (the value marked on the main chain is molar ratio. Resin with acid group, weight average molecular weight 10000, acid value 110 mgKOH/g)
(添加劑) A-1:EHPE3150(Daicel Corporation製造,2,2’-雙(羥甲基)-1-丁醇的1,2-環氧-4-(2-環氧乙烷基)環己烷加成物) UV-1:下述結構的化合物(紫外線吸收劑) [化學式70] (Additive) A-1: EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4-(2-oxiranyl)cyclohexanol of 2,2'-bis(hydroxymethyl)-1-butanol Alkane adduct) UV-1: Compound with the following structure (ultraviolet absorber) [Chemical Formula 70]
(界面活性劑) Su-1:KF-6001(Shin-Etsu Chemical Co., Ltd.製造,聚矽氧系界面活性劑,雙末端甲醇改質聚二甲基矽氧烷,羥基值62mgKOH/g) (surfactant) Su-1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., polysiloxane surfactant, double-terminal methanol-modified polydimethylsiloxane, hydroxyl value 62 mgKOH/g)
(聚合抑制劑) In-1:對甲氧基苯酚 (polymerization inhibitor) In-1: p-methoxyphenol
(溶劑) S-1:丙二醇單甲醚乙酸酯(PGMEA) (solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA)
<顯影殘渣的評價> 在玻璃基板上,使用旋塗機塗布基底層形成用組成物(CT-4000,FUJIFILM Electronic Materials Co.,Ltd.製造)以使其後烘烤後的厚度達到0.1μm,並使用加熱板在220℃下加熱1小時形成基底層,以獲得了附基底層之玻璃基板(支撐體)。接著,藉由旋塗法塗布各樹脂組成物以使其後烘烤後的膜厚達到0.4μm。接著,使用加熱板在100℃下加熱了3分鐘。接著,將玻璃基板載置於旋轉/噴淋顯影機(DW-30型,CHEMITRONICS CO., LTD.製造)的水平旋轉台上,使用顯影液(CD-2000,FUJIFILM Electronic Materials Co.,Ltd.製造)在23℃下進行60秒鐘的旋覆浸沒顯影之後,用真空吸盤方式將玻璃基板固定於水平旋轉台上,一邊藉由旋轉裝置使玻璃基板以轉速50rpm旋轉,一邊從其旋轉中心上方從噴出噴嘴以噴淋狀供給純水進行沖洗處理,之後進行了噴霧乾燥。進而,使用200℃的加熱板進行了5分鐘的加熱處理(後烘烤)。 使用分光光度計分別測定了塗布樹脂組成物之前的玻璃基板的吸光度A1及後烘烤後的玻璃基板的吸光度A1,並由以下式算出吸光度的變化量ΔA,並且使用吸光度的變化量ΔA的最大值評價了顯影殘渣。再者,吸光度的變化量ΔA的最大值係指吸光度的變化量ΔA變得最大的波長處的吸光度的變化量。係指吸光度的變化量ΔA的最大值愈小顯影殘渣愈少。 吸光度的變化量ΔA=|吸光度A1-吸光度A2| A:吸光度的變化量ΔA的最大值為0.01以下 B:吸光度的變化量ΔA的最大值超過0.01且為0.03以下 C:吸光度的變化量ΔA的最大值超過0.03且為0.05以下 D:吸光度的變化量ΔA的最大值超過0.05 <Evaluation of development residue> On the glass substrate, a base layer forming composition (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied using a spin coater so that the thickness after post-baking reached 0.1 μm, and a heating plate was used to heat the substrate at 220 The base layer was formed by heating at ℃ for 1 hour, and a glass substrate (support) with a base layer was obtained. Next, each resin composition was applied by spin coating so that the film thickness after post-baking would be 0.4 μm. Next, it was heated at 100° C. for 3 minutes using a hot plate. Next, the glass substrate was placed on the horizontal rotating stage of a spin/spray developing machine (model DW-30, manufactured by CHEMITRONICS CO., LTD.), and a developer (CD-2000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used. (Manufacture) After spin-immersion development for 60 seconds at 23°C, the glass substrate was fixed on a horizontal rotating table using a vacuum suction cup. While rotating the glass substrate at 50 rpm using a rotating device, the glass substrate was rotated from above its rotation center. Pure water was supplied in a spray form from the discharge nozzle for rinsing, and then spray drying was performed. Furthermore, heat processing (post-baking) was performed for 5 minutes using a 200°C hot plate. The absorbance A1 of the glass substrate before coating the resin composition and the absorbance A1 of the glass substrate after post-baking were measured using a spectrophotometer, and the change in absorbance ΔA was calculated according to the following formula, and the maximum change in absorbance ΔA was used. The value of development residue was evaluated. In addition, the maximum value of the absorbance change amount ΔA refers to the absorbance change amount at the wavelength where the absorbance change amount ΔA becomes maximum. It means that the smaller the maximum value of the change in absorbance ΔA, the smaller the development residue. The change in absorbance ΔA=|Absorbance A1-Absorbance A2| A: The maximum value of the change in absorbance ΔA is 0.01 or less B: The maximum value of absorbance change ΔA exceeds 0.01 and is 0.03 or less C: The maximum value of absorbance change ΔA exceeds 0.03 and is 0.05 or less D: The maximum value of absorbance change ΔA exceeds 0.05
[表20]
[表21]
如上述表所示,實施例的樹脂組成物能夠形成顯影殘渣少的像素。 再者,實施例1001~1222的樹脂組成物中所含之顏料衍生物的BET比表面積在2~300m 2/g的範圍內。又,實施例1001~1222中所含之顏料的平均一次粒徑在10~100nm的範圍內,並且顏料衍生物的平均一次粒徑在5~200nm的範圍內。 另一方面,比較例1001的樹脂組成物中所含之顏料衍生物的BET比表面積未達2m 2/g,並且比較例1002的樹脂組成物中所含之顏料衍生物的BET比表面積超過了300m 2/g。 As shown in the above table, the resin compositions of the Examples can form pixels with less development residue. Furthermore, the BET specific surface area of the pigment derivative contained in the resin compositions of Examples 1001 to 1222 is in the range of 2 to 300 m 2 /g. Furthermore, the average primary particle diameter of the pigments contained in Examples 1001 to 1222 is in the range of 10 to 100 nm, and the average primary particle diameter of the pigment derivative is in the range of 5 to 200 nm. On the other hand, the BET specific surface area of the pigment derivative contained in the resin composition of Comparative Example 1001 is less than 2 m 2 /g, and the BET specific surface area of the pigment derivative contained in the resin composition of Comparative Example 1002 exceeds 300m 2 /g.
由實施例的樹脂組成物獲得之膜能夠較佳地用於濾光器、固體攝像元件及圖像顯示裝置中。The film obtained from the resin composition of the Example can be suitably used in optical filters, solid-state imaging devices, and image display devices.
無。without.
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