WO2018070477A1 - 感光性着色組成物、硬化物、着色スペーサー、画像表示装置 - Google Patents
感光性着色組成物、硬化物、着色スペーサー、画像表示装置 Download PDFInfo
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- WO2018070477A1 WO2018070477A1 PCT/JP2017/037013 JP2017037013W WO2018070477A1 WO 2018070477 A1 WO2018070477 A1 WO 2018070477A1 JP 2017037013 W JP2017037013 W JP 2017037013W WO 2018070477 A1 WO2018070477 A1 WO 2018070477A1
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- 0 *OC(COC(C=C)=O)COc(cc(c(-c1cc(cccc2)c2cc1)c1)OCC(COC(C=C)=O)O*)c1-c1cc(cccc2)c2cc1 Chemical compound *OC(COC(C=C)=O)COc(cc(c(-c1cc(cccc2)c2cc1)c1)OCC(COC(C=C)=O)O*)c1-c1cc(cccc2)c2cc1 0.000 description 1
Classifications
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to a photosensitive coloring composition and the like.
- a photosensitive coloring composition preferably used for forming a colored spacer or the like in an image display device, a cured product obtained by curing the photosensitive coloring composition, a colored spacer formed from the cured product
- the present invention relates to an image display device provided with a colored spacer.
- Liquid crystal display utilizes the property that the arrangement of liquid crystal molecules is switched by turning on / off the voltage to the liquid crystal.
- each member constituting the LCD cell is often formed by a method using a photosensitive composition typified by photolithography.
- This photosensitive composition tends to form a fine structure and is easy to process a substrate for a large screen, and therefore, the application range of the photosensitive composition tends to further expand in the future.
- Patent Document 1 describes a method using a light-shielding spacer (colored spacer).
- Patent Document 2 discloses a specific combination in which a colored spacer having excellent light-shielding properties and voltage holding ratio of liquid crystal can be controlled and shape and level difference can be obtained and adhesion with a substrate is obtained.
- a colored photosensitive composition containing the above pigment has been proposed.
- the method for increasing the light shielding property include a method for increasing the content of the colorant in the photosensitive coloring composition.
- the present inventors examined, when forming a colored spacer using the photosensitive coloring composition which made the content rate of a coloring agent high, the coloring agent origin with respect to the solvent at the time of forming the alignment film used as the upper layer film
- This invention is made
- the content ratio of the colorant is not less than a specific value, and by using a specific alkali-soluble resin, the above-mentioned problems are solved.
- the inventors have found that the problem can be solved and have reached the present invention.
- the present invention has the following configurations [1] to [16].
- Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant.
- a composition comprising: The content ratio of the colorant (a) in the total solid content of the photosensitive coloring composition is 20% by mass or more, The photosensitive coloring composition, wherein the (b) alkali-soluble resin contains an alkali-soluble resin (b-1) having a partial structure (1) represented by the following formula (I).
- R 1 represents a hydrogen atom or a methyl group
- R 2 , R 3 , R 5 and R 6 each independently represents an alkylene group which may have a substituent
- R 4 represents an n + 1 valent linking group
- R 7 represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an aromatic ring group that may have a substituent
- l and m each independently represents an integer of 0 to 12
- n represents an integer of 3 or more
- Photosensitive coloring containing (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) ethylenically unsaturated compound, (e) solvent, and (f) dispersant.
- a composition comprising: The content ratio of the colorant (a) in the total solid content of the photosensitive coloring composition is 20% by mass or more, The photosensitive coloring composition, wherein the (b) alkali-soluble resin contains an alkali-soluble resin (b-1) having a double bond equivalent of 400 or less.
- Photosensitive coloring composition. [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the (b) alkali-soluble resin further contains an epoxy (meth) acrylate resin (b-2).
- the epoxy (meth) acrylate resin (b-2) is an epoxy (meth) acrylate resin (b-2-ii) having a partial structure represented by the following general formula (ii): [5] The photosensitive coloring composition as described in 2.
- each R c independently represents a hydrogen atom or a methyl group
- R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R e and R f each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represents an integer of 0 to 2; * Represents a bond.
- the organic coloring pigment contains at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment.
- Photosensitive coloring composition [9] The photosensitive coloring composition according to any one of [1] to [8], wherein the colorant (a) contains a black pigment.
- the black pigment contains one or both of carbon black and an organic black pigment.
- the organic black pigment is at least one selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound.
- the photosensitive coloring composition as described in [10] which is an organic black pigment containing seeds.
- R 11 and R 16 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom, a halogen atom, R 21 , COOH, COOR 21 , COO ⁇ , CONH 2 , CONHR 21.
- [14] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [13].
- An image display device comprising the colored spacer according to [15].
- a photosensitive coloring composition that can form a pattern with high light shielding properties and excellent solvent resistance and mechanical properties. Further, it is possible to provide a cured product and a colored spacer that are excellent in light-shielding properties, excellent in solvent resistance and mechanical properties, and it is possible to provide an image display device including such a colored spacer.
- (meth) acryl means “one or both of acrylic and methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
- (co) polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer).
- acid (anhydride) means to include both acids and anhydrides.
- acrylic resin means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.
- the term “monomer” is a term corresponding to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, etc. in addition to a monomer (monomer) in a narrow sense. It is.
- the “total solid content” means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
- “weight average molecular weight” refers to polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography).
- the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.
- the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
- the photosensitive coloring composition of the present invention is (A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compound (e) Solvent (f) A dispersant is contained as an essential component.
- the photosensitive coloring composition of the present invention may further comprise an adhesion improver such as a silane coupling agent, a surfactant (applicability improver), a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto, if necessary. It may contain other compounding components such as a compound, a development improver, an ultraviolet absorber, an antioxidant and the like, and each compounding component is usually used in a state dissolved or dispersed in a solvent.
- the content of (a) the colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more, and (b) alkali-soluble
- the resin contains an alkali-soluble resin (b-1) having a partial structure (1) represented by the following formula (I).
- the content of (a) the colorant in the total solid content of the photosensitive coloring composition is 20% by mass or more, and (b)
- the alkali-soluble resin contains an alkali-soluble resin (b-1) having a double bond equivalent of 400 or less.
- the “photosensitive coloring composition of the present invention” refers to both the photosensitive coloring composition according to the first aspect and the photosensitive coloring composition according to the second aspect.
- “alkali-soluble resin (b-1)” means “alkali-soluble resin (b-1)” according to the first embodiment and “alkali-soluble resin (b-)” according to the second embodiment. 1) ".
- the photosensitive coloring composition of the present invention contains (a) a colorant.
- (A) By containing a coloring agent, moderate light-absorbing property, especially when used for the purpose of forming a light-shielding member such as a colored spacer, moderate light-shielding property can be obtained.
- the photosensitive coloring composition of this invention is 20 mass% or more of content rate of the (a) coloring agent which occupies for all the solid content.
- cured material obtained, especially a coloring spacer becomes high by containing a predetermined amount or more of (a) coloring agent.
- the proportion of the colorant in the total solid content is high, the content of curable components such as resins and monomers that contribute to photocuring is relatively low, and the content of the colorant is high.
- the proportion of ultraviolet light absorbed by the colorant at the time of exposure also tends to increase, and as a result, the crosslink density of the cured product decreases, and the solvent resistance and mechanical properties tend to deteriorate. .
- the type of the colorant used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.
- the pigment contained in the colorant may be used alone or in combination of two or more. In particular, two or more types are preferable from the viewpoint of uniformly shielding light in the visible region.
- the kind of pigment which can be used as a coloring agent is not specifically limited, For example, an organic pigment and an inorganic pigment are mentioned. Among these, it is preferable to use an organic pigment from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and controlling the shape and level difference by suppressing the absorption of ultraviolet rays.
- Organic pigments include organic color pigments and organic black pigments.
- the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, and a yellow pigment.
- organic coloring pigments it is preferable to use an organic coloring pigment from the viewpoint of light shielding properties and ultraviolet absorption properties.
- One organic coloring pigment may be used alone, or two or more organic coloring pigments may be used in combination.
- organic pigments are not particularly limited, and examples thereof include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene.
- CI Pigment Red 2 refers to the color index (CI).
- C.I. I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
- C.I. I. Pigment Red 177, 254, and 272 are preferably used.
- the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate.
- CI pigment red 254 and 272 are used.
- C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
- C.I. I. Pigment Orange 13, 43, 64, 72 are preferably used.
- the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate, from this viewpoint.
- C. I. More preferably, CI pigment oranges 64 and 72 are used.
- blue pigments examples include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
- C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60 and more preferably C.I. I. Pigment blue 15: 6.
- C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used.
- the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate.
- C. I. More preferably, CI Pigment Blue 60 is used.
- Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
- C.I. I. Pigment Violet 23 and 29 are preferably used.
- the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. I. More preferably, pigment violet 29 is used.
- organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
- green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
- yellow pigments include C.I. I.
- C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
- Red pigment Color index pigment red 177, 254, 272
- Orange pigment Color index pigment orange 43, 64, 72
- Blue pigment Color index pigment blue 15: 6, 60 Purple pigment: Color index pigment violet 23, 29
- the combination of the organic coloring pigments when two or more organic coloring pigments are used in combination is not particularly limited, but from the viewpoint of light shielding properties, at least one selected from the group consisting of a red pigment and an orange pigment, and a blue pigment And at least one selected from the group consisting of purple pigments.
- the combination of colors is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a purple pigment can be mentioned. .
- black pigments may be used.
- a black pigment may be further used.
- the black pigment include inorganic black pigments and organic black pigments, but it is preferable to contain one or both of carbon black and organic black pigments from the viewpoint of light shielding properties.
- organic black pigments it is preferable to use organic black pigments from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to easily control the shape and level difference, and particularly the light shielding property.
- compound (1) the compound represented by the following general formula (1)
- organic black pigment represented by the general formula (1) it is preferable to use an organic black pigment containing at least one selected from the group consisting of salts of geometrical isomers (hereinafter referred to as “organic black pigment represented by the general formula (1)”).
- R 11 and R 16 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 are each independently a hydrogen atom, a halogen atom, R 21 , COOH, COOR 21 , COO ⁇ , CONH 2 , CONHR 21.
- compound (1) When compound (1) is anionic, its charge can be transferred to any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium Preferred is a salt compensated by tertiary ammonium such as secondary ammonium or trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Further, when the geometric isomer of the compound (1) is anionic, it is preferably a similar salt.
- R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
- R 13 and R 18 are each independently preferably a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3) (C 2 H 5) , N (C 2 H 5) 2, ⁇ - naphthyl, beta-naphthyl, SO 3 H or SO 3 - and, still more preferably a hydrogen atom or SO 3 H, and particularly preferably Is a hydrogen atom.
- R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
- at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is the same as R 20 Are the same.
- alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2 -Ethylhexyl, nonyl, decyl, undecyl or dodecyl.
- Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, tuzyl group, norbornyl group, bornyl group, norcaryl group. , Caryl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.
- alkenyl group having 2 to 12 carbon atoms examples include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene.
- Examples of the cycloalkenyl group having 3 to 12 carbon atoms include a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, , 4-Cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4 (10) -tgen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -An yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.
- alkynyl group having 2 to 12 carbon atoms examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl.
- the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- the organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2) (hereinafter also referred to as “compound (2)”) and geometric isomerism of the compound (2).
- organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
- This organic black pigment is preferably used after being dispersed by a dispersant, a solvent and a method described later.
- a sulfonic acid derivative of compound (1) particularly a sulfonic acid derivative of compound (2), is present at the time of dispersion, the dispersibility and storage stability may be improved. It is preferable to contain.
- Examples of the organic black pigment other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.
- examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
- carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics.
- examples of carbon black include the following carbon black.
- Carbon black coated with resin may be used. When carbon black coated with resin is used, there is an effect that adhesion to a glass substrate and volume resistance are improved.
- carbon black coated with the resin for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
- Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
- the total content of Na and Ca is preferably 100 ppm or less.
- Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, and Na, Ca, K, Mg, Al, Fe, etc. mixed from the reactor furnace material, etc. Ashes are contained in the composition.
- Na and Ca are generally contained in a few hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electricity Tend to prevent mechanical short circuit.
- the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 mL / 100 g or less. By setting it within the above range, a coating film having good light shielding properties tends to be obtained.
- Average particle size means number average particle size. Photographs taken with tens of thousands of magnifications by electron microscope observation are taken in several fields of view, and particle image analysis in which about 2000 to 3000 particles of these photographs are measured by an image processing apparatus. This means the equivalent circle diameter obtained by.
- the method for preparing carbon black coated with resin is not particularly limited. For example, after appropriately adjusting the blending amount of carbon black and resin, After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, the carbon black and water are separated, 1. A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried; A method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and the resin, then separating and heating the obtained granular material, and removing the remaining solvent and water; 3.
- a carboxylic acid such as maleic acid or fumaric acid is dissolved in the above exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and then a resin is added thereto.
- dry blending method A reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension.
- a method of adding carbon black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.
- the type of resin to be coated is not particularly limited, but a synthetic resin is common, and since a resin having a benzene ring in the structure has a stronger function as an amphoteric surfactant, From the viewpoint of dispersibility and dispersion stability, it is preferable.
- Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene.
- Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used.
- the amount of the coating resin is preferably 1 to 30% by mass with respect to the total amount of carbon black and resin. There exists a tendency which can make coating
- the carbon black thus coated with a resin can be used as a coloring agent for a colored spacer according to a conventional method, and a color filter having this colored spacer as a constituent element can be prepared by a conventional method.
- a coloring agent for a colored spacer according to a conventional method
- a color filter having this colored spacer as a constituent element can be prepared by a conventional method.
- carbon black is used, there is a tendency that a colored spacer having a high light shielding rate and a low surface reflectance can be formed at a low cost. It is also presumed that ash containing Na and Ca is contained in carbon black by coating the surface of carbon black with resin.
- the average particle size of the pigment is usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less.
- the standard of the average particle diameter is the number of pigment particles.
- the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS).
- the particle size is measured by fully diluting the photosensitive coloring composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass, provided that there is a concentration recommended by the measuring instrument. , According to the concentration) and measured at 25 ° C.
- dyes may be used.
- the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
- the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I.
- anthraquinone dyes examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
- Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
- the alkali-soluble resin is an alkali-soluble resin (b-1) having the partial structure (1) represented by the following formula (I) (hereinafter, The “alkali-soluble resin (b-1)” in the first embodiment is sometimes referred to as “alkali-soluble resin (b-1-1)”. Since the alkali-soluble resin (b-1-1) has 3 or more (meth) acryloyloxy groups in the partial structure represented by the formula (I), the amount of ethylenic double bonds in one molecule of the resin is large.
- the crosslink density is increased, elution of impurities into the solvent is suppressed, and high display reliability can be secured. Similarly, the crosslink density of the spacer is increased. It is considered that the mechanical properties are also excellent.
- R 1 represents a hydrogen atom or a methyl group
- R 2 , R 3 , R 5 and R 6 each independently represents an alkylene group which may have a substituent
- R 4 represents an n + 1 valent linking group
- R 7 represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an aromatic ring group that may have a substituent
- l and m each independently represents an integer of 0 to 12
- n represents an integer of 3 or more
- R 2 , R 3 , R 5 and R 6 each independently represents an alkylene group which may have a substituent.
- the alkylene group may be linear, branched, cyclic, or a combination thereof.
- the carbon number is not specifically limited, it is 1 or more, and is usually 6 or less, preferably 4 or less, more preferably 2 or less. There exists a tendency for compatibility with another component to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 2.
- alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, and a cyclohexylene group. From the viewpoint of compatibility with other components, a methylene group or an ethylene group is preferable, and a methylene group is more preferable. .
- alkylene group may have an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, It is preferably unsubstituted.
- R 4 represents an n + 1 valent linking group.
- the chemical structure of the n + 1 valent linking group is not particularly limited, and examples thereof include an n + 1 valent hydrocarbon group which may have a substituent.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group from the viewpoint of developability.
- the carbon-carbon single bond in the hydrocarbon group may be interrupted with at least one selected from the group consisting of —O—, CO—, and —NH—.
- n + 1 valent linking group examples include the following. * In the chemical formula represents a bond.
- R 7 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or a divalent aromatic ring which may have a substituent. Represents a group.
- the alkylene group for R 7 may be linear, branched, cyclic, or a combination thereof.
- the carbon number is not particularly limited, it is 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, more preferably 4 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 8, more preferably 1 to 6, and further preferably 2 to 4.
- alkylene group examples include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
- alkylene group may have an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.
- the alkenylene group for R 7 may be linear, branched, cyclic, or a combination thereof.
- the carbon number is not particularly limited, it is 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 2 to 8, and more preferably 4 to 6.
- alkenylene group examples include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferable, and an ethenylene group is more preferable.
- alkenylene group may have an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.
- Examples of the divalent aromatic ring group for R 7 include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, and more preferably 10 or less. Particularly preferred.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 5 to 30, more preferably 6 to 20, still more preferably 6 to 15, and particularly preferably 6 to 10.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
- the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
- Examples of the substituent that the divalent aromatic ring group may have include an alkyl group, an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. . Among these, unsubstituted is preferable from the viewpoint of curability.
- R 7 is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and even more preferably an ethylene group.
- l and m each independently represents an integer of 0 to 12. From the viewpoint of development adhesion, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of curability, it is preferably 8 or less, more preferably 6 or less. The following is more preferable, and 2 or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 0 to 8, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 2. On the other hand, it is preferably 0 from the viewpoint of curability.
- n represents an integer of 3 or more.
- n is preferably 4 or more, more preferably 5 or more, and is preferably 10 or less, more preferably 8 or less, still more preferably 7 or less, and particularly preferably 6 or less.
- the combination of the upper limit and the lower limit is preferably 3 to 10, more preferably 4 to 8, further preferably 5 to 7, and particularly preferably 5 to 6.
- the alkali-soluble resin (b-1-1) preferably has a partial structure (2) represented by the following formula (II) from the viewpoint of development solubility.
- R 8 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an aromatic ring group which may have a substituent. ; * Represents a bond.
- R 8 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or a divalent aromatic ring which may have a substituent. Represents a group.
- the alkylene group for R 8 may be linear, branched, cyclic, or a combination thereof.
- the carbon number is not particularly limited, it is 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 8, and more preferably 2 to 6.
- alkylene group examples include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
- alkylene group may have an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.
- the alkenylene group for R 8 may be linear, branched, cyclic, or a combination thereof.
- the carbon number is not particularly limited, it is 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less.
- alkenylene group examples include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferable, and a cyclohexenylene group is more preferable.
- alkenylene group may have an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.
- Examples of the divalent aromatic ring group for R 8 include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, and more preferably 10 or less. Particularly preferred.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 5 to 30, more preferably 6 to 20, still more preferably 6 to 15, and particularly preferably 6 to 10.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
- the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
- Examples of the substituent that the divalent aromatic ring group may have include an alkyl group, an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. . Among these, unsubstituted is preferable from the viewpoint of curability.
- R 8 is preferably an alkenylene group which may have a substituent, more preferably an unsubstituted alkenylene group, and further preferably a cyclohexenylene group. preferable.
- the alkali-soluble resin (b-1-1) preferably has a partial structure (3) represented by the following formula (III) from the viewpoint of curability.
- R 9 represents an epoxy resin residue.
- the epoxy resin residue means a residue obtained by removing an epoxy group from an epoxy resin.
- the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins.
- the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react.
- the phenolic compound is preferably a compound having a dihydric or higher phenolic hydroxyl group, and may be a monomer or a polymer.
- bisphenol A epoxy resin bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxyoxyfluorene type epoxy resin, dihydroxyalkyleneoxyl fluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy) Phenyl) adamantane diglycidyl ether, and the like, and those having an aromatic ring in the main chain like these can be suitably used.
- p represents an integer of 1 or more. From the viewpoint of achieving both curability and development solubility, p is preferably 2. On the other hand, from the viewpoint of curability, p is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and 20 or less from the viewpoint of development solubility. Is more preferable, 15 or less is more preferable, and 10 or less is further preferable. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 2 to 15, and further preferably 2 to 10.
- the partial structure (3) represented by the formula (III) is preferably a partial structure (3-1) represented by the following formula (III-1) from the viewpoint of development solubility.
- ⁇ represents a divalent linking group
- the benzene ring in formula (III-1) may be further substituted with an optional substituent; * Represents a bond.
- ⁇ represents a divalent linking group.
- the divalent linking group include a single bond, an alkylene group which may have a substituent, —CO— or —SO 2 — from the viewpoint of development solubility.
- the alkylene group may be linear, branched, cyclic, or a combination thereof.
- the number of carbon atoms is not particularly limited, but is 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 8, and more preferably 2 to 6.
- alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, a heptylene group, an octylene group, and a dodecylene group.
- a methylene group or a propylene group is preferable.
- a propylene group is preferable, and a propane-2,2-diyl group is more preferable.
- alkylene group may have examples include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred. When it has a substituent, the number is not limited and may be 1 or 2 or more.
- both of the two hydrogen atoms of the methylene group (—CH 2 —) in the alkylene group are substituted with a substituent, the two substituents may be linked to form a hydrocarbon ring.
- ⁇ in that case include a group represented by the following formula (IV) and a group represented by the following formula (V). * In the chemical formula represents a bond.
- Examples of the optional substituent that the benzene ring in formula (III-1) may have include, for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Is mentioned.
- the number of substituents is not particularly limited, either one or two or more.
- the two benzene rings in the formula (III-1) may be linked by the substituent. For example, they may be linked by —O—.
- ⁇ is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and a propylene group. Is more preferred, and propane-2,2-diyl is more preferred.
- ⁇ is preferably a group represented by the formula (IV).
- the partial structure (3) represented by the formula (III) is preferably a partial structure (3-2) represented by the following formula (III-2) from the viewpoint of curability.
- the benzene ring in the above formula (III-2) may be further substituted with an arbitrary substituent; * Represents a bond.
- Examples of the optional substituent that the benzene ring in formula (III-2) may have include a hydroxyl group, an alkyl group, and an alkoxy group.
- the number of substituents is not particularly limited, either one or two or more. Among these, from the viewpoint of development adhesion, an alkyl group is preferable, a cycloalkyl group is more preferable, and an adamantyl group is more preferable.
- the partial structure (3) represented by the formula (III) preferably includes a partial structure (3-3) represented by the following formula (III-3) from the viewpoint of curability.
- R 10 represents a divalent hydrocarbon group which may have a substituent;
- the benzene ring in formula (III-3) may be further substituted with an optional substituent; * Represents a bond.
- R 10 represents a divalent hydrocarbon group which may have a substituent.
- the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.
- Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, while a cyclic one is preferable from the viewpoint of development adhesion.
- the number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10.
- divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
- a methylene group is preferable from the viewpoint of curability.
- divalent branched aliphatic group examples include the above-mentioned divalent linear aliphatic group, a side chain of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is 1 or more, preferably 2 or more, and usually 20 or less, preferably 10 or less, and more preferably 5 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 20, and more preferably 2 to 10.
- divalent aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
- a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 4 to 20, more preferably 5 to 15, and further preferably 6 to 10.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
- the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
- benzene ring or naphthalene ring examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. That. Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring or naphthalene ring or thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring,
- Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of curability.
- divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
- a group in which one or more cyclic groups are linked is not particularly limited, but is 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- sclerosis hardenability to become favorable by setting it as the said lower limit or more
- developability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the benzene ring in formula (III-3) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of curability.
- the partial structure (3) represented by the formula (III) preferably includes a partial structure (3-4) represented by the following formula (III-4) from the viewpoint of curability.
- ⁇ represents a divalent linking group
- the benzene ring in formula (III-4) may be further substituted with an optional substituent; * Represents a bond.
- ⁇ in the formula (III-4) those described as ⁇ in the formula (III-1) can be preferably used.
- the optional substituent that the benzene ring in the formula (III-4) may have is the optional substituent that the benzene ring in the formula (III-1) may have. What has been described can be preferably employed.
- the alkali-soluble resin (b-1-1) has a partial structure (3-1) from the viewpoint of development solubility. Is preferred.
- the alkali-soluble resin (b) contains an alkali-soluble resin (b-1-1), and the alkali-soluble resin (b-1-1).
- the compound (p1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy resin (A) is optionally reacted with an isocyanate group-containing compound (p3), and then a polyvalent carboxylic acid and its compound A method of reacting one or both of the anhydrides (p2) can be mentioned.
- epoxy resin (A) As the epoxy resin (A), those described as the epoxy resin in the epoxy resin residue of R 9 in the formula (III) can be used. Specifically, the epoxy resin described in the following formula (III-5) Can be used.
- the compound (p1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy resin (A) as described above is reacted with the above epoxy resin (A) as a raw material, resulting in an ethylenically unsaturated group. If the containing carbonyloxy group is formed, the production method is not limited. Specifically, the above-mentioned epoxy resin (A) is reacted with an ethylenically unsaturated group-containing carboxylic acid (B).
- a method of reacting a compound (D) having a functional group reactive with a hydroxyl group to form an ethylenically unsaturated group-containing carbonyloxy group, Etc. can be mentioned.
- ethylenically unsaturated group-containing carboxylic acids (B) examples include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include (meth) acrylic acid, crotonic acid, o-, m -, P-vinylbenzoic acid, monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of (meth) acrylic acid, reaction products of (meth) acrylic acid with lactone or polylactone; Succinic anhydride, adipic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylen
- half esters obtained by reacting pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are particularly preferable. These may be used alone or in combination of two or more.
- Carboxylic acids not containing ethylenically unsaturated groups (C) examples include hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and anhydrides thereof, dicarboxylic acids such as succinic acid, phthalic acid, and tartaric acid, and anhydrides thereof. It is done. These may be used alone or in combination of two or more.
- Compound (D) having a functional group that reacts with a hydroxyl group or a carboxyl group After reacting the epoxy resin (A) with a carboxylic acid (C) that does not contain an ethylenically unsaturated group, the compound (D) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted, As the compound (D) having a functional group that reacts with a hydroxyl group or a carboxyl group used when forming an ethylenically unsaturated group-containing carbonyloxy group, a compound having an epoxy group, a carboxyl group, or an isocyanate group is preferable.
- examples thereof include, but are not limited to, ethylenically unsaturated group-containing compounds such as the above-mentioned ethylenically unsaturated group-containing carboxylic acids and the above-mentioned unsaturated group-containing glycidyl compounds. These may be used alone or in combination of two or more.
- the compound (p1) having an ethylenically unsaturated group-containing hydroxyl group obtained from the epoxy resin (A) may optionally be combined with an isocyanate group-containing compound (p3). ) May be reacted.
- the isocyanate group-containing compound (p3) includes butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, organic monoisocyanates such as 3-isopropenoyl- ⁇ , ⁇ -dimethylbenzyl isocyanate; paraphenylene diisocyanate, 2,4-tolylene diisocyanate Aromatic diisocyanates such as 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate; hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid Aliphatic diisocyanates such as diisocyanates; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as ⁇ ,
- dimers or trimers of organic diisocyanates preferred are dimers or trimers of organic diisocyanates, and most preferred are trimethylolpropane adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and trimers of isophorone diisocyanate. . These may be used alone or in combination of two or more.
- the alkali-soluble resin (b-1-1) is obtained by adding the above-mentioned isocyanate group-containing compound (p3) to the compound (p1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy resin (A).
- polyvalent carboxylic acid and its anhydride examples include succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthal Saturated or unsaturated dicarboxylic acids such as acids and phthalic acids and acid anhydrides thereof; trimellitic acid and anhydrides thereof, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, butane Examples include tetracarboxylic acids such as tetracarboxylic acids and acid anhydrides thereof.
- dicarboxylic acids such as succinic acid, tetrahydrophthalic acid, and phthalic acid, and acid anhydrides thereof, trimellitic acid and anhydrides thereof.
- Etc Carboxyl oxides of trivalent or less It is used.
- an acid anhydride of a polyvalent carboxylic acid having an acid dissociation constant (first dissociation constant) of 3.5 or more is more preferable.
- the acid dissociation constant is further preferably 3.8 or more, and particularly preferably 4.0 or more.
- succinic acid and an acid anhydride of tetrahydrophthalic acid are particularly preferable.
- polyvalent carboxylic acid and its acid anhydride may be used individually by 1 type, or may use 2 or more types together.
- the alkali-soluble resin (b-1-1) is further added to a part of the carboxyl group in the compound obtained by reacting one or both of the polyvalent carboxylic acid and its anhydride (p2) in this way.
- the compound which added the said epoxy resin (A) may be sufficient.
- alkali-soluble resin (b-1-1) As a specific method for producing the alkali-soluble resin (b-1-1), methods described in Japanese Patent Application Laid-Open Nos. 2006-312704 and 2007-119718 can be employed.
- alkali-soluble resin (b-1-1) those having a partial structure derived from an epoxy resin and those obtained by modifying an epoxy resin as a raw material have been described in detail. Not limited. For example, what added the said ethylenically unsaturated group containing carboxylic acid (B) to the acrylic resin which contains a glycidyl ether group in a side chain, etc. are mentioned.
- the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but is 1000 or more.
- 1500 or more is more preferable, 2000 or more is further preferable, 2500 or more is particularly preferable, 6000 or less is preferable, 5000 or less is more preferable, 4000 or less is further preferable, and 3500 or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 1000 to 6000, more preferably 1500 to 5000, further preferably 2000 to 4000, and particularly preferably 2500 to 3500.
- the acid value of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, 15 mgKOH / g or more is more preferable, 20 mgKOH / g or more is particularly preferable, 60 mgKOH / g or less is preferable, 50 mgKOH / g or less is more preferable, 40 mgKOH / g or less is more preferable, and 30 mgKOH / g or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g, further preferably 15 to 40 mgKOH / g, and particularly preferably 20 to 30 mgKOH / g.
- the double bond equivalent of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but is preferably 20 or more, more preferably 50 or more, and 80 or more. Is more preferably 100 or more, more preferably 600 or less, more preferably 400 or less, still more preferably 300 or less, still more preferably 200 or less, particularly preferably 180 or less, and most preferably 150 or less. There exists a tendency for development solubility to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis
- the combination of the upper limit and the lower limit is preferably 20 to 600, more preferably 50 to 400, still more preferably 80 to 300, and particularly preferably 100 to 200.
- the double bond equivalent of the alkali-soluble resin (b-1) can be calculated from the following formula (x).
- the number of ethylenically unsaturated double bonds contained in one molecule of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the first aspect is not particularly limited, but 2 or more Is preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 8 or more, preferably 20 or less, more preferably 18 or less, further preferably 14 or less, and 12 or less. Particularly preferred. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.
- the combination of the upper limit and the lower limit is preferably 2 to 20, more preferably 4 to 18, still more preferably 6 to 14, and particularly preferably 8 to 12.
- the photosensitive coloring composition of the present invention according to the first aspect is such that (b) the alkali-soluble resin has the partial structure (1) represented by the formula (I) (b- 1), the alkali-soluble resin (b-1) may contain one kind alone, or may contain two or more kinds in combination.
- the alkali-soluble resin is an alkali-soluble resin (b-1) having a double bond equivalent of 400 or less (hereinafter referred to as “ The alkali-soluble resin (b-1) ”may be referred to as“ alkali-soluble resin (b-1-2) ”. Since the alkali-soluble resin (b-1-2) has a double bond equivalent of 400 or less, the amount of ethylenic double bonds in one molecule of the resin is large, and coloring is performed using a photosensitive coloring composition containing the resin. When the spacer is formed, the crosslink density is increased, elution of impurities into the solvent is suppressed, and high display reliability can be secured. Similarly, it is considered that the mechanical property is also excellent by increasing the crosslink density of the spacer.
- the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second embodiment is not particularly limited, but is 1000 or more.
- 1500 or more is more preferable, 2000 or more is further preferable, 2500 or more is particularly preferable, 6000 or less is preferable, 5000 or less is more preferable, 4000 or less is further preferable, and 3500 or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 1000 to 6000, more preferably 1500 to 5000, further preferably 2000 to 4000, and particularly preferably 2500 to 3500.
- the acid value of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, 15 mgKOH / g or more is more preferable, 20 mgKOH / g or more is particularly preferable, 60 mgKOH / g or less is preferable, 50 mgKOH / g or less is more preferable, 40 mgKOH / g or less is more preferable, and 30 mgKOH / g or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g, further preferably 15 to 40 mgKOH / g, and particularly preferably 20 to 30 mgKOH / g.
- the double bond equivalent of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited as long as it is 400 or less, but is preferably 20 or more, more preferably 50 or more. More preferably, 80 or more is more preferable, 100 or more is particularly preferable, 350 or less is preferable, 300 or less is next preferable, 200 or less is more preferable, 180 or less is more preferable, 160 or less is further preferable, and 160 or less is more preferable. Is particularly preferable, 140 or less is particularly preferable, and 130 or less is most preferable.
- the combination of the upper limit and the lower limit is preferably 20 to 400, more preferably 50 to 400, still more preferably 80 to 300, and particularly preferably 100 to 200.
- the double bond equivalent of the alkali-soluble resin (b-1) in the second embodiment can be calculated from the above formula (x).
- the number of ethylenically unsaturated double bonds contained in one molecule of the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited. Or more, preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 8 or more, preferably 20 or less, more preferably 18 or less, still more preferably 14 or less, and 12 or less Is particularly preferred. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.
- the combination of the upper limit and the lower limit is preferably 2 to 20, more preferably 4 to 18, still more preferably 6 to 14, and particularly preferably 8 to 12.
- the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is an alkali-soluble resin contained in the photosensitive coloring composition of the present invention according to the first aspect.
- Those listed as (b-1) can be preferably used.
- the alkali-soluble resin (b-1) contained in the photosensitive coloring composition of the present invention according to the second aspect is not particularly limited as long as the double bond equivalent is 400 or less.
- Alkali-soluble resins other than the alkali-soluble resin (b-1) according to the embodiment may be employed.
- Examples of the repeating unit containing an ethylenic double bond in the side chain include a repeating unit represented by the following formula (IV).
- R 11 and R 12 each independently represents a hydrogen atom or a methyl group; * Represents a bond.
- the alkali-soluble resin further includes an epoxy (meth) acrylate resin (b-2) other than the alkali-soluble resin (b-1) (hereinafter referred to as “epoxy (meth) acrylate resin”).
- epoxy (meth) acrylate resin (B-2) "may be abbreviated.).
- the epoxy (meth) acrylate resin (b-2) is obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to the epoxy resin, optionally reacting with an isocyanate group-containing compound, and then a polybasic acid or an anhydride thereof. It is the resin which reacted. For example, by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (—COO—). The thing which one carboxy group of the polybasic acid anhydride was added to the hydroxyl group produced in that case is mentioned.
- the epoxy (meth) acrylate resin (b-2) also includes a resin obtained by reacting a compound having a functional group capable of further reaction with the carboxyl group of the resin obtained by the above reaction.
- the epoxy (meth) acrylate resin has substantially no epoxy group in terms of chemical structure and is not limited to “(meth) acrylate”, but an epoxy compound (epoxy resin) is a raw material.
- (meth) acrylate” is a representative example, it is named in accordance with conventional usage.
- the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react.
- the phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
- bisphenol A epoxy resin bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxyoxyfluorene type epoxy resin, dihydroxyalkyleneoxyl fluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy) Phenyl) adamantane diglycidyl ether, and the like, and those having an aromatic ring in the main chain can be suitably used.
- bisphenol A epoxy resin bisphenol A epoxy resin, phenol novolac epoxy resin, biphenyl novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, 9,9-bis (4′-hydroxyphenyl) ) Diglycidyl etherified product of fluorene, an epoxy resin having an adamantyl group, and the like are preferable, and an epoxy resin having an adamantyl group is more preferable.
- Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adduct, penta Erythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydro Examples thereof include phthalic anhydride adducts and reaction products of (meth) acrylic acid and ⁇ -caprolactone. Among these, (meth) acrylic acid is preferable and acrylic acid is
- polybasic acid examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , Benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof.
- succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or biphenyltetracarboxylic dianhydride are preferable, succinic anhydride, tetrahydrophthalic acid.
- An anhydride or biphenyltetracarboxylic dianhydride is more preferable, and tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride is more preferable.
- the molecular weight of the epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced.
- the rate of introduction of acid groups into the molecule can be increased, and there is a tendency that balances such as sensitivity and adhesiveness are easily obtained.
- the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably there is.
- the acid value of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 50 mgKOH / g or more, and more preferably 80 mgKOH / g or more.
- 90 mgKOH / g or more is particularly preferable, 100 mgKOH / g or more is most preferable, 300 mgKOH / g or less is preferable, 200 mgKOH / g or less is more preferable, 150 mgKOH / g or less is more preferable, and 130 mgKOH / g or less is particularly preferable. .
- the combination of the upper limit and the lower limit is preferably 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, further preferably 50 to 150 mgKOH / g, and particularly preferably 80 to 130 mgKOH / g.
- the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, and still more preferably 5000. Above, especially preferably 6000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, further preferably 10,000 or less, particularly preferably 8000 or less. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, still more preferably 3000 to 15000, still more preferably 4000 to 10,000, and particularly preferably 5000 to 8000.
- the double bond equivalent of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but is preferably 400 or more, more preferably 450 or more, further preferably 500 or more, more preferably 800 or less, and more preferably 700 or less. 600 or less is more preferable. When the amount is not less than the lower limit, the development solubility tends to be good, and when the amount is not more than the upper limit, the sensitivity tends to be high.
- the double bond equivalent of the epoxy (meth) acrylate resin (b-2) can be calculated in the same manner as in the above formula (x).
- the combination of the upper limit and the lower limit is preferably 400 to 800, more preferably 450 to 700, and further preferably 500 to 600.
- the epoxy (meth) acrylate resin (b-2) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added and subjected to an addition reaction, and further a polybasic acid or its A method of continuing the reaction by adding an anhydride can be used.
- examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
- examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, and tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride.
- thermal polymerization inhibitor examples include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.
- the acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy resin.
- the amount can be.
- the temperature during the addition reaction is usually 60 to 150 ° C., preferably 80 to 120 ° C.
- the polybasic acid (anhydride) is used in an amount of usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, based on 1 chemical equivalent of the hydroxyl group generated in the addition reaction.
- the amount can be a chemical equivalent.
- the chemical structure of the epoxy (meth) acrylate resin (b-2) is not particularly limited, but from the viewpoint of curability, an epoxy (meth) acrylate resin (b-2) having a repeating unit structure represented by the following formula (i): One or both of -i) and an epoxy (meth) acrylate resin (b-2-ii) having a partial structure represented by the following formula (ii) are preferred. From the viewpoint of display reliability, an epoxy (meth) acrylate resin having a partial structure represented by the following formula (ii) is more preferable.
- One or both of the repeating unit structure represented by the following formula (i) and the partial structure represented by the following formula (ii) have high compatibility with the alkali-soluble resin (b-1), It is considered that development solubility is improved.
- R a represents a hydrogen atom or a methyl group
- R b represents a divalent hydrocarbon group which may have a substituent
- the benzene ring in formula (i) may be further substituted with an optional substituent
- each R c independently represents a hydrogen atom or a methyl group
- R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R e and R f each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represents an integer of 0 to 2
- an epoxy (meth) acrylate resin having a unit structure represented by the following formula (ii-a) is preferable.
- epoxy (meth) acrylate resin (b-2-i) an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (i) (hereinafter abbreviated as “epoxy (meth) acrylate resin (b-2-i)”) will be described in detail. .
- R a represents a hydrogen atom or a methyl group
- R b represents a divalent hydrocarbon group which may have a substituent
- the benzene ring in formula (i) may be further substituted with an optional substituent
- R b represents a divalent hydrocarbon group which may have a substituent.
- the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.
- Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, while a cyclic one is preferable from the viewpoint of development adhesion.
- the number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10.
- divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
- a methylene group is preferable from the viewpoint of curability.
- divalent branched aliphatic group examples include the above-mentioned divalent linear aliphatic group, a side chain of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is 1 or more, preferably 2 or more, and usually preferably 10 or less and 5 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
- divalent aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
- a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 4 to 20, more preferably 5 to 15, and further preferably 6 to 10.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
- the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
- benzene ring or naphthalene ring examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. That. Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring or naphthalene ring or thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring,
- Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of curability.
- divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
- a group in which one or more cyclic groups are linked is not particularly limited, but is 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the benzene ring in formula (i) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of curability.
- the repeating unit structure represented by the formula (i) is preferably a repeating unit structure represented by the following formula (i-1) from the viewpoint of curability.
- R a and R b have the same meaning as in formula (i);
- R X represents a hydrogen atom or a polybasic acid residue; * Represents a bond;
- the benzene ring in formula (i-1) may be further substituted with an arbitrary substituent.
- the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid derived from a polybasic acid or an anhydride thereof.
- Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
- One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
- tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.
- Epoxy (meth) acrylate resin (b-2-i) in one molecule the repeating unit structure of Formula (i-1) may be one kind or two or more species, for example, R X is The thing of a hydrogen atom and the thing of R ⁇ X > may be a polybasic acid residue may be mixed.
- the number of the repeating unit structure represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (b-2-i) is not particularly limited, but is preferably 1 or more, preferably 3 or more. More preferably, it is preferably 20 or less, and more preferably 15 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.
- the combination of the upper limit and the lower limit is preferably 1 to 20, and more preferably 3 to 15.
- the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin (b-2-i) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more.
- 3000 or more is more preferable, 4000 or more is more preferable, 5000 or more is particularly preferable, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, 8000 or less is more preferable, and 7000 or less is preferable.
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, still more preferably 3000 to 10000, still more preferably 4000 to 8000, and particularly preferably 5000 to 7000.
- the acid value of the epoxy (meth) acrylate resin (b-2-i) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 60 mgKOH / g or more, and 80 mgKOH / g or more. Is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and particularly preferably 130 mgKOH / g or less. There exists a tendency for development solubility to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis
- the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 80 to 130 mgKOH / g.
- epoxy (meth) acrylate resin (b-2-i) Specific examples of the epoxy (meth) acrylate resin (b-2-i) are given below.
- epoxy (meth) acrylate resin (b-2-ii) an epoxy (meth) acrylate resin having a partial structure represented by the formula (ii) (hereinafter abbreviated as “epoxy (meth) acrylate resin (b-2-ii)”) will be described in detail.
- each R c independently represents a hydrogen atom or a methyl group
- R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R e and R f each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represents an integer of 0 to 2
- an epoxy (meth) acrylate resin having a unit structure represented by the following formula (ii-a) is preferable.
- R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic ring group has is not particularly limited, but is 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and still more preferably 8 to 20.
- aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
- an adamantane ring is preferable from the viewpoint of display reliability.
- the number of rings of the aromatic ring group is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more preferably 4 or less. preferable.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 4.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 10 to 15.
- aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
- the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited.
- divalent aliphatic group examples include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of compatibility, and a cyclic one is preferable from the viewpoint of display reliability.
- the divalent aliphatic group has 1 or more carbon atoms, preferably 3 or more, more preferably 6 or more, more preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 25, more preferably 3 to 20, and further preferably 6 to 15.
- divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
- a methylene group is preferable from the viewpoint of curability.
- divalent branched aliphatic group examples include the above-mentioned divalent linear aliphatic group, a side chain of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- divalent aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
- a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of display reliability.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
- the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
- Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
- a benzene ring, naphthalene ring or fluorene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.
- Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- unsubstituted is preferable from the viewpoints of development solubility and moisture absorption resistance.
- divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
- a group in which one or more cyclic groups are linked is not particularly limited, but is 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (iA) to (iE), etc. Is mentioned. Among these, from the viewpoint of display reliability, the group represented by the formula (iC) is preferable.
- the bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited.
- the mode in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a side chain is mentioned.
- R e and R f each independently represent a divalent aliphatic group which may have a substituent.
- Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion.
- the number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10.
- divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
- a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
- divalent branched aliphatic group examples include the above-mentioned divalent linear aliphatic group, a side chain of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is 1 or more, preferably 2 or more, and usually 12 or less and 10 or less.
- the amount is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good.
- the value is not more than the upper limit value, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film, and resolution. Tend to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 12, and more preferably 2 to 10.
- divalent cyclic aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom.
- a group in which two are removed Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- M, n each independently represents an integer of 0 to 2.
- M and n are preferably 0 from the viewpoint of developability, and m and n are preferably 1 or 2 from the viewpoint of patterning suitability and surface roughness.
- the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of compatibility.
- R c has the same meaning as in formula (ii); R alpha represents optionally may be monovalent cyclic hydrocarbon group having a substituent; n is an integer greater than or equal to 1; The benzene ring in formula (ii-1) may be further substituted with an arbitrary substituent.
- R ⁇ represents a monovalent cyclic hydrocarbon group.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic ring group has is not particularly limited, but is 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 2 to 4, and further preferably 2 to 3.
- the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and still more preferably 8 to 20.
- aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
- an adamantane ring is preferable from the viewpoint of compatibility.
- the number of rings that the aromatic ring group has is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 3 or more, and usually preferably 10 or less and 5 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.
- Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of display reliability.
- Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- n represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis
- n is preferably 2 or 3, more preferably 2 as an embodiment, and more preferably 3 as another embodiment. When n is 2 or more, two or more R ⁇ may be the same or different.
- R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
- the benzene ring in formula (ii-1) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
- the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of display reliability.
- R c has the same meaning as in formula (ii);
- R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent;
- the benzene ring in formula (ii-2) may be further substituted with an arbitrary substituent.
- R ⁇ represents a divalent cyclic hydrocarbon group.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic ring group has is not particularly limited, but is 1 or more, preferably 2 or more, and usually preferably 10 or less and 5 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
- carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and still more preferably 8 to 30.
- aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
- an adamantane ring is preferable from the viewpoint of compatibility.
- the number of rings that the aromatic ring group has is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 3 or more, and usually preferably 10 or less and 5 or less.
- image development adhesiveness to become favorable by setting it as the said lower limit or more
- sclerosis hardenability to become favorable by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 10
- the above is more preferable, 40 or less is preferable, 30 or less is more preferable, 20 or less is further preferable, and 15 or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 10 to 15.
- aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
- a fluorene ring is preferable from the viewpoint of display reliability.
- Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.
- R beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
- R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
- the benzene ring in formula (ii-2) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more.
- two benzene rings in the formula (ii-2) may be linked via these substituents. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
- the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of compatibility.
- R c and R d have the same meaning as in formula (ii); R Z represents a hydrogen atom or a polybasic acid residue.
- the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid derived from a polybasic acid or an anhydride thereof. Further, another OH group may be removed and shared with R Z in other molecules represented by the formula (ii-3), that is, a plurality of formulas (ii-3) are connected via R Z. ) May be linked.
- Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
- One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
- tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.
- the partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (b-2-ii) may be one type or two or more types.
- R Z is hydrogen.
- the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (b-2-ii) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 3 to 10.
- the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin (b-2-ii) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. Preferably, 2000 or more is more preferable, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is more preferable, 8000 or less is more preferable, 5000 or less is especially preferable. When it is at least the lower limit value, the development adhesion tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1000 to 20000, still more preferably 1500 to 15000, still more preferably 1500 to 10000, particularly preferably 2000 to 8000, and most preferably 2000 to 5000. It is done.
- the acid value of the epoxy (meth) acrylate resin (b-2-ii) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 60 mgKOH / g or more, and 80 mgKOH / g or more. Is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and particularly preferably 130 mgKOH / g or less. When it is at least the lower limit, the development solubility tends to be good, and when it is at most the upper limit, the development adhesion tends to be good.
- the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 80 to 130 mgKOH / g.
- the (b) alkali-soluble resin used in the present invention may contain other alkali-soluble resins in addition to the alkali-soluble resin (b-1) and the epoxy (meth) acrylate resin (b-2). .
- alkali-soluble resins examples include acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolac resins, and polyvinylphenol resins.
- acrylic resins are preferably used from the viewpoint of compatibility with pigments, dispersants, and the like, and those described in Japanese Patent Application Laid-Open No. 2014-137466 can be preferably used.
- acrylic resin examples include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b1)”) and other copolymerizable ethylenically unsaturated monomers. Examples thereof include a copolymer with a monomer (hereinafter referred to as “unsaturated monomer (b2)”).
- Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl]; ⁇ -carboxypolycaprolactone mono (meth) acrylate, etc.
- unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinna
- Examples of the unsaturated monomer (b2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ - Aromatic vinyl compounds such as methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;
- Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane
- a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane and the like.
- These unsaturated monomers (b2) can be used alone or in admixture of two or more.
- the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass.
- copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japan Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Japanese Unexamined Patent Publication No. 11-174224, Japanese Unexamined Patent Publication No. 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japan Examples thereof include copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728.
- the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method.
- Japanese Unexamined Patent Publication No. 2003-222717 Japanese Unexamined Patent Publication No.
- the structure, Mw, and Mw / Mn can be controlled by the methods disclosed in Japanese Patent Application Publication No. 2006-259680 and International Publication No. 2007/029871.
- the photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
- photopolymerization initiator examples include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; Japanese Patent Application Laid-Open No.
- titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny) 1-yl), dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadieny
- hexaarylbiimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl). ) Imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′- And methoxyphenyl) -4,5-diphenylimidazole dimer.
- halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
- halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.
- ⁇ -aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is
- oxime ester compounds are particularly effective in terms of sensitivity and plate making properties, and when using an alkali-soluble resin containing a phenolic hydroxyl group, it is disadvantageous in terms of sensitivity. Therefore, an oxime ester compound excellent in such sensitivity is particularly useful.
- the oxime ester compound include those described in International Publication No. 2008/077554, those described in International Publication No. 2009/131189, those described in Japanese Patent Application Laid-Open No. 2011-132215, and International Publication No. And those described in Japanese Patent Application Publication No. 2008/078678, and Japanese Patent Publication No. 2014-500852.
- oxime ester compounds it is preferable to include an oxime ester compound represented by the following formula (CI) from the viewpoint of high sensitivity.
- R c1 represents an aromatic ring group which may have a substituent
- R c2 represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent
- R c3 represents a hydrogen atom or an alkyl group which may have a substituent
- R c4 represents an aromatic ring group which may have a substituent
- R c5 and R c6 each independently represents an optionally substituted benzene ring or an optionally substituted naphthalene ring, provided that at least one of R c5 and R c6 Is a naphthalene ring which may have a substituent
- At least one of R c1 and R c4 has a —OR c7 group, wherein R c7 represents a halogenoalkyl group;
- X represents a direct bond or a carbonyl group;
- Z represents a direct bond or a carbonyl group.
- Examples of the aromatic ring group for R c1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more.
- the combination of the upper limit and the lower limit is preferably 4 to 30, and more preferably 6 to 12.
- the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
- the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
- Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group, and a —OR c7 group described later.
- An atom, a halogenoalkyl group or an —OR c7 group is preferred, and a —OR c7 group is more preferred, while from the viewpoint of ease of synthesis, unsubstituted is preferred.
- an aromatic hydrocarbon ring group which may have a substituent is preferable, and an aromatic hydrocarbon ring group substituted with an —OR c7 group is more preferable.
- a benzene ring group substituted with an —OR c7 group is more preferable.
- the number of carbon atoms of the alkanoyl group in R c2 is not particularly limited, but is preferably 2 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, further preferably 7 or less, still more preferably 5 or less, and particularly preferably 3 or less. .
- the combination of the upper limit and the lower limit is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 7, still more preferably 2 to 5, and particularly preferably 2 to 3.
- the alkanoyl group examples include an acetyl group, a propanoyl group, and a butanoyl group. Among these, from the viewpoint of sensitivity, an acetyl group or a propanoyl group is preferable, and an acetyl group is more preferable.
- the substituent that the alkanoyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like, and it is preferably unsubstituted from the viewpoint of sensitivity.
- the carbon number of the aryloyl group in R c2 is not particularly limited, but is preferably 7 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
- the combination of the upper limit and the lower limit is preferably 7 to 20, more preferably 7 to 12, and further preferably 7 to 10.
- the aryloyl group examples include a benzoyl group, a methylbenzoyl group, and a naphthoyl group.
- a benzoyl group is more preferable from the viewpoint of sensitivity.
- the substituent that the aryloyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like, and it is preferably unsubstituted from the viewpoint of sensitivity.
- R c2 is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
- the carbon number of the alkyl group in R c3 is not particularly limited, but is preferably 1 or more from the viewpoint of solubility, more preferably 2 or more, further preferably 5 or more, and 7 or more. Is particularly preferred. Moreover, it is preferable that it is 20 or less from a compatible viewpoint, It is more preferable that it is 15 or less, It is further more preferable that it is 10 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 2 to 15, and further preferably 5 to 10.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group.
- a methyl group an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group.
- An octyl group or a 2-ethylhexyl group is preferable, and a 2-ethylhexyl group is more preferable.
- R c3 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and a 2-ethylhexyl group. Further preferred.
- Examples of the aromatic ring group for R c4 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more.
- the combination of the upper limit and the lower limit is preferably 4 to 30, and more preferably 6 to 12.
- the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
- the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
- Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, and a halogen atom. From the viewpoint of solubility, an alkyl group or an alkoxy group is preferable, and an alkyl group is more preferable. A methyl group is more preferable.
- the number of substituents is not particularly limited, but from the viewpoint of solubility, it is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. Moreover, from a compatible viewpoint, 10 or less are preferable, 5 or less are more preferable, and 4 or less are more preferable.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 4.
- R c4 is preferably an aromatic hydrocarbon ring group which may have a substituent, and an aromatic hydrocarbon ring group having two or more methyl groups. Is more preferable, and a mesityl group is more preferable.
- R c5 and R c6 each independently represent an optionally substituted benzene ring or naphthalene ring. However, at least one of R c5 and R c6 is a naphthalene ring which may have a substituent. As a specific combination, R c5 is a benzene ring which may have a substituent, R c6 is a naphthalene ring which may have a substituent, and R c5 has a substituent. A combination in which R c6 is an optionally substituted benzene ring, R c5 is an optionally substituted naphthalene ring, and R c6 represents a substituent.
- the combination which is the naphthalene ring which may have is mentioned.
- R c5 is a naphthalene ring which may have a substituent
- R c6 is a benzene ring which may have a substituent
- R c5 is a benzene ring which may have a substituent group
- the N atom bonded to the 1-position of the benzene ring, R c6 is bonded to the 2-position
- the N atom bonded to the 1-position of the benzene ring, R c5 is bonded to the 2-position, the manner Z is attached to the 4-position Can be mentioned.
- R c5 is an optionally substituted naphthalene ring
- the X, N atom and R c6 bonded to R c5 in the formula (CI) are located at the position of the naphthalene ring represented by R c5. It may be bonded.
- R c6 is bonded to the 2-position
- X is bonded to the 4-position
- R c6 is bonded to the 1-position of the naphthalene ring
- R c6 is an optionally substituted naphthalene ring
- Z, N atom and R 5 bonded to R c6 in the formula (CI) are bonded to any position of the naphthalene ring. It may be.
- Examples of the substituent that the benzene ring or naphthalene ring in R c5 and R c6 may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like. From the viewpoint of sensitivity, it is more preferably unsubstituted.
- At least one of R c1 and R c4 has a —OR c7 group.
- R c1 may have an —OR c7 group
- R c4 may have a —OR 7 group
- R c1 and R c4 may each independently have a —OR c7 group.
- R c7 represents a halogenoalkyl group
- the number of carbon atoms of the halogenoalkyl group in R c7 is not particularly limited, but is preferably 1 or more from the viewpoint of solubility, more preferably 2 or more, and 3 or more. More preferably. Moreover, it is preferable that it is 10 or less from a compatible viewpoint, It is more preferable that it is 7 or less, It is further more preferable that it is 5 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 7, and further preferably 3 to 5.
- the carbon chain in the halogenoalkyl group may be linear, branched or cyclic, but is preferably linear from the viewpoint of ease of production.
- the number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more from the viewpoint of solubility. Moreover, it is preferable that it is 7 or less from a compatible viewpoint, It is more preferable that it is 6 or less, It is further more preferable that it is 5 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 7, more preferably 2 to 6, and further preferably 3 to 5.
- halogenoalkyl group examples include 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,4,4,5,5-octa
- examples thereof include a fluoropentyl group, and among these, 2,2,3,3-tetrafluoropropyl group is more preferable from the viewpoint of ease of production.
- substituent that the halogenoalkyl group may have include a hydroxyl group and an alkoxy group. From the viewpoint of ease of production, the substituent is preferably unsubstituted.
- X represents a direct bond or a carbonyl group, but as one embodiment, a direct bond is preferable from the viewpoint of adhesion, and as another embodiment, a carbonyl group is preferable from the viewpoint of sensitivity.
- Z represents a direct bond or a carbonyl group, but as one embodiment, it is preferably a direct bond from the viewpoint of adhesion, and as another embodiment, it is preferably a carbonyl group from the viewpoint of sensitivity.
- oxime ester compounds it is preferable to include an oxime ester compound having a diphenyl sulfide skeleton from the viewpoint of solvent resistance.
- the oxime ester compound having a diphenyl sulfide skeleton by including the oxime ester compound having a diphenyl sulfide skeleton, light absorption at a short wavelength is strong and surface curability is improved, so that it is difficult to dissolve in a solvent and solvent resistance is considered to increase. Further, by preventing the penetration of the solvent, it is possible to suppress the dissolution of the colorant from the inside of the coating film.
- the oxime ester-based compound having a diphenyl sulfide skeleton has a short conjugated system, increases the energy of the whole molecule, increases the radical generation efficiency by thermal decomposition, promotes the polymerization reaction, and further unreacted initiator. Therefore, it is considered that elution of the initiator itself into the solvent can be suppressed.
- the chemical structure of the oxime ester-based compound having a diphenyl sulfide skeleton is not particularly limited, but from the viewpoint of solvent resistance, a compound represented by the following general formula (C-II) is preferably used.
- R 23 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent
- R 24 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent
- R 25 represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (C-II-1); h represents an integer of 0 to 5;
- the benzene ring represented by the formula (C-II) may further have a substituent.
- R 25a represents —O—, —S—, —OCO— or —COO—
- R 25b represents an alkylene group which may have a substituent
- the alkylene part of R 25b may be interrupted 1 to 5 times by —O—, —S—, —COO— or —OCO—
- the alkylene portion of R 25 may have a branched side chain or cyclohexylene
- R 25c represents a hydroxyl group or a carboxyl group.
- the carbon number of the alkyl group in R 23 is not particularly limited, but is preferably 1 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, further preferably 8 or less, still more preferably 5 or less, and particularly preferably 3 or less. preferable.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 5, and particularly preferably 1 to 3.
- the alkyl group examples include a methyl group, a hexyl group, and a cyclopentylmethyl group. Among these, a methyl group or a hexyl group is preferable, and a methyl group is more preferable from the viewpoint of developability.
- the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of alkali developability.
- a carboxyl group is more preferred. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
- Examples of the aromatic ring group for R 23 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.
- the combination of the upper limit and the lower limit is preferably 5 to 30, more preferably 5 to 20, and further preferably 5 to 12.
- aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group.
- a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
- substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable. Groups are more preferred.
- R 23 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group. .
- the number of carbon atoms of the alkyl group in R 24 is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3.
- the alkyl group examples include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable from the viewpoint of sensitivity.
- the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, and an amide group. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. On the other hand, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
- Examples of the aromatic ring group for R 24 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more.
- the combination of the upper limit and the lower limit is preferably 4 to 30, and more preferably 6 to 12.
- the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
- the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
- R 24 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.
- R 24 is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent. Further, an unsubstituted aromatic hydrocarbon group is more preferable, and a phenyl group is particularly preferable.
- R 25 is a hydroxyl group, a carboxyl group, or a group represented by the general formula (C-II-1).
- the general formula (C-II-1) It is preferable that it is group represented by these.
- R 25a represents —O—, —S—, —OCO—, or —COO—.
- —O— or —OCO— is preferable, and —O— is more preferable.
- R 25b represents an alkylene group which may have a substituent.
- the number of carbon atoms of the alkylene group in R 25b is not particularly limited, but is preferably 1 or more from the viewpoint of solubility in the photosensitive coloring composition, more preferably 2 or more, and 20 or less. Is preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 1 to 10, still more preferably 2 to 5, and particularly preferably 2 or 3.
- the alkylene group may be a straight chain, may be branched, or may contain an aliphatic ring. Among these, a straight chain is preferable from the viewpoint of solubility in the photosensitive coloring composition.
- alkylene group examples include a methylene group, an ethylene group, and a propylene group.
- an ethylene group is more preferable from the viewpoint of solubility in the photosensitive coloring composition.
- R 25c is a hydroxyl group or a carboxyl group. From the viewpoint of solvent resistance (liquid crystal stain resistance), R 25c is preferably a hydroxyl group.
- h represents an integer of 0 to 5.
- h is preferably 1 or more, preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and preferably 1.
- the combination of the upper limit and the lower limit is preferably 0 to 4, more preferably 1 to 3, and further preferably 1 to 2.
- h is preferably 0.
- a photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
- a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity.
- sensitizing dyes xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335
- amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone.
- Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethi) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazol
- polymerization accelerator examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. It is done.
- a polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.
- the photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound.
- the ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, ester of polyhydric or monohydric alcohol, and the like can be mentioned. It is done.
- a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly desirable.
- the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 8, more preferably 2 to 8, and further preferably 5 to 7.
- polyfunctional ethylenic monomer examples include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound.
- esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
- ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.
- itaconic acid ester replaced by itaconate
- ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
- the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
- a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted.
- urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical).
- (meth) acrylic acid alkyl ester as (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.
- the photosensitive coloring composition of the present invention contains (e) a solvent.
- a pigment can be disperse
- the photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary.
- Various other materials used according to the above are used in a state dissolved or dispersed in a solvent.
- organic solvents are preferable from the viewpoints of dispersibility and coatability.
- organic solvents those having a boiling point in the range of 100 to 300 ° C. are preferably selected from the viewpoint of applicability, and those having a boiling point in the range of 120 to 280 ° C. are more preferable.
- the boiling point here means the boiling point at a pressure of 1013.25 hPa.
- organic solvents include the following. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl Ether, tri Chi glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol mono
- acetone Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones; Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentan
- Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxy
- organic solvents corresponding to the above include mineral spirits, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cerosolve” is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name). These organic solvents may be used alone or in combination of two or more.
- an organic solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 1013.25 hPa. The same applies to the boiling points hereinafter). More preferably, it has a boiling point of 120 to 170 ° C.
- glycol alkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is more preferable from the viewpoints of good balance in coating properties, surface tension, and the like, and relatively high solubility of the components in the composition.
- Glycol alkyl ether acetates may be used alone.
- Glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
- glycol monoalkyl ethers are particularly preferable.
- propylene glycol monomethyl ether is preferable, and 3-methoxybutanol is more preferable because of the solubility of the components in the composition.
- glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease.
- the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
- an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”).
- high boiling point solvent an organic solvent having a boiling point of 150 ° C. or higher
- the photosensitive coloring composition is difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle.
- diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effects.
- the content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass.
- the drying temperature of the composition Is suppressed, and problems such as defective tact time in the reduced-pressure drying process and prebaked pin marks (dry unevenness caused by substrate support pins of the prebaking apparatus) tend to be suppressed.
- the high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
- Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
- ⁇ (F) Dispersant> In the photosensitive coloring composition of the present invention, (a) it is important to finely disperse the colorant and stabilize its dispersion state to ensure the stability of the quality. .
- a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxyl group; a phosphate group; a sulfonate group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable.
- a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, disperses the pigment.
- a basic functional group such as a primary, secondary or tertiary amino group
- a quaternary ammonium base such as pyridine, pyrimidine or pyrazine
- polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
- examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.
- a dispersant examples include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
- the dispersant preferably contains one or both of a urethane polymer dispersant having a functional group and an acrylic polymer dispersant. It is particularly preferable to include an agent. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having one or both of a polyester bond and a polyether bond is preferred.
- urethane and acrylic polymer dispersants examples include DISPERBYK-160 to 167, 182 series (both urethane), DISPERBYK-2000, 2001, BYK-LPN21116, etc. (both acrylic) (all manufactured by BYK Chemie) ).
- Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include, for example, the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000.
- examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an active hydrogen and a tertiary amino group in the molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
- polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
- Aromatic diisocyanates such as hexamethylene diisocyanates, lysine methyl ester diisocyanates, 2,4,4-trimethylhexamethylene diisocyanates, dimer acid diisocyanates and other aliphatic diisocyanates, isophorone diisocyanates, 4,4'-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ Aliphatic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates
- polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
- the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
- an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like.
- Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
- Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
- polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
- Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.
- alkylene oxides such as poly (poly And oxytetramethylene) adipate.
- the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
- Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,
- Polycarbonate glycol includes poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
- Polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. Is mentioned. These may be used alone or in combination of two or more.
- the number average molecular weight of a compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
- Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
- the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
- Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl
- examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned.
- nitrogen-containing heterocycles preferred are an imidazole ring or a triazole ring.
- these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
- specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.
- N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole preferable. These may be used alone or in combination of two or more.
- the preferred blending ratio of the raw materials for producing the urethane polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. ⁇ 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 ⁇ 24 parts by mass.
- the production of the urethane-based polymer dispersant is performed according to a known method for producing a polyurethane resin.
- a solvent for production usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of
- a urethanization reaction catalyst is usually used.
- the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned. These may be used alone or in combination of two or more.
- the introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g.
- the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amount is not less than the lower limit value, the dispersing ability tends to be improved, and when the amount is not more than the upper limit value, the developability tends to be improved.
- the weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Dispersibility and dispersion stability tend to be improved by setting the lower limit value or more, and dispersibility is improved and dispersibility tends to be improved by setting the upper limit value or less.
- an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.
- Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid.
- Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.
- Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives
- the acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group.
- the block may contain a partial structure derived from the unsaturated group-containing monomer not containing the functional group. May be contained in the A block in any form of random copolymerization or block copolymerization.
- content in the A block of the partial structure which does not contain a functional group is 80 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less.
- the B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but a partial structure derived from two or more types of monomers is contained in one B block. These may be contained in the B block in any form of random copolymerization or block copolymerization.
- the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
- the living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.
- Ar 1 is a monovalent organic group
- Ar 2 is a monovalent organic group different from Ar 1
- M is a metal atom
- s and t are each an integer of 1 or more.
- the polymerization active species is a radical, and is represented by the following scheme, for example.
- Ar 1 is a monovalent organic group
- Ar 2 is a monovalent organic group different from Ar 1
- j and k are each an integer of 1 or more
- R a is a hydrogen atom or 1
- R b is a hydrogen atom different from R a or a monovalent organic group.
- the acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer.
- the / B block ratio is preferably 1/99 to 80/20, and particularly preferably 5/95 to 60/40 (mass ratio), and within this range, a balance between dispersibility and storage stability can be ensured.
- the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. There exists a tendency which can ensure favorable dispersibility by making it in the range.
- Such a block copolymer usually contains an amino group generated in the production process, but its amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, Preferably it is 10 mgKOH / g or more, More preferably, it is 30 mgKOH / g or more, More preferably, it is 50 mgKOH / g or more, Preferably it is 90 mgKOH / g or less, More preferably, it is 80 mgKOH / g or less, More preferably, it is 75 mgKOH / g or less.
- the amine value of the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
- Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [W: Dispersant sample weighed amount [g], V: Titration amount at the end of titration [mL], S: Dispersant This represents the solid content concentration [% by mass] of the sample. ]
- the acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. There exists a tendency which can ensure favorable dispersibility by setting it as the said range.
- the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating” It is preferable to have a unit (i) ”.
- R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an optional aralkyl group; Two or more of R 31 to R 33 may be bonded to each other to form a cyclic structure; R 34 is a hydrogen atom or a methyl group; X is a divalent linking group; Y ⁇ is a counter anion.
- the number of carbon atoms of the alkyl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is preferably 1 or more and preferably 10 or less. The following is more preferable.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
- It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms of the aryl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 6 or more and preferably 16 or less. The following is more preferable.
- Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
- a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
- the carbon number of the aralkyl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less. The following is more preferable.
- Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
- a phenylmethyl group and a phenylethyl group Group a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
- R 31 to R 33 are preferably each independently an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently a methyl group, Or an ethyl group, and R 32 is preferably a phenylmethyl group or a phenylethyl group, more preferably R 31 and R 33 are a methyl group, and R 32 is a phenylmethyl group. .
- the polymer dispersant when it has a tertiary amine as a functional group, from the viewpoint of dispersibility, it may be a repeating unit represented by the following formula (ii) (hereinafter, referred to as “repeating unit (ii)”). .).
- R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
- An aralkyl group which may be R 35 and R 36 may combine with each other to form a cyclic structure;
- R 37 is a hydrogen atom or a methyl group;
- Z is a divalent linking group.
- alkyl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
- aryl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
- aralkyl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.
- R 35 and R 36 are preferably each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
- alkyl group, aralkyl group or aryl group in R 31 to R 33 of the above formula (i) and R 35 and R 36 of the above formula (ii) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, etc. are mentioned.
- examples of the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, A —COOR 44 — group (wherein R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms). Is a —COO—R 44 — group.
- the counter anion of Y - The, Cl -, Br -, I -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - , and the like.
- the content rate of the repeating unit represented by the said formula (i) is not specifically limited, From a dispersible viewpoint, it is represented by the content rate of the repeating unit represented by the said formula (i), and the said formula (ii). Preferably, it is 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, based on the total content of repeating units. Further, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.
- the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more from the viewpoint of dispersibility, and 5 mol. % Or more, more preferably 10 mol% or more, more preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. Is more preferable, and it is especially preferable that it is 15 mol% or less.
- the content ratio of the repeating unit represented by the formula (ii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more from the viewpoint of dispersibility. % Or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, more preferably 60 mol% or less, and 40 mol% or less. Is more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
- the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (iii)” from the viewpoint of improving compatibility with binder components such as a solvent and improving dispersion stability. It is preferable that it has.
- R 40 is an ethylene group or a propylene group
- R 41 is an alkyl group which may have a substituent
- R 42 is a hydrogen atom or a methyl group
- n is an integer of 1 to 20.
- the number of carbon atoms of the alkyl group which may have a substituent in R 41 of the above formula (iii) is not particularly limited, but is 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
- It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- n in the above formula (iii) is 1 or more, preferably 2 or more, and preferably 10 or less, preferably 5 or less, from the viewpoint of compatibility and dispersibility with respect to the binder component such as a solvent. It is more preferable that
- the content ratio of the repeating unit represented by the formula (iii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. More preferably, it is 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
- the amount is within the above range, compatibility with a binder component such as a solvent tends to be compatible with dispersion stability.
- the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv)” from the viewpoint of improving the compatibility of the dispersing agent with a binder component such as a solvent and improving dispersion stability. ) ").).
- R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent;
- R 39 is a hydrogen atom or a methyl group.
- the number of carbon atoms of the alkyl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, and more preferably 8 or less.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
- It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms of the aryl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 8 or less.
- Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
- a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
- the carbon number of the aralkyl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferred is 10 or less.
- Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
- a phenylmethyl group and a phenylethyl group Group a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
- R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group.
- substituents that the alkyl group may have in R 38 include a halogen atom and an alkoxy group.
- the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
- the linear alkyl group represented by R 38 includes both linear and branched chains.
- the content of the repeating unit represented by the formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol% or more and 40 mol% or more from the viewpoint of dispersibility. More preferably, it is more preferably 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less.
- the polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv).
- repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.
- the polymer dispersant is composed of an A block having the repeating unit (i) and the repeating unit (ii), and a B block not having the repeating unit (i) and the repeating unit (ii). It is preferable that it is a block copolymer which has these.
- the block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be remarkably improved.
- the B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).
- the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization and block copolymerization.
- the repeating unit (i) and the repeating unit (ii) may be contained in two or more kinds in one A block. In that case, each repeating unit is randomly copolymerized in the A block. It may be contained in any form of block copolymerization.
- a repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block.
- Examples of such a repeating unit include the aforementioned (meth) acrylic acid ester-based unit.
- Examples include a repeating unit derived from a monomer.
- the content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
- Repeating units other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid Ether; repeating units derived from monomers such as N-methacryloylmorpholine.
- styrene monomers such as styrene and ⁇ -methylstyrene
- (Meth) acrylate monomers such as (meth) acrylic acid chloride
- (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide
- vinyl acetate acrylon
- the content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
- the dispersant is preferably used in combination with a pigment derivative described later.
- the photosensitive coloring composition of the present invention includes an adhesion improver such as a silane coupling agent, a surfactant (applicability improver), a pigment derivative, a photoacid generator, a crosslinking agent, and a mercapto compound.
- an adhesion improver such as a silane coupling agent, a surfactant (applicability improver), a pigment derivative, a photoacid generator, a crosslinking agent, and a mercapto compound.
- Development improvers, ultraviolet absorbers, antioxidants, and the like can be appropriately blended.
- the photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate.
- an adhesion improver a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
- types of silane coupling agents various types such as epoxy-based, (meth) acrylic-based, and amino-based ones can be used alone or in admixture of two or more.
- Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- Epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Isocyanate silanes such as 3-isocyanatopropyltriethoxysilane are mentioned, and epoxy silane silane coupling agents are particularly preferable.
- the phosphoric acid group-containing compound (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.
- R 51 represents a hydrogen atom or a methyl group
- l and l ′ represent an integer of 1 to 10
- m represents 1, 2 or 3.
- the photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability.
- surfactant for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used.
- nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.
- fluorine-based and silicon-based surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone).
- 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
- Pigment derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
- a pigment derivative as a dispersion aid
- As pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine
- derivatives such as phthalocyanines and quinophthalones are preferable.
- Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
- pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.
- a photoacid generator is a compound capable of generating an acid by ultraviolet rays, and has a crosslinking agent such as a melamine compound due to the action of an acid generated upon exposure. The crosslinking reaction will proceed.
- a photoacid generator those having a high solubility in a solvent, particularly in a solvent used in a photosensitive coloring composition, are preferable, for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl).
- Iodonium bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphen
- Crosslinking agent can be further added to the photosensitive coloring composition of the present invention.
- a melamine or guanamine compound can be used.
- these cross-linking agents include melamine or guanamine compounds represented by the following general formula (6).
- R 61 represents a —NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms;
- R 61 is a —NR 66 R 67 group, one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 represents a —CH 2 OR 68 group;
- R 61 is an aryl group having 6 to 12 carbon atoms, one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group;
- the remainder of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 each independently represents hydrogen or a —CH 2 OR 68 group;
- R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the aryl group having 6 to 12 carbon atoms in R 61 is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and these phenyl group and naphthyl group include an alkyl group, an alkoxy group, a halogen atom. Or a substituent such as Each of the alkyl group and the alkoxy group may have about 1 to 6 carbon atoms.
- Alkyl group represented by R 68 is, among the above, methyl group or an ethyl group, especially a methyl group.
- Melamine compounds corresponding to the general formula (6) that is, compounds of the following general formula (6-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.
- R 62 , R 63 , R 64 , R 65 , R 66 and R 67 when one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is an aryl group: one of R 62 , R 63 , R 64 and R 65 is —CH 2 Represents the OR 68 group; The rest of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 each independently represents a hydrogen atom or a —CH 2 OR 68 group; R 68 represents a hydrogen atom or an alkyl group.
- guanamine compounds corresponding to the general formula (6) that is, compounds in which R 61 in the general formula (6) is aryl having 6 to 12 carbon atoms include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl. Benzoguanamine, tetraethoxymethyl benzoguanamine and the like are included.
- a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used.
- examples thereof include 2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl).
- Perhydro-1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1 , 3,5-oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.
- crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.
- the amount of the crosslinking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.
- Mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis 3-mercaptobutyrate), butanediol bis (3-mercapto
- the content of the colorant (a) in the total solid content of the photosensitive coloring composition is 20% by mass or more, preferably 30% by mass or more, and preferably 35% by mass. More preferably, it is more preferably 40% by mass or more, usually 60% by mass or less, more preferably 50% by mass or less.
- (A) By making the content rate of a coloring agent more than the said lower limit, there exists a tendency for sufficient optical density (OD) to be obtained, and sufficient platemaking characteristics and solvent resistance are made by making it below the said upper limit. , Tend to be able to ensure mechanical properties.
- the combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, further preferably 35 to 50% by mass, and particularly preferably 40 to 50% by mass.
- the content of the organic color pigment in the (a) colorant is preferably 20% by mass or more, and more preferably 40% by mass or more. 60 mass% or more, more preferably 80 mass% or more, most preferably 99 mass% or less, more preferably 90 mass% or less, and 85 mass% or less. More preferably.
- the amount is not less than the lower limit, a sufficient optical density (OD) tends to be obtained, and when the amount is not more than the upper limit, solvent resistance and mechanical properties tend to be ensured.
- the combination of the upper limit and the lower limit is preferably 20 to 99% by mass, more preferably 40 to 90% by mass, further preferably 60 to 85% by mass, and particularly preferably 80 to 85% by mass.
- the total content of at least one pigment selected from the group consisting of a red pigment and an orange pigment in (a) the colorant is preferably 1% by mass or more, and preferably 2% by mass or more. More preferably, it is 3% by mass or more, more preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and more preferably 10% by mass. % Or less is more preferable, and 8% by mass or less is particularly preferable.
- OD optical density
- the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, still more preferably 3 to 10% by mass, and 3 to 8% by mass. Particularly preferred is mentioned.
- the total content of at least one pigment selected from the group consisting of a blue pigment and a purple pigment in (a) the colorant is preferably 20% by mass or more, and more preferably 30% by mass or more. More preferably, it is more preferably 40% by mass or more, still more preferably 50% by mass or more, particularly preferably 60% by mass or more, most preferably 70% by mass or more, It is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less.
- the combination of the upper limit and the lower limit is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, further preferably 40 to 85% by mass, still more preferably 50 to 85% by mass, and 60 to 85% by mass. Particularly preferred is 70 to 80% by mass.
- the content of the black pigment in (a) the colorant is preferably 1% by mass or more, more preferably 5% by mass or more. More preferably, it is more preferably at least 15% by mass, particularly preferably at least 15% by mass, more preferably at most 50% by mass, even more preferably at most 40% by mass, and at most 30% by mass. More preferably, it is most preferable that it is 20 mass% or less.
- the amount is not less than the above lower limit value, a sufficient optical density (OD) tends to be obtained, and when the amount is not more than the above upper limit value, plate making characteristics and mechanical properties tend to be ensured.
- the combination of the upper limit and the lower limit is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 30% by mass and 15 to 20% by mass.
- the content of the organic black pigment in (a) the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 More preferably, it is 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and further preferably 20% by mass or less. It is particularly preferred. There exists a tendency for sufficient optical density (OD) to be obtained by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 10 to 30% by mass.
- the content ratio of carbon black in the (a) colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass. More preferably, it is more preferably 15% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass or less. More preferably, it is particularly preferably 20% by mass or less.
- a sufficient optical density (OD) can be obtained by setting it to the lower limit value or more, and there is a tendency that plate making characteristics and mechanical characteristics can be secured by setting the upper limit value or less.
- the combination of the upper limit and the lower limit is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass.
- the content of the (b) alkali-soluble resin in the total solid content of the photosensitive coloring composition is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25%. It is usually not more than 80% by mass, preferably not more than 70% by mass, more preferably not more than 50% by mass, still more preferably not more than 40% by mass.
- the combination of the upper limit and the lower limit is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, further preferably 25 to 50% by mass, and particularly preferably 25 to 40% by mass.
- the content of the alkali-soluble resin (b-1) in the total solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, usually 30%. It is not more than mass%, preferably not more than 20 mass%, more preferably not more than 15 mass%, and further preferably not more than 10 mass%.
- the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass.
- the content of the epoxy (meth) acrylate resin (b-2) in the total solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass. % Or less, more preferably 20% by mass or less.
- the combination of the upper limit and the lower limit is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, further preferably 8 to 30% by mass, and particularly preferably 10 to 20% by mass.
- the content ratio of the photopolymerization initiator (c) in the total solid content of the photosensitive coloring composition is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 2% by mass or more, and Preferably it is 4 mass% or more, Most preferably, it is 6 mass% or more, Usually 15 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less.
- C There exists a tendency which can suppress a sensitivity fall by making the content rate of a photoinitiator more than the said lower limit, and it suppresses the fall of the solubility with respect to the developing solution of an unexposed part by making it the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, further preferably 2 to 10% by mass, and particularly preferably 4 to 8% by mass.
- the content of the oxime ester compound in the total solid content of the photosensitive coloring composition is usually 0. 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably. Is 6% by mass or less, more preferably 5% by mass or less.
- the content of the oxime ester compound represented by the formula (C-1) is not less than the lower limit, there is a tendency to suppress a decrease in sensitivity, and when it is not more than the upper limit, development of an unexposed portion is likely to occur.
- the combination of the upper limit and the lower limit is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, further preferably 2 to 6% by mass, and particularly preferably 3 to 5% by mass.
- the content of the oxime ester compound in the total solid content of the photosensitive coloring composition is usually 0.5% by mass or more, preferably Is 1% by mass or more, more preferably 2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less.
- Sufficient solvent resistance tends to be obtained when the content of the oxime ester-based compound having a diphenyl sulfide skeleton is equal to or higher than the lower limit, and when the content is equal to or lower than the upper limit, the unexposed portion is dissolved in the developer.
- the combination of the upper limit and the lower limit is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, and further preferably 2 to 5% by mass.
- the content ratio of the polymerization accelerator in the total solid content of the photosensitive coloring composition is preferably 0.05% by mass or more, usually 10% by mass or less, The amount is preferably 5% by mass or less, and the polymerization accelerator is usually used in a proportion of 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (c). preferable.
- the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. Preferably it is 10 mass% or less.
- the content of the (d) ethylenically unsaturated compound in the total solid content of the photosensitive coloring composition is usually 30% by mass or less, preferably 20% by mass or less.
- (D) By making the content rate of an ethylenically unsaturated compound below the said upper limit, it becomes the tendency which suppresses that the permeability of the developing solution to an exposure part becomes high, and obtains a favorable image easily. is there.
- the lower limit of the content rate of (d) ethylenically unsaturated compound is 1 mass% or more normally, Preferably it is 5 mass% or more.
- the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
- the content rate of alkali-soluble resin with respect to 100 mass parts of ethylenically unsaturated compounds is not specifically limited, 100 mass parts or more are preferable, 150 mass parts or more are more preferable, 200 mass parts or more are more preferable, 250 mass parts
- the above is particularly preferable, 800 parts by mass or less is preferable, 600 parts by mass or less is more preferable, 500 parts by mass or less is further preferable, and 400 parts by mass or less is particularly preferable.
- the upper limit and the lower limit is preferably 100 to 800 parts by mass, more preferably 150 to 600 parts by mass, further preferably 200 to 500 parts by mass, and particularly preferably 250 to 400 parts by mass.
- the photosensitive coloring composition of the present invention is prepared by using (e) a solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
- the content of the dispersant (f) in the total solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less. 20 mass% or less is preferable and 15 mass% or less is especially preferable.
- the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 5 to 15% by mass.
- the content ratio of the (f) dispersant with respect to 100 parts by mass of the (a) colorant is usually preferably 5 parts by mass or more and 10 parts by mass or more, and usually 50 parts by mass or less, particularly 30 parts by mass or less. preferable.
- the combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass.
- (F) By making the content rate of a dispersing agent more than the said lower limit, there exists a tendency for sufficient dispersibility to be easy to be obtained, and the ratio of another component reduces relatively by making it below the said upper limit. There exists a tendency which can suppress that a sensitivity, platemaking property, etc. fall.
- the content of the adhesion improver in the total solid content of the photosensitive coloring composition is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4. ⁇ 2% by weight.
- the effect of improving the adhesion can be sufficiently obtained by setting the content ratio of the adhesion improver to the above lower limit value or more, and the sensitivity is lowered by setting it to the upper limit value or less, or a residue remains after development. There exists a tendency which can suppress becoming a defect.
- the content of the surfactant in the total solid content of the photosensitive coloring composition is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0. 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass.
- the content of the surfactant is more than the lower limit value, there is a tendency that the smoothness and uniformity of the coating film tend to be expressed, and by setting it to the upper limit value or less, the smoothness and uniformity of the coating film are expressed. It tends to be easy to suppress deterioration of other characteristics.
- the photosensitive coloring composition of the present invention can be suitably used for forming a colored spacer, and is preferably black from the viewpoint of being used as a colored spacer.
- the optical density (OD) per 1 ⁇ m thickness of the cured coating film is preferably 1.0 or more, more preferably 1.2 or more, and further preferably 1.5 or more. 1.8 or more, usually 4.0 or less, and more preferably 3.0 or less.
- the combination of the upper limit and the lower limit is preferably 1.0 to 4.0, more preferably 1.2 to 4.0, still more preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. Can be mentioned.
- the photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
- the colorant is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the colorant (a) is finely divided by the dispersion treatment, the resist coating characteristics are improved.
- the dispersion treatment is usually preferably carried out in a system in which a part or all of (a) a colorant, (e) a solvent, (f) a dispersant, and (b) an alkali-soluble resin are used together (hereinafter referred to as dispersion).
- the mixture used for the treatment and the composition obtained by the dispersion treatment may be referred to as “ink”, “colorant dispersion” or “pigment dispersion”).
- a colorant dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.
- a colorant, (e) the organic solvent, and (f) the dispersant that can be used in the colorant dispersion those described as those that can be used in the photosensitive coloring composition are preferably employed. be able to.
- a dispersion treatment when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
- the colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used.
- the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.
- the dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus.
- the standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300.
- the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like.
- the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
- the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
- the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform mixed solution.
- fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
- a cured product can be obtained by curing the photosensitive coloring composition of the present invention.
- a cured product obtained by curing the photosensitive coloring composition can be suitably used as a colored spacer.
- the material thereof is not particularly limited.
- Transparent substrates are mainly used.
- materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, sheets made of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy.
- thermosetting resin sheets such as resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glasses.
- glass and heat resistant resin are preferable from the viewpoint of heat resistance.
- a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
- the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesiveness.
- the thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process of various resins is performed, the film thickness is usually 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
- the photosensitive colored composition of the present invention is used for the same applications as known photosensitive colored compositions for color filters. Hereinafter, it is used as a colored spacer (black photospacer). The method for forming a black photospacer using the photosensitive coloring composition of the present invention will be described below.
- a photosensitive coloring composition is supplied in a film shape or a pattern shape by a method such as coating on a substrate on which a black photospacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as photolithography for performing exposure and development. Thereafter, a black photo spacer is formed on the substrate by performing additional exposure or thermosetting treatment as necessary.
- the photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent.
- a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. Above all, the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.
- the coating amount varies depending on the application, but in the case of a black photospacer, for example, the dry film thickness is usually in the range of 0.5 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 9 ⁇ m, particularly preferably 1 ⁇ m to 7 ⁇ m.
- the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel.
- the final height of the black photo spacers is different.
- a known substrate such as a glass substrate can be used as the substrate.
- the substrate surface is preferably a flat surface.
- Drying method The drying after supplying the photosensitive coloring composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.
- Drying conditions can be appropriately selected according to the type of solvent component and the performance of the dryer used.
- the drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used.
- the temperature is selected in the range of 30 seconds to 3 minutes.
- Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating with an ultraviolet light source or a visible light source through this mask pattern.
- the exposure mask is placed close to the coating film of the photosensitive coloring composition, or the exposure mask is arranged at a position away from the coating film of the photosensitive coloring composition.
- a method of projecting exposure light through a mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used.
- the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.
- a light shielding portion (light transmittance 0%) and a plurality of openings have the highest average light transmittance.
- An exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to a high opening (complete transmission opening) is used.
- a difference in the residual film ratio is caused by a difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in exposure amount.
- a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known.
- a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.
- the light source used for the above exposure is not particularly limited.
- the light source for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser,
- laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser.
- An optical filter can also be used when used by irradiating light of a specific wavelength.
- a thin film may be of a type capable of controlling the light transmittance at the exposure wavelength, and as a material in that case, for example, Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
- Energy of exposure generally, 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, usually 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 or less, more preferably 150 mJ / cm 2 or less.
- the distance between the exposure target and the mask pattern is usually 10 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more, and usually 500 ⁇ m or less, preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less.
- an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
- This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
- Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
- Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine
- TMAH tetramethyl ammonium hydro
- surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.
- nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters
- Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfon
- organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
- the organic solvent can be used alone or in combination with an aqueous solution.
- the development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C.
- the development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
- thermosetting treatment If necessary, the substrate after development may be subjected to additional exposure by the same method as the exposure method described above, or may be subjected to thermosetting treatment.
- the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 ° C. to 280 ° C., preferably in the range of 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.
- the size and shape of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which the colored spacer is applied, but the photosensitive colored composition of the present invention is particularly suitable for the height of the spacer and the sub-spacer by photolithography. It is useful for simultaneously forming different black photo spacers, in which case the height of the spacer is usually about 2 to 7 ⁇ m, and the sub-spacer is usually about 0.2 to 1.5 ⁇ m lower than the spacer.
- the optical density (OD) per 1 ⁇ m of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, further preferably 1.8 or more, from the viewpoint of light-shielding properties. It is 0 or less, and preferably 3.0 or less.
- the optical density (OD) is a value measured by a method described later.
- the color filter of the present invention is provided with the colored spacer of the present invention as described above.
- a black matrix, a red, green, and blue pixel coloring layer, and an overcoat layer are stacked to form a colored spacer, and then an alignment film is formed.
- the pixel coloring layer and the coloring spacer may be formed on the liquid crystal driving side substrate, or may be separately formed on the transparent substrate and the liquid crystal driving side substrate.
- the liquid crystal provided with the colored spacer of the present invention is formed by bonding the color filter having the colored spacer of the present invention and the liquid crystal driving side substrate to form a liquid crystal cell, and injecting the liquid crystal into the formed liquid crystal cell.
- An image display device such as a display device can be manufactured.
- the case where the pixel coloring layer and the coloring spacer are formed on the liquid crystal driving side substrate can be similarly manufactured.
- the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
- THPA tetrahydrophthalic anhydride
- the weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was about 8400, the acid value was 80 mgKOH / g, and the double bond equivalent was 480 g / mol.
- TMP trimethylolpropane
- BPDA biphenyltetracarboxylic dianhydride
- THPA tetrahydrophthalic anhydride
- the resin solution When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, acid value 113 mgKOH / g, weight average molecular weight (Mw) 2600 in terms of polystyrene measured by GPC, double A carboxyl group-containing epoxy acrylate resin (alkali-soluble resin-III) having a binding equivalent of 520 g / mol was obtained.
- a mixture (a-1) containing a polyfunctional acrylate having one carboxyl group and five acryloyl groups in one molecule is obtained. Obtained.
- alkali-soluble resin-IV By reacting for 4 hours, an alkali-soluble resin-IV was obtained.
- the obtained alkali-soluble resin-IV had an acid value of 23 mgKOH / g, a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of 3000, and a double bond equivalent of 120 g / mol.
- the alkali-soluble resin-IV contained an alkali-soluble resin having the following structure, and its double bond equivalent was 189 g / mol.
- alkali-soluble resin-V had an acid value of 54 mgKOH / g, a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of 2500, and a double bond equivalent of 219 g / mol.
- the alkali-soluble resin-V contained an alkali-soluble resin having the following structure, and its double bond equivalent was 261 g / mol.
- Block copolymer, amine value is 70 mgKOH / g
- acid value is 1 mgKOH / g or less.
- the A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a).
- the content of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.
- the evaluation method and conditions of the photosensitive coloring composition are as follows.
- the optical density per unit film thickness was measured by the following procedure.
- the optical density (OD) of a glass substrate having pattern 2 and pattern 2 ′ described later is measured by a transmission densitometer Gretag Macbeth D200-II, and the film thickness is a non-contact surface / layer cross-sectional shape measurement system VertScan (manufactured by Ryoka Systems Inc.) R) measured by 2.0.
- the optical density per unit film thickness (unit OD value) was calculated from the optical density (OD) and film thickness. In Tables 2 and 3, it is expressed as “unit OD”.
- the OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.
- NMP dissolution test The N-methylpyrrolidone (NMP) dissolution test was performed according to the following procedure. Two measurement substrates (2.5 cm ⁇ 1.0 cm square) were cut out from a glass substrate having pattern 2 and pattern 2 ′ described below, and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). And the NMP elution test was implemented in the state which left the vial container containing the board
- the vial is taken out from the heat bath, and the absorbance is measured every 1 nm in the wavelength range of 300 to 800 nm with a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation) using the NMP elution solution (sample solution).
- a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation) using the NMP elution solution (sample solution).
- a halogen lamp and a deuterium lamp (switching wavelength: 360 nm) were used as a light source, and a photomultiplier was used as a detector, and a slit width of 2 nm was set as a measurement condition.
- the sample solution was measured by placing it in a 1 cm square quartz cell.
- Absorbance is a dimensionless quantity indicating how much light intensity is attenuated when light passes through an object in spectroscopy, and is defined by the following equation.
- a (absorbance) ⁇ log 10 (I / I 0 ) (I: transmitted light intensity, I 0 : incident light intensity)
- the light intensity transmitted through the NMP single solution can be regarded as I 0
- the light intensity transmitted through the sample solution can be regarded as I. Therefore, (I / I 0 ) in the above formula represents the light transmittance
- the absorbance A is a value obtained by logarithmically expressing the reciprocal of the transmittance.
- NMP resistance the evaluation result of NMP resistance is shown in the upper part, and the actual area value is shown in the lower part.
- the spectral area of absorbance can be expressed as the sum of absorbance at each wavelength, and means the total sum of the eluted resist components.
- NMP resistance evaluation criteria Judgment by area value of absorption spectrum of NMP elution solution A: Less than 30 (nm) B: 30 (nm) or more
- the elastic recovery rate was measured in the following procedures.
- Shimadzu Corporation Shimadzu Dynamic Ultramicrohardness Tester DUH-W201S
- a flat indenter with a measurement temperature of 23 ° C. and a diameter of 50 ⁇ m was used. / Sec
- a load was applied to the spacer.
- the spacer was held for 5 seconds, and then unloaded at the same speed to obtain a load-displacement curve. From this load-displacement curve, the maximum displacement ( ⁇ m) and final displacement ( ⁇ m) were measured, the elastic recovery rate (%) was calculated by the following formula, and the compression characteristics were evaluated according to the following evaluation criteria.
- Elastic recovery rate (%) ⁇ (maximum displacement ⁇ final displacement) / maximum displacement ⁇ ⁇ 100
- Viscosity increase rate is 10% or less
- Viscosity increase rate is over 10%
- the development form was evaluated according to the following procedure.
- the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2.3 ⁇ m, dried under reduced pressure for 1 minute, and then dried at 80 ° C. for 70 seconds with a hot plate. Thereafter, exposure and development processes were performed, and the dissolution of the non-image area (unexposed area) during development was visually observed.
- the non-image area is roughly divided into a type in which the non-image area is uniformly dissolved in the developer and a type in which the non-image area is peeled off into a film shape, and whether the developability is good or bad is determined according to the following evaluation criteria.
- resist strips remain in the developer and may be contaminated as particles, which may reduce the yield during the production of the colored spacer.
- the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2.3 ⁇ m, dried under reduced pressure for 1 minute, and then dried at 80 ° C. for 70 seconds with a hot plate. . After passing through the exposure and development steps, it was heated in an oven at 230 ° C. for 20 minutes to obtain a resist-coated substrate. About the produced resist coating board
- ⁇ Evaluation of surface roughness> With respect to the resist coated substrate prepared in the above ⁇ Evaluation of surface smoothness>, a three-dimensional non-contact surface shape measurement system Micromap manufactured by Ryoka System Co., Ltd. is used with a 50 ⁇ optical lens and 70 ⁇ m ⁇ 70 ⁇ m in Focus mode. The surface roughness Sa (arithmetic mean roughness, ⁇ m) was measured in the visual field.
- Table 1 Abbreviations in Table 1 represent the following meanings. Or64: C.I. I. Pigment orange 64, V29: C.I. I. Pigment violet 29, B60: C.I. I. Pigment blue 60, CB: Carbon black. Moreover, all the mixture ratios in Table 1 are expressed in parts by mass, and values other than the solvent are values in terms of solid content.
- Examples 1 to 9 and Comparative Examples 1 and 2 Using the colorant dispersions 1 to 3 prepared above, each component is added so that the ratio in the solid content is the mixing ratio in Tables 2 to 3, and the total solid content is 19% by mass. As described above, PGMEA was added, and stirred and dissolved to prepare a photosensitive coloring composition. Using the obtained photosensitive coloring composition, a pattern was prepared by the method described later and evaluated by the method described above.
- ⁇ Method for forming spacer pattern> The photosensitive coloring compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were coated on a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) using a spin coater. Subsequently, it dried by heating on a hot plate at 100 ° C. for 70 seconds to form a coating film having a film thickness of 2.7 ⁇ m. The obtained coating film was subjected to exposure treatment using an exposure mask having a circular transmission pattern having a circular pattern with various diameters of 5 to 50 ⁇ m (5 to 20 ⁇ m: every 1 ⁇ m, 25 ⁇ m to 50 ⁇ m: every 5 ⁇ m). .
- the exposure gap (distance between the mask and the coated surface) was 300 ⁇ m.
- the irradiation light intensity at a wavelength 365nm is used ultraviolet is 32 mW / cm 2, the exposure amount was 60 mJ / cm 2.
- ultraviolet irradiation was performed under air.
- a developer comprising an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used, and the water pressure was 0 at 25 ° C.
- A-60 a nonionic surfactant manufactured by Kao Corporation
- the shower development time was adjusted between 10 and 120 seconds, and was 1.3 times the time required for dissolving and removing the unexposed film.
- a substantially cylindrical spacer pattern (pattern 1) having a height of 2.3 ⁇ m and a bottom diameter of 30 ⁇ 2 ⁇ m is obtained. Obtained. Further, an entire surface covering pattern (pattern 2) having a film thickness of 2.3 ⁇ m was prepared in the same procedure except that no exposure mask was used. The diameter of the bottom surface of the spacer pattern was measured using an ultra-deep color 3D shape measuring microscope “VK-9500” manufactured by Keyence Corporation. Similarly, in Examples 5 to 9, a coating film having a film thickness of 2.7 ⁇ m was formed, and a substantially cylindrical spacer pattern (pattern) having a bottom diameter of 30 ⁇ 2 ⁇ m under the same exposure, development and heating conditions. 1 ′) and a full-coverage pattern (pattern 2 ′) were prepared.
- the optical density (OD) per unit film thickness (1 ⁇ m) of the pattern 2 and the pattern 2 ′ was measured by the method described above. Further, an NMP dissolution test was performed by the above-described method using the pattern 2 and the pattern 2 '. Further, the compression characteristics of the pattern 1 and the pattern 1 'were evaluated by the method described above. The results are shown in Tables 2 to 3, respectively.
- Example 1 The results of surface smoothness are shown in Tables 2-3.
- the results of surface roughness were 0.003 ⁇ m for Example 1, 0.004 ⁇ m for Example 2, 0.807 ⁇ m for Example 5, 0.001 ⁇ m for Example 6, 0.002 ⁇ m for Example 7, and 0.002 ⁇ m for Example 7. 8 was 0.003 ⁇ m, and Example 9 was 0.002 ⁇ m.
- the coated substrates using the photosensitive coloring compositions of Examples 1 to 9 had a high unit OD and excellent light shielding properties, and excellent NMP elution and mechanical properties.
- the coated substrate using the photosensitive coloring composition of Comparative Example 1 has good NMP elution and mechanical properties, but has a low unit OD and insufficient light shielding properties.
- the value of unit OD was the same as the Example in the comparative example 2, it was confirmed that NMP elution and mechanical characteristics are bad.
- the photosensitive coloring composition of the present invention it is possible to provide a cured product and a colored spacer that have high light-shielding properties and excellent solvent resistance and mechanical properties, and further, an image display provided with such a colored spacer.
- An apparatus can be provided. Therefore, the present invention has very high industrial applicability in the fields of photosensitive coloring composition, cured product, coloring spacer and image display device.
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Abstract
Description
2016年10月14日に日本国特許庁に出願された日本国特願2016-202697、及び2017年9月7日に日本国特許庁に出願された日本国特願2017-172544の明細書、特許請求の範囲、図面、及び要約書の全内容、並びに、本明細書で引用された文献等に開示された内容の一部又は全部をここに引用し、本明細書の開示内容として取り入れる。
また、機械的特性に優れ、さらにパターン精度、基板密着性にすぐれるものとして、特定の樹脂を含有する硬化性組成物等が提案されている(特許文献4参照)。
前記感光性着色組成物の全固形分に占める前記(a)着色剤の含有割合が20質量%以上であり、
前記(b)アルカリ可溶性樹脂が、下記式(I)で表される部分構造(1)を有するアルカリ可溶性樹脂(b-1)を含有することを特徴とする感光性着色組成物。
R2、R3、R5及びR6は各々独立に、置換基を有していてもよいアルキレン基を表し;
R4はn+1価の連結基を表し;
R7は置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基又は置換基を有していてもよい芳香族環基を表し;
l及びmは各々独立に、0~12の整数を表し;
nは3以上の整数を表し;
*は結合手を表す。)
前記感光性着色組成物の全固形分に占める前記(a)着色剤の含有割合が20質量%以上であり、
前記(b)アルカリ可溶性樹脂が、二重結合当量が400以下であるアルカリ可溶性樹脂(b-1)を含有することを特徴とする感光性着色組成物。
[4]前記感光性着色組成物の全固形分に占める前記アルカリ可溶性樹脂(b-1)の含有割合が1質量%以上である、[1]~[3]のいずれか1項に記載の感光性着色組成物。
[5]前記(b)アルカリ可溶性樹脂が、さらにエポキシ(メタ)アクリレート樹脂(b-2)を含有する、[1]~[4]のいずれか1項に記載の感光性着色組成物。
[6]前記エポキシ(メタ)アクリレート樹脂(b-2)が、下記一般式(ii)で表される部分構造を有するエポキシ(メタ)アクリレート樹脂(b-2-ii)である、[5]に記載の感光性着色組成物。
Rdは、環状炭化水素基を側鎖として有する2価の炭化水素基を表し;
Re及びRfは各々独立に、置換基を有していてもよい2価の脂肪族基を表し;
m及びnは各々独立に、0~2の整数を表し;
*は結合手を表す。)
[8]前記有機着色顔料が、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも1種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも1種とを含有する、[7]に記載の感光性着色組成物。
[9]前記(a)着色剤が、黒色顔料を含有する、[1]~[8]のいずれか1項に記載の感光性着色組成物。
[10]前記黒色顔料が、カーボンブラック及び有機黒色顔料の一方又は両方を含有する、[9]に記載の感光性着色組成物。
[11]前記有機黒色顔料が、下記一般式(1)で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料である、[10]に記載の感光性着色組成物。
R12、R13、R14、R15、R17、R18、R19及びR20は各々独立に、水素原子、ハロゲン原子、R21、COOH、COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22、N=CH2、N=CHR21、N=CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21又はSO2NR21R22を表し;
かつ、R12とR13、R13とR14、R14とR15、R17とR18、R18とR19、及びR19とR20からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合し、又は酸素原子、硫黄原子、NH若しくはNR21ブリッジによって互いに結合することもでき;
R21及びR22は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基である。)
[13]着色スペーサー形成用である、[1]~[12]のいずれか1項に記載の感光性着色組成物。
[15][14]の硬化物から形成される着色スペーサー。
[16][15]の着色スペーサーを備える画像表示装置。
なお、本発明において、「(メタ)アクリル」とは「アクリル及びメタクリルの一方又は両方」を意味し、「(メタ)アクリレート」、「(メタ)アクリロイル」についても同様である。
本発明において「全固形分」とは、感光性着色組成物中又は後述するインク中に含まれる、溶剤以外の全成分を意味するものとする。
本発明において、「重量平均分子量」とは、GPC(ゲルパーミエーションクロマトグラフィー)によるポリスチレン換算の重量平均分子量(Mw)をさす。
また、本発明において、「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分1gあたりの塩基量と当量のKOHの質量で表される値である。なお、測定方法については後述する。一方、「酸価」とは、特に断りのない限り有効固形分換算の酸価を表し、中和滴定により算出される。
本発明の感光性着色組成物は、
(a)着色剤
(b)アルカリ可溶性樹脂
(c)光重合開始剤
(d)エチレン性不飽和化合物
(e)溶剤
(f)分散剤
を必須成分として含有する。
また、本発明の感光性着色組成物は、必要に応じて、さらにシランカップリング剤等の密着向上剤、界面活性剤(塗布性向上剤)、顔料誘導体、光酸発生剤、架橋剤、メルカプト化合物、現像改良剤、紫外線吸収剤、酸化防止剤等、その他の配合成分を含むものであってもよく、通常、各配合成分が、溶剤に溶解又は分散した状態で使用される。
他方、本発明の第2の態様に係る感光性着色組成物は、感光性着色組成物の全固形分に占める(a)着色剤の含有割合が20質量%以上であり、かつ、(b)アルカリ可溶性樹脂が、二重結合当量が400以下であるアルカリ可溶性樹脂(b-1)を含有する。
以下、特に断りがない限り、「本発明の感光性着色組成物」は、前記第1の態様に係る感光性着色組成物と、第2の態様に係る感光性着色組成物の両方を指す。また、特に断りがない限り「アルカリ可溶性樹脂(b-1)」とは、第1の態様に係る「アルカリ可溶性樹脂(b-1)」と第2の態様に係る「アルカリ可溶性樹脂(b-1)」の両方を指す。
本発明の感光性着色組成物は、(a)着色剤を含有する。(a)着色剤を含有することで、適度な光吸収性、特に着色スペーサーなどの遮光部材を形成する用途に用いる場合には適度な遮光性を得ることができる。
また、本発明の感光性着色組成物は、全固形分に占める(a)着色剤の含有割合が20質量%以上である。このように(a)着色剤を所定量以上含有することにより、得られる硬化物、特に着色スペーサーの遮光性が高くなる。一方で、全固形分中に占める着色剤の割合が高くなる反面、光硬化に寄与する樹脂やモノマー等の硬化性成分の含有割合が相対的に低くなり、さらに、着色剤の含有割合が高くなることで露光時に着色剤に吸収される紫外光の割合も高くなる傾向にもあり、それらの結果として、硬化物の架橋密度が低くなり、耐溶剤性や機械的特性が悪化する傾向がある。
(a)着色剤として用いることができる顔料の種類は特に限定されないが、例えば、有機顔料や無機顔料が挙げられる。これらの中でも、液晶の電圧保持率の低下を抑制し、また、紫外線の吸収を抑制して形状や段差をコントロールしやすくするとの観点からは、有機顔料を用いることが好ましい。
有機顔料としては、有機着色顔料や有機黒色顔料が挙げられる。ここで、有機着色顔料とは、黒色以外の色を呈する有機顔料のことを意味し、赤色顔料、橙色顔料、青色顔料、紫色顔料、緑色顔料、黄色顔料等が挙げられる。
有機着色顔料は、1種を単独で使用してもよいが、2種以上を併用してもよい。特に、遮光性の用途に用いる場合には、色の異なる有機着色顔料を組み合わせて用いることがより好ましく、黒に近い色を呈する有機着色顔料の組み合わせを用いることがさらに好ましい。
なお、分散性や遮光性の点で、C.I.ピグメントブルー15:6、16、60を用いることが好ましく、感光性着色組成物を紫外線で硬化させる場合には、青色顔料としては紫外線吸収率の低いものを使用することが好ましく、かかる観点からはC.I.ピグメントブルー60を用いることがより好ましい。
なお、分散性や遮光性の点で、C.I.ピグメントバイオレット23、29を用いることが好ましく、感光性着色組成物を紫外線で硬化させる場合には、紫色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはC.I.ピグメントバイオレット29を用いることがより好ましい。
緑色顔料としては、C.I.ピグメントグリーン1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55を挙げることができる。この中でも、好ましくはC.I.ピグメントグリーン7、36を挙げることができる。
黄色顔料としては、C.I.ピグメントイエロー1、1:1、2、3、4、5、6、9、10、12、13、14、16、17、24、31、32、34、35、35:1、36、36:1、37、37:1、40、41、42、43、48、53、55、61、62、62:1、63、65、73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、126、127、127:1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191:1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208を挙げることができる。この中でも、好ましくはC.I.ピグメントイエロー83、117、129、138、139、150、154、155、180、185、さらに好ましくはC.I.ピグメントイエロー83、138、139、150、180を挙げることができる。
赤色顔料:カラーインデックスピグメントレッド177、254、272
橙色顔料:カラーインデックスピグメントオレンジ43、64、72
青色顔料:カラーインデックスピグメントブルー15:6、60
紫色顔料:カラーインデックスピグメントバイオレット23、29
なお、色の組み合わせについては特に限定されないが、遮光性の観点からは例えば、赤色顔料と青色顔料の組み合わせ、青色顔料と橙色顔料の組み合わせ、青色顔料と橙色顔料と紫色顔料の組み合わせなどが挙げられる。
黒色顔料としては、無機黒色顔料や有機黒色顔料が挙げられるが、遮光性の観点から、カーボンブラック及び有機黒色顔料の一方又は両方を含有することが好ましい。
R12、R13、R14、R15、R17、R18、R19及びR20は各々独立に、水素原子、ハロゲン原子、R21、COOH、COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22、N=CH2、N=CHR21、N=CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21又はSO2NR21R22を表し;かつ、R12とR13、R13とR14、R14とR15、R17とR18、R18とR19、及びR19とR20からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合し、又は酸素原子、硫黄原子、NH若しくはNR21ブリッジによって互いに結合することもでき;R21及びR22は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基である。
R12、R14、R15、R17、R19及びR20は各々独立に、好ましくは水素原子、フッ素原子、又は塩素原子であり、さらに好ましくは水素原子である。
R13及びR18は各々独立に、好ましくは水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3H又はSO3 -であり、さらに好ましくは水素原子又はSO3Hであり、特に好ましくは水素原子である。
好ましくは、R11とR16、R12とR17、R13とR18、R14とR19、及びR15とR20からなる群から選ばれる少なくとも1つの組み合わせが同一であり、より好ましくは、R11はR16と同一であり、R12はR17と同一であり、R13はR18と同一であり、R14はR19と同一であり、かつ、R15はR20と同一である。
この有機黒色顔料は、好ましくは後述される分散剤、溶剤、方法によって分散して使用される。また、分散の際に化合物(1)のスルホン酸誘導体、特に化合物(2)のスルホン酸誘導体が存在すると、分散性や保存性が向上する場合があるため、有機黒色顔料がこれらのスルホン酸誘導体を含むことが好ましい。
デグサ社製:Printex(登録商標、以下同じ。)3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black
FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
キャボット社製:Monarch(登録商標、以下同じ。)120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL(登録商標、以下同じ。)99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN(登録商標、以下同じ。) XC72R、ELFTEX(登録商標)-8
ビルラー社製:RAVEN(登録商標、以下同じ。)11、RAVEN14、RAVEN15、RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000
具体的な合成樹脂としては、フェノール樹脂、メラミン樹脂、キシレン樹脂、ジアリルフタレート樹脂、グリプタル樹脂、エポキシ樹脂、アルキルベンゼン樹脂等の熱硬化性樹脂や、ポリスチレン、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、変性ポリフェニレンオキサイド、ポリスルフォン、ポリパラフェニレンテレフタルアミド、ポリアミドイミド、ポリイミド、ポリアミノビスマレイミド、ポリエーテルスルフォポリフェニレンスルフォン、ポリアリレート、ポリエーテルエーテルケトン、等の熱可塑性樹脂が使用できる。被覆樹脂の量は、カーボンブラックと樹脂の合計量に対し1~30質量%が好ましい。前記下限値以上とすることで被覆を十分なものとすることができる傾向がある。一方、前記上限値以下とすることで、樹脂同士の粘着を防ぎ、分散性が良好なものとすることができる傾向がある。
また、顔料の平均粒子径は、動的光散乱(DLS)により測定された顔料粒子径から求めた値である。粒子径測定は、十分に希釈された感光性着色組成物(通常は希釈して、顔料濃度0.005~0.2質量%程度に調製する。但し、測定機器により推奨された濃度があれば、その濃度に従う。)に対して行い、25℃にて測定する。
アゾ系染料としては、例えば、C.I.アシッドイエロー11、C.I.アシッドオレンジ7、C.I.アシッドレッド37、C.I.アシッドレッド180、C.I.アシッドブルー29、C.I.ダイレクトレッド28、C.I.ダイレクトレッド83、C.I.ダイレクトイエロー12、C.I.ダイレクトオレンジ26、C.I.ダイレクトグリーン28、C.I.ダイレクトグリーン59、C.I.リアクティブイエロー2、C.I.リアクティブレッド17、C.I.リアクティブレッド120、C.I.リアクティブブラック5、C.I.ディスパースオレンジ5、C.I.ディスパースレッド58、C.I.ディスパースブルー165、C.I.ベーシックブルー41、C.I.ベーシックレッド18、C.I.モルダントレッド7、C.I.モルダントイエロー5、C.I.モルダントブラック7等が挙げられる。
この他、フタロシアニン系染料として、例えば、C.I.パッドブルー5等が、キノンイミン系染料として、例えば、C.I.ベーシックブルー3、C.I.ベーシックブルー9等が、キノリン系染料として、例えば、C.I.ソルベントイエロー33、C.I.アシッドイエロー3、C.I.ディスパースイエロー64等が、ニトロ系染料として、例えば、C.I.アシッドイエロー1、C.I.アシッドオレンジ3、C.I.ディスパースイエロー42等が挙げられる。
{アルカリ可溶性樹脂(b-1)}
(第1の態様)
第1の態様に係る本発明の感光性着色組成物において、(b)アルカリ可溶性樹脂は、下記式(I)で表される部分構造(1)を有するアルカリ可溶性樹脂(b-1)(以下、第1の態様における「アルカリ可溶性樹脂(b-1)」を「アルカリ可溶性樹脂(b-1-1)」と称する場合がある。)を含有する。アルカリ可溶性樹脂(b-1-1)は、式(I)で表される部分構造中に(メタ)アクリロイルオキシ基を3以上有するため、樹脂1分子中のエチレン性二重結合量が多く、当該樹脂を含む感光性着色組成物を用いて着色スペーサーを形成すると架橋密度が高くなり、溶剤への不純物の溶出が抑制され高い表示信頼性を確保でき、同様にスペーサーの架橋密度が高くなることで機械的特性も優れるものと考えられる。
R2、R3、R5及びR6は各々独立に、置換基を有していてもよいアルキレン基を表し;
R4はn+1価の連結基を表し;
R7は置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、又は置換基を有していてもよい芳香族環基を表し;
l及びmは各々独立に、0~12の整数を表し;
nは3以上の整数を表し;
*は結合手を表す。
前記式(I)において、R2、R3、R5及びR6は各々独立に、置換基を有していてもよいアルキレン基を表す。
アルキレン基は直鎖状でも、分岐鎖状でも、環状でも、それらの組み合わせでもよい。その炭素数は特に限定されないが、1以上であって、また、通常6以下、好ましくは4以下、より好ましくは2以下である。前記上限値以下とすることで他の成分との相溶性が良好となる傾向がある。上限と下限の組み合わせとしては、1~6が好ましく、1~4がより好ましく、1~2がさらに好ましく挙げられる。
前記一般式(I)において、R4はn+1価の連結基を表す。n+1価の連結基の化学構造は特に限定されないが、置換基を有していてもよいn+1価の炭化水素基が挙げられる。炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよく、現像性の観点から脂肪族炭化水素基であることが好ましい。また、炭化水素基中の炭素-炭素単結合は、-O-、CO-及び-NH-からなる群から選ばれる少なくとも1種で中断されていてもよい。
前記式(I)において、R7は置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、又は置換基を有していてもよい2価の芳香族環基を表す。
また、2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
これらの中でも光硬化性の観点から、2個の遊離原子価を有するベンゼン又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
前記一般式(I)において、l及びmは各々独立に、0~12の整数を表す。現像密着性の観点から、0以上であることが好ましく、1以上であることがより好ましく、また、硬化性の観点から、8以下であることが好ましく、6以下であることがより好ましく、4以下がさらに好ましく、2以下が特に好ましい。上限と下限の組み合わせとしては、0~8が好ましく、1~6がより好ましく、1~4がさらに好ましく、1~2が特に好ましく挙げられる。一方で、硬化性の観点からは0であることが好ましい。
前記一般式(I)において、nは3以上の整数を表す。nは4以上が好ましく、5以上がより好ましく、また、10以下が好ましく、8以下がより好ましく、7以下がさらに好ましく、6以下が特に好ましい。前記下限値以上とすることで硬化性が良好となる傾向があり、また、前記上限値以下とすることで現像溶解性が良好となる傾向がある。上限と下限の組み合わせとしては、3~10が好ましく、4~8がより好ましく、5~7がさらに好ましく、5~6が特に好ましく挙げられる。
また、アルカリ可溶性樹脂(b-1-1)は、現像溶解性の観点から、下記式(II)で表される部分構造(2)を有することが好ましい。
*は結合手を表す。
前記式(II)において、R8は置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、又は置換基を有していてもよい2価の芳香族環基を表す。
また、2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
これらの中でも光硬化性の観点から、2個の遊離原子価を有するベンゼン又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
また、アルカリ可溶性樹脂(b-1-1)は、硬化性の観点から、下記式(III)で表される部分構造(3)を有することが好ましい。
pは1以上の整数を表し;
*は結合手を表す。
上記式(III)中、R9はエポキシ樹脂残基を表す。エポキシ樹脂残基とは、エポキシ樹脂からエポキシ基を除した残基を意味する。
ここで、エポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。
また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、2価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
具体的には、例えば、ビスフェノールAエポキシ樹脂、ビスフェノールFエポキシ樹脂、ビスフェノールSエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタンとの重合エポキシ樹脂、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、9,9-ビス(4’-ヒドロキシフェニル)フルオレンのジグリシジルエーテル化物、1,1-ビス(4’-ヒドロキシフェニル)アダマンタンのジグリシジルエーテル化物、などが挙げられ、これらのように主鎖に芳香族環を有するものを好適に用いることができる。
前記式(III)中、pは1以上の整数を表す。硬化性と現像溶解性の両立の観点から、pは2であることが好ましい。一方で、硬化性の観点から、pは2以上であることが好ましく、3以上であることがより好ましく、5以上であることがさらに好ましく、また、現像溶解性の観点から20以下であることが好ましく、15以下であることがより好ましく、10以下であることがさらに好ましい。前記下限値以上とすることで硬化性が良好となるとなる傾向があり、前記上限値以下とすることで現像溶解性が良好となる傾向がある。上限と下限の組み合わせとしては、1~20が好ましく、2~15がより好ましく、2~10がさらに好ましく挙げられる。
前記式(III)で表される部分構造(3)は、現像溶解性の観点から、下記式(III-1)で表される部分構造(3-1)であることが好ましい。
式(III-1)中のベンゼン環は、さらに任意の置換基により置換されていてもよく;
*は結合手を表す。
前記式(III-1)中、γは2価の連結基を表す。2価の連結基としては、現像溶解性の観点から、単結合、置換基を有していてもよいアルキレン基、-CO-又は-SO2-が挙げられる。
アルキレン基は直鎖状でも、分岐鎖状でも、環状でも、それらの組み合わせでもよい。その炭素数は特に限定されないが、1以上であって、2以上が好ましく、また、通常8以下、好ましくは6以下である。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~8が好ましく、2~6がより好ましく挙げられる。
置換基を有する場合、その数は限定されず、1でもよく、2以上でもよい。
中でも、式(IV)で記載される構造を有する樹脂が、硬化性の観点から好ましい。
前記式(III)で表される部分構造(3)は、硬化性の観点から、下記式(III-2)で表される部分構造(3-2)であることが好ましい。
*は結合手を表す。
前記式(III)で表される部分構造(3)は、硬化性の観点から、下記式(III-3)で表される部分構造(3-3)を含むことが好ましい。
式(III-3)中のベンゼン環は、さらに任意の置換基により置換されていてもよく;
*は結合手を表す。
前記式(III-3)において、R10は置換基を有していてもよい2価の炭化水素基を表す。
2価の炭化水素基としては、2価の脂肪族基、2価の芳香族環基、1以上の2価の脂肪族基と1以上の2価の芳香族環基とを連結した基が挙げられる。
2価の分岐鎖状脂肪族基の具体例としては、前述の2価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上であって、2以上が好ましく、また、通常20以下、10以下が好ましく、5以下がより好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~20が好ましく、2~10がより好ましく挙げられる。2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を2つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、アダマンタン環から水素原子を2つ除した基が好ましい。
また、2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
これらの中でも光硬化性の観点から、2個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、1以上であって、2以上が好ましく、通常10以下、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで硬化性が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の芳香族環基の数は特に限定されないが、1以上であって、2以上が好ましく、通常10以下、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで硬化性が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
これらの中でも硬化性の観点から、無置換であることが好ましい。
前記式(III)で表される部分構造(3)は、硬化性の観点から、下記式(III-4)で表される部分構造(3-4)を含むことが好ましい。
式(III-4)中のベンゼン環は、さらに任意の置換基により置換されていてもよく;
*は結合手を表す。
また、前記式(III-4)中のベンゼン環が有していてもよい任意の置換基としては、前記式(III-1)中のベンゼン環が有していてもよい任意の置換基として記載したものを好ましく採用することができる。
第1の態様に係る本発明の感光性着色組成物において、(b)アルカリ可溶性樹脂は、アルカリ可溶性樹脂(b-1-1)を含有するが、該アルカリ可溶性樹脂(b-1-1)は、例えば、エポキシ樹脂(A)より得られるエチレン性不飽和基含有カルボニルオキシ基を有する化合物(p1)に、場合によりイソシアネート基含有化合物(p3)を反応させた後、多価カルボン酸及びその無水物の一方又は両方(p2)を反応させる方法を挙げることができる。
エポキシ樹脂(A)としては、前記式(III)のR9のエポキシ樹脂残基におけるエポキシ樹脂として説明したものを用いることができ、具体的には下記式(III-5)に記載したエポキシ樹脂を用いることができる。
pは1以上の整数を表し;
*は結合手を表す。)
上述のようなエポキシ樹脂(A)より得られるエチレン性不飽和基含有カルボニルオキシ基を有する化合物(p1)は、上述のエポキシ樹脂(A)を原料とした反応により、結果としてエチレン性不飽和基含有カルボニルオキシ基が形成されていれば、その製造方法は限定されるものではないが、具体的には、上述のエポキシ樹脂(A)に、エチレン性不飽和基含有カルボン酸類(B)を反応させる方法、あるいは、上述のエポキシ樹脂にまずエチレン性不飽和基を含有しないカルボン酸類(C)を反応させた後に、続く反応によりエチレン性不飽和基含有カルボニルオキシ基を形成させる方法、例えば、生成した水酸基に反応する官能基を有する化合物(D)を反応させて、エチレン性不飽和基含有カルボニルオキシ基を形成させる方法、などを挙げる事ができる。
そのエチレン性不飽和基含有カルボン酸類(B)としては、エチレン性不飽和二重結合を有する不飽和カルボン酸が挙げられ、具体例としては、(メタ)アクリル酸、クロトン酸、o-、m-、p-ビニル安息香酸、(メタ)アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体などのモノカルボン酸、(メタ)アクリル酸とラクトンあるいはポリラクトンとの反応生成物類;
無水コハク酸、無水アジピン酸、無水マレイン酸、無水フマル酸、無水イタコン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、無水フタル酸等の飽和若しくは不飽和ジカルボン酸無水物と、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート等の(メタ)アクリレート等の1分子中に1個以上のヒドロキシル基を有する(メタ)アクリレート誘導体とを反応させて得られる半エステル類;
飽和若しくは不飽和ジカルボン酸無水物と、フェニルグリシジルエーテル、グリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、8,9-エポキシ〔ビシクロ[4.3.0]ノナン-3-イル〕(メタ)アクリレート、8,9-エポキシ〔ビシクロ[4.3.0]ノナン-3-イル〕オキシメチル(メタ)アクリレート等の不飽和基含有グリシジル化合物とを反応させて得られる半エステル類;等が挙げられる。
これらの中で、本発明においては、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート等とを反応させて得られる半エステル類が特に好ましい。
これらは1種を単独で用いても、2種以上を併用してもよい。
そのエチレン性不飽和基を含有しないカルボン酸類(C)としては、乳酸、ジヒドロキシプロピオン酸などの水酸基含有カルボン酸及びその無水物、コハク酸、フタル酸、酒石酸等のジカルボン酸及びその無水物が挙げられる。
これらは1種を単独で用いても、2種以上を併用してもよい。
前述のエポキシ樹脂(A)に、エチレン性不飽和基を含有しないカルボン酸類(C)を反応させた後、生成した水酸基やカルボキシル基に反応する官能基を有する化合物(D)を反応させて、エチレン性不飽和基含有カルボニルオキシ基を形成させる際に用いられる、水酸基やカルボキシル基に反応する官能基を有する化合物(D)としては、エポキシ基、カルボキシル基、イソシアネート基を有する化合物が好ましく、具体的には、前記のエチレン性不飽和基含有カルボン酸類、前記の不飽和基含有グリシジル化合物等のエチレン性不飽和基含有化合物などを挙げる事ができるが、これらに限定されるものではない。
これらは1種を単独で用いても、2種以上を併用してもよい。
得られる感光性着色組成物の現像性の調整などのため、前記のエポキシ樹脂(A)より得られるエチレン性不飽和基含有ヒドロキシル基を有する化合物(p1)に、場合によりイソシアネート基含有化合物(p3)を反応させてもよい。
これらは1種を単独で用いても、2種以上を併用してもよい。
アルカリ可溶性樹脂(b-1-1)は、前記のエポキシ樹脂(A)より得られるエチレン性不飽和基含有カルボニルオキシ基を有する化合物(p1)に、場合により前述のイソシアネート基含有化合物(p3)を反応させた後、4価以上のカルボン酸及びその無水物を実質的に含まない多価カルボン酸及びその無水物の一方又は両方(p2)を反応させることにより、得ることができる。
本発明において、多価カルボン酸及びその酸無水物(p2)は1種を単独で用いても、2種以上を併用してもよい。
第1の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)のゲルパーミエーションクロマトグラフィーで測定したポリスチレン換算の重量平均分子量は特に限定されないが、1000以上が好ましく、1500以上がより好ましく、2000以上がさらに好ましく、2500以上が特に好ましく、また、6000以下が好ましく、5000以下がより好ましく、4000以下がさらに好ましく、3500以下が特に好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1000~6000が好ましく、1500~5000がより好ましく、2000~4000がさらに好ましく、2500~3500が特に好ましく挙げられる。
第1の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)の酸価は特に限定されないが、5mgKOH/g以上が好ましく、10mgKOH/g以上がより好ましく、15mgKOH/g以上がさらに好ましく、20mgKOH/g以上が特に好ましく、また、60mgKOH/g以下が好ましく、50mgKOH/g以下がより好ましく、40mgKOH/g以下がさらに好ましく、30mgKOH/g以下が特に好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、5~60mgKOH/gが好ましく、10~50mgKOH/gがより好ましく、15~40mgKOH/gがさらに好ましく、20~30mgKOH/gが特に好ましく挙げられる。
第1の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)の二重結合当量は特に限定されないが、20以上が好ましく、50以上がより好ましく、80以上がさらに好ましく、100以上が特に好ましく、また、600以下が好ましく、400以下がより好ましく、300以下がさらに好ましく、200以下がよりさらに好ましく、180以下が特に好ましく、150以下が最も好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、20~600が好ましく、50~400がより好ましく、80~300がさらに好ましく、100~200が特に好ましく挙げられる。
また、アルカリ可溶性樹脂(b-1)の二重結合当量は下記式(x)から算出することができる。
=(樹脂(b-1)の分子量)/(樹脂(b-1)1分子あたりのエチレン性不飽和二重結合の数) ・・・(x)
第1の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)の1分子中に含まれるエチレン性不飽和二重結合の数は特に限定されないが、2以上が好ましく、3以上がより好ましく、4以上がさらに好ましく、6以上がよりさらに好ましく、8以上が特に好ましく、また、20以下が好ましく、18以下がより好ましく、14以下がさらに好ましく、12以下が特に好ましい。前記下限値以上とすることで硬化性が良好となる傾向があり、また、前記上限値以下とすることで現像溶解性が良好となる傾向がある。上限と下限の組み合わせとしては、2~20が好ましく、4~18がより好ましく、6~14がさらに好ましく、8~12が特に好ましく挙げられる。
第2の態様に係る本発明の感光性着色組成物において、(b)アルカリ可溶性樹脂は、二重結合当量が400以下であるアルカリ可溶性樹脂(b-1)(以下、第2の態様における「アルカリ可溶性樹脂(b-1)」を「アルカリ可溶性樹脂(b-1-2)」と称する場合がある。)を含有する。アルカリ可溶性樹脂(b-1-2)は、二重結合当量が400以下であるため、樹脂1分子中のエチレン性二重結合量が多く、当該樹脂を含む感光性着色組成物を用いて着色スペーサーを形成すると架橋密度が高くなり、溶剤への不純物の溶出が抑制され高い表示信頼性を確保でき、同様にスペーサーの架橋密度が高くなることで機械的特性も優れるものと考えられる。
第2の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)のゲルパーミエーションクロマトグラフィーで測定したポリスチレン換算の重量平均分子量は特に限定されないが、1000以上が好ましく、1500以上がより好ましく、2000以上がさらに好ましく、2500以上が特に好ましく、また、6000以下が好ましく、5000以下がより好ましく、4000以下がさらに好ましく、3500以下が特に好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1000~6000が好ましく、1500~5000がより好ましく、2000~4000がさらに好ましく、2500~3500が特に好ましく挙げられる。
第2の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)の酸価は特に限定されないが、5mgKOH/g以上が好ましく、10mgKOH/g以上がより好ましく、15mgKOH/g以上がさらに好ましく、20mgKOH/g以上が特に好ましく、また、60mgKOH/g以下が好ましく、50mgKOH/g以下がより好ましく、40mgKOH/g以下がさらに好ましく、30mgKOH/g以下が特に好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、5~60mgKOH/gが好ましく、10~50mgKOH/gがより好ましく、15~40mgKOH/gがさらに好ましく、20~30mgKOH/gが特に好ましく挙げられる。
第2の態様に係る本発明の感光性着色組成物に含有されるアルカリ可溶性樹脂(b-1)の二重結合当量は400以下であれば特に限定されないが、20以上が好ましく、50以上がより好ましく、80以上がさらに好ましく、100以上が特に好ましく、また、350以下が好ましく、300以下が次に好ましく、200以下がより好ましく、180以下がよりさらに好ましく、160以下がさらに好ましく、150以下が特に好ましく、140以下が殊さらに好ましく、130以下が最も好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、20~400が好ましく、50~400がより好ましく、80~300がさらに好ましく、100~200が特に好ましく挙げられる。
また、第2の態様におけるアルカリ可溶性樹脂(b-1)の二重結合当量は前記式(x)から算出することができる。
第2の態様に係る本発明の感光性着色組成物に含有される、アルカリ可溶性樹脂(b-1)の1分子中に含まれるエチレン性不飽和二重結合の数は特に限定されないが、2以上が好ましく、3以上がより好ましく、4以上がさらに好ましく、6以上がよりさらに好ましく、8以上が特に好ましく、また、20以下が好ましく、18以下がより好ましく、14以下がさらに好ましく、12以下が特に好ましい。前記下限値以上とすることで硬化性が良好となる傾向があり、また、前記上限値以下とすることで現像溶解性が良好となる傾向がある。上限と下限の組み合わせとしては、2~20が好ましく、4~18がより好ましく、6~14がさらに好ましく、8~12が特に好ましく挙げられる。
*は結合手を表す。
本発明の感光性着色組成物において、(b)アルカリ可溶性樹脂はさらに、アルカリ可溶性樹脂(b-1)以外のエポキシ(メタ)アクリレート樹脂(b-2)(以下、「エポキシ(メタ)アクリレート樹脂(b-2)」と略記する場合がある。)を含有していてもよい。
エポキシ(メタ)アクリレート樹脂(b-2)を含有することで、感光性着色組成物の酸価を高くすることができ、現像溶解性と硬化性の両立ができる傾向があると考えられる。
また上記反応で得られた樹脂のカルボキシル基に、さらに反応し得る官能基を有する化合物を反応させて得られる樹脂も、上記エポキシ(メタ)アクリレート樹脂(b-2)に含まれる。
このように、エポキシ(メタ)アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「(メタ)アクリレート」に限定されるものではないが、エポキシ化合物(エポキシ樹脂)が原料であり、かつ、「(メタ)アクリレート」が代表例であるので慣用に従いこのように命名されている。
また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、2価もしくは2価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
具体的には、例えば、ビスフェノールAエポキシ樹脂、ビスフェノールFエポキシ樹脂、ビスフェノールSエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタンとの重合エポキシ樹脂、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、9,9-ビス(4’-ヒドロキシフェニル)フルオレンのジグリシジルエーテル化物、1,1-ビス(4’-ヒドロキシフェニル)アダマンタンのジグリシジルエーテル化物、などが挙げられ、このように主鎖に芳香族環を有するものを好適に用いることができる。
多価アルコールとしては、例えばトリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、1,2,3-プロパントリオールの中から選ばれる1種又は2種以上の多価アルコールであることが好ましい。
また、上記触媒としては、トリエチルアミン、ベンジルジメチルアミン、トリベンジルアミン等の第3級アミン類、テトラメチルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライドなどの第4級アンミニウム塩類、トリフェニルホスフィンなどの燐化合物、トリフェニルスチビンなどのスチビン類などの1種又は2種以上が挙げられる。
さらに、熱重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノンなどの1種又は2種以上が挙げられる。
Rbは置換基を有していてもよい2価の炭化水素基を表し;
式(i)中のベンゼン環は、さらに任意の置換基により置換されていてもよく;
*は結合手を表す。
Rdは、環状炭化水素基を側鎖として有する2価の炭化水素基を表し;
Re及びRfは各々独立に、置換基を有していてもよい2価の脂肪族基を表し;
m及びnは各々独立に、0~2の整数を表し;
*は結合手を表す。
次に、前記式(i)で表される繰り返し単位構造を有するエポキシ(メタ)アクリレート樹脂(以下、「エポキシ(メタ)アクリレート樹脂(b-2-i)」と略記する。)について詳述する。
Rbは置換基を有していてもよい2価の炭化水素基を表し;
式(i)中のベンゼン環は、さらに任意の置換基により置換されていてもよく;
*は結合手を表す。
前記式(i)において、Rbは置換基を有していてもよい2価の炭化水素基を表す。
2価の炭化水素基としては、2価の脂肪族基、2価の芳香族環基、1以上の2価の脂肪族基と1以上の2価の芳香族環基とを連結した基が挙げられる。
2価の分岐鎖状脂肪族基の具体例としては、前述の2価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上であって、2以上が好ましく、また、通常10以下、5以下が好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく挙げられる。2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を2つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、アダマンタン環から水素原子を2つ除した基が好ましい。
また、2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
これらの中でも光硬化性の観点から、2個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、1以上であって、2以上が好ましく、通常10以下、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の芳香族環基の数は特に限定されないが、通常1以上、2以上が好ましく、通常10以下、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで硬化性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
これらの中でも硬化性の観点から、無置換であることが好ましい。
RXは水素原子又は多塩基酸残基を表し;
*は結合手を表し;
式(i-1)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。
次に、前記式(ii)で表される部分構造を有するエポキシ(メタ)アクリレート樹脂(以下、「エポキシ(メタ)アクリレート樹脂(b-2-ii)」と略記する。)について詳述する。
Rdは、環状炭化水素基を側鎖として有する2価の炭化水素基を表し;
Re及びRfは各々独立に、置換基を有していてもよい2価の脂肪族基を表し;
m及びnは各々独立に、0~2の整数を表し;
*は結合手を表す。
前記式(ii)において、Rdは、環状炭化水素基を側鎖として有する2価の炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
また、脂肪族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく挙げられる。
脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも表示信頼性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、10以上がよりさらに好ましく、12以上が特に好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく、10~15が特に好ましく挙げられる。
芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等が挙げられる。これらの中でもパターニング特性の観点から、フルオレン環が好ましい。
2価の脂肪族基の炭素数は1以上であって、3以上が好ましく、6以上がより好ましく、また、25以下が好ましく、20以下がより好ましく、15以下がさらに好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~25が好ましく、3~20がより好ましく、6~15がさらに好ましく挙げられる。
2価の分岐鎖状脂肪族基の具体例としては、前述の2価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上であって、2以上が好ましく、また、通常10以下、好ましくは5以下、さらに好ましくは3以下が好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を2つ除した基が挙げられる。これらの中でも表示信頼性の観点から、アダマンタン環から水素原子を2つ除した基が好ましい。
また、2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
これらの中でもパターニング特性の観点から、2個の遊離原子価を有するベンゼン環、ナフタレン環又はフルオレン環が好ましく、2個の遊離原子価を有するフルオレン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、1以上であって、2以上が好ましく、通常10以下、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の芳香族環基の数は特に限定されないが、1以上であって、2以上が好ましく、通常10以下、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
前記一般式(ii)において、Re及びRfは各々独立に、置換基を有していてもよい2価の脂肪族基を表す。
2価の分岐鎖状脂肪族基の具体例としては、前述の2価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上であって、2以上が好ましく、また、通常12以下、10以下が好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。上限と下限の組み合わせとしては、1~12が好ましく、2~10がより好ましく挙げられる。2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環、ジシクロペンタジエン等の環から水素原子を2つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、ジシクロペンタジエン環、アダマンタン環から水素原子を2つ除した基が好ましい。
前記一般式(ii)において、m及びnは各々独立に、0~2の整数を表す。前記下限値以上とすることでパターニング適正が良好となり、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。現像性の観点からm及びnが0であることが好ましく、一方で、パターニング適正、表面荒れの観点からm及びnが1又は2であることが好ましい。
Rαは、置換基を有していてもよい1価の環状炭化水素基を表し;
nは1以上の整数であり;
式(ii-1)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
前記式(ii-1)において、Rαは、1価の環状炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
また、脂肪族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく挙げられる。
脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも相溶性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられるまた、芳香族環基の炭素数は通常4以上であり、5以上が好ましく、6以上がより好ましく、また、30以下が好ましく、20以下がより好ましく、15以下がさらに好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、4~30が好ましく、5~20がより好ましく、6~15がさらに好ましく挙げられる。
芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも表示信頼性の観点から、フルオレン環が好ましい。
nが2以上である場合、2以上のRαはそれぞれ同一でも、異なっていてもよい。
これらの中でもパターニング特性の観点から、無置換であることが好ましい。
Rβは、置換基を有していてもよい2価の環状炭化水素基を表し;
式(ii-2)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
前記式(ii-2)において、Rβは、2価の環状炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
また、脂肪族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、また、40以下が好ましく、35以下がより好ましく、30以下がさらに好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、4~40が好ましく、6~35がより好ましく、8~30がさらに好ましく挙げられる。
脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも相溶性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられるまた、芳香族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、10以上がさらに好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで現像密着性が良好となる傾向があり、また、前記上限値以下とすることで硬化性が良好となる傾向がある。上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく、10~15が特に好ましく挙げられる。
芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも表示信頼性の観点から、フルオレン環が好ましい。
一方で、表示信頼性の観点から、Rβが2価の芳香族環基であることが好ましく、2価のフルオレン環基であることがより好ましい。
これらの中でもパターニング特性の観点から、無置換であることが好ましい。
RZは水素原子又は多塩基酸残基を表す。
多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた1種又は2種以上が挙げられる。
これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。
本発明で用いる(b)アルカリ可溶性樹脂としては、前記アルカリ可溶性樹脂(b-1)や前記エポキシ(メタ)アクリレート樹脂(b-2)以外に、その他のアルカリ可溶性樹脂を含有していてもよい。
不飽和単量体(b1)としては、例えば、(メタ)アクリル酸、クロトン酸、α-クロルアクリル酸、けい皮酸等の不飽和モノカルボン酸;マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和ジカルボン酸又はその無水物;コハク酸モノ〔2-(メタ)アクリロイロキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイロキシエチル〕等の2価以上の多価カルボン酸のモノ〔(メタ)アクリロイロキシアルキル〕エステル;ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ(メタ)アクリレート;p-ビニル安息香酸等を挙げることができる。
これらの不飽和単量体(b1)は、単独で又は2種以上を混合して使用することができる。
これらの不飽和単量体(b2)は、単独で又は2種以上を混合して使用することができる。
不飽和単量体(b1)と不飽和単量体(b2)の共重合体は、公知の方法により製造することができるが、例えば、日本国特開2003-222717号公報、日本国特開2006-259680号公報、国際公開第2007/029871号パンフレット等に開示されている方法により、その構造やMw、Mw/Mnを制御することもできる。
(c)光重合開始剤は、光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。必要に応じて重合促進剤(連鎖移動剤)、増感色素等の付加剤を添加して使用してもよい。
オキシムエステル系化合物としては、例えば、国際公開第2008/075564号に記載のもの、国際公開第2009/131189号に記載のもの、日本国特開2011-132215号公報に記載のもの、国際公開第2008/078678号に記載のもの、日本国特表2014-500852号公報に記載のものなどが挙げられる。
Rc2は、置換基を有していてもよいアルカノイル基、又は置換基を有していてもよいアリーロイル基を表し;
Rc3は水素原子、又は置換基を有していてもよいアルキル基を表し;
Rc4は、置換基を有していてもよい芳香族環基を表し;
Rc5及びRc6は各々独立に、置換基を有していてもよいベンゼン環、又は置換基を有していてもよいナフタレン環を表し、ただし、Rc5及びRc6の少なくともいずれか1つは、置換基を有していてもよいナフタレン環であり;
Rc1及びRc4の少なくともいずれか1つは、-ORc7基を有し、ただしRc7はハロゲノアルキル基を表し;
Xは、直接結合、又はカルボニル基を表し;
Zは、直接結合、又はカルボニル基を表す。
また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、1個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
芳香族環基が有していてもよい置換基としては、アルキル基、水酸基、アルコキシ基、ハロゲン原子、ハロゲノアルキル基、後述の-ORc7基などが挙げられ、表面硬化性の観点からはハロゲン原子、ハロゲノアルキル基又は-ORc7基が好ましく、-ORc7基がより好ましく、一方で、合成容易性の観点からは無置換であることが好ましい。
これらの中でも、感度の観点からは、置換基を有していてもよい芳香族炭化水素環基であることが好ましく、-ORc7基で置換された芳香族炭化水素環基であることがより好ましく、-ORc7基で置換されたベンゼン環基であることがさらに好ましい。
アルカノイル基が有していてもよい置換基としては、水酸基、アルコキシ基、ハロゲン原子などが挙げられ、感度の観点から無置換であることが好ましい。
アリーロイル基が有していてもよい置換基としては、水酸基、アルコキシ基、ハロゲン原子などが挙げられ、感度の観点から無置換であることが好ましい。
これらの中でも、感度の観点からRc2を、置換基を有していてもよいアルカノイル基とすることが好ましく、無置換のアルカノイル基とすることがより好ましく、アセチル基とすることがさらに好ましい。
これらの中でも、溶解性の観点からRc3を、置換基を有していてもよいアルキル基とすることが好ましく、無置換のアルキル基とすることがより好ましく、2-エチルヘキシル基とすることがさらに好ましい。
ハロゲノアルキル基における炭素鎖は、直鎖であっても、分岐鎖であっても、環状であってもよいが、製造容易性の観点からは直鎖であることが好ましい。
ハロゲノアルキル基が有していてもよい置換基としては、水酸基、アルコキシ基などが挙げられ、製造容易性の観点からは無置換であることが好ましい。
また、Zは、直接結合又はカルボニル基を表すが、ある態様として、密着性の観点から直接結合であることが好ましく、別の態様として、感度の観点からカルボニル基であることが好ましい。
R24は、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表し;
R25は、水酸基、カルボキシル基又は下記一般式(C-II-1)で表される基を表し;
hは、0~5の整数を表し;
式(C-II)中に示されるベンゼン環は、さらに置換基を有していてもよい。
R25bは、置換基を有していてもよいアルキレン基を表し;
R25bのアルキレン部分は、-O-、-S-、-COO-又は-OCO-により1~5回中断されていてもよく;
R25のアルキレン部分は分岐側鎖があってもよく、シクロヘキシレンであってもよく;
R25cは、水酸基又はカルボキシル基を表す。
アルキル基が有していてもよい置換基としては、芳香族環基、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基などが挙げられ、アルカリ現像性の観点から水酸基、カルボキシル基が好ましく、カルボキシル基がより好ましい。また、合成容易性の観点からは、無置換であることが好ましい。
芳香族環基が有していてもよい置換基としては、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基、アルキル基などが挙げられ、現像性の観点から水酸基、カルボキシル基が好ましく、カルボキシル基がより好ましい。
これらの中でも、現像性の観点から、R23が置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、メチル基であることがさらに好ましい。
アルキル基が有していてもよい置換基としては、ハロゲン原子、水酸基、カルボキシル基、アミノ基、アミド基などが挙げられ、アルカリ現像性の観点から水酸基、カルボキシル基が好ましく、カルボキシル基がより好ましく、他方合成容易性の観点からは無置換であることが好ましい。
また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、1個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
芳香族環基が有していてもよい置換基としては、アルキル基、ハロゲン原子、水酸基、カルボキシル基などが挙げられる。
これらの中でも、感度の観点から、R24が置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、メチル基であることがさらに好ましい。
他方、製版性の観点から、R24が置換基を有していてもよい芳香族環基であることが好ましく、置換基を有していてもよい芳香族炭化水素基であることがより好ましく、無置換の芳香族炭化水素基であることがさらに好ましく、フェニル基であることが特に好ましい。
前記一般式(C-II-1)において、前述のとおり、R25aは、-O-、-S-、-OCO-又は-COO-を表すが、これらの中でも、感度及び現像性の観点から、-O-又は-OCO-が好ましく、-O-がより好ましい。
R25bにおけるアルキレン基の炭素数は特に限定されないが、感光性着色組成物への溶解性の観点から1以上であることが好ましく、2以上であることがより好ましく、また、20以下であることが好ましく、10以下であることがより好ましく、5以下であることがさらに好ましく、3以下であることが特に好ましい。上限と下限の組み合わせとしては、1~20が好ましく、1~10がより好ましく、2~5がさらに好ましく、2又は3が特に好ましく挙げられる。
アルキレン基は、直鎖でもよく、分岐していてもよく、脂肪族環を含むものであってもよい。これらの中でも、感光性着色組成物への溶解性の観点から、直鎖であることが好ましい。
他方、合成容易性の観点からは、hは0であることが好ましい。
光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、日本国特開平4-221958号公報、日本国特開平4-219756号公報に記載のキサンテン色素、日本国特開平3-239703号公報、日本国特開平5-289335号公報に記載の複素環を有するクマリン色素、日本国特開平3-239703号公報、日本国特開平5-289335号公報に記載の3-ケトクマリン化合物、日本国特開平6-19240号公報に記載のピロメテン色素、その他、日本国特開昭47-2528号公報、日本国特開昭54-155292号公報、日本国特公昭45-37377号公報、日本国特開昭48-84183号公報、日本国特開昭52-112681号公報、日本国特開昭58-15503号公報、日本国特開昭60-88005号公報、日本国特開昭59-56403号公報、日本国特開平2-69号公報、日本国特開昭57-168088号公報、日本国特開平5-107761号公報、日本国特開平5-210240号公報、日本国特開平4-288818号公報に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。
増感色素もまた1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の感光性着色組成物は、(d)エチレン性不飽和化合物を含む。(d)エチレン性不飽和化合物を含むことで、感度が向上する。
本発明に用いられるエチレン性不飽和化合物は、分子内にエチレン性不飽和基を少なくとも1個有する化合物である。具体的には、例えば(メタ)アクリル酸、(メタ)アクリル酸アルキルエステル、アクリロニトリル、スチレン、及びエチレン性不飽和結合を1個有するカルボン酸と、多価又は1価アルコールのエステル、等が挙げられる。
多官能エチレン性単量体の例としては、例えば脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル;芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル;脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられる。
これらは1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の感光性着色組成物は、(e)溶剤を含む。(e)溶剤を含むことで、顔料を溶剤中に分散でき、また、塗布が容易となる。
本発明の感光性着色組成物は、通常、(a)着色剤、(b)アルカリ可溶性樹脂、(c)光重合開始剤、(d)エチレン性不飽和化合物、(f)分散剤、及び必要に応じて使用されるその他の各種材料が、溶剤に溶解又は分散した状態で使用される。溶剤の中でも、分散性や塗布性の観点から有機溶剤が好ましい。
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-ブチルエーテル、プロピレングリコール-t-ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、3-メトキシブタノール、3-メチル-3-メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類;
エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類;
エチレングリコールジアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキサノールジアセテートなどのグリコールジアセテート類;
シクロヘキサノールアセテートなどのアルキルアセテート類;
アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類;
エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような1価又は多価アルコール類;
n-ペンタン、n-オクタン、ジイソブチレン、n-ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類;
シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類;
アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、γ-ブチロラクトンのような鎖状又は環状エステル類;
3-メトキシプロピオン酸、3-エトキシプロピオン酸のようなアルコキシカルボン酸類;
ブチルクロリド、アミルクロリドのようなハロゲン化炭化水素類;
メトキシメチルペンタノンのようなエーテルケトン類;
アセトニトリル、ベンゾニトリルのようなニトリル類等。
これらの有機溶剤は、単独で用いてもよく、2種以上を併用してもよい。
グリコールアルキルエーテルアセテート類は、単独で使用してもよいが、他の有機溶剤を併用してもよい。併用する有機溶剤として、特に好ましいのはグリコールモノアルキルエーテル類である。中でも、組成物中の構成成分の溶解性からプロピレングリコールモノメチルエーテルが好ましく、3-メトキシブタノールがより好ましい。
なお、グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると顔料が凝集しやすく、後に得られる着色樹脂組成物の粘度が上がっていくなどの保存安定性が低下する傾向があるので、グリコールモノアルキルエーテル類を併用する場合、溶剤中のグリコールモノアルキルエーテル類の割合は5質量%~30質量%が好ましく、5質量%~20質量%がより好ましい。
好ましい高沸点溶剤として、例えば前述の各種溶剤の中ではジエチレングリコールモノ-n-ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキサノールジアセテート、トリアセチンなどが挙げられる。
本発明の感光性着色組成物においては、(a)着色剤を微細に分散させ、かつその分散状態を安定化させることが品質の安定性確保には重要なため、(f)分散剤を含む。
(f)分散剤としては、官能基を有する高分子分散剤が好ましく、さらに、分散安定性の面からカルボキシル基;リン酸基;スルホン酸基;又はこれらの塩基;一級、二級又は三級アミノ基;四級アンモニウム塩基;ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。中でも特に、一級、二級又は三級アミノ基;四級アンモニウム塩基;ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が顔料を分散する際に少量の分散剤で分散することができるとの観点から特に好ましい。
これらの高分子分散剤は1種を単独で使用してもよく、又は2種以上を併用してもよい。
これらの内、顔料の分散性の観点から、(f)分散剤は官能基を有するウレタン系高分子分散剤及びアクリル系高分子分散剤の一方又は両方を含むことが好ましく、アクリル系高分子分散剤を含むことが特に好ましい。
また分散性、保存性の面から、塩基性官能基を有し、ポリエステル結合及びポリエーテル結合の一方又は両方を有する高分子分散剤が好ましい。
ウレタン系高分子分散剤として好ましい化学構造を具体的に例示するならば、例えば、ポリイソシアネート化合物と、分子内に水酸基を1個又は2個有する数平均分子量300~10,000の化合物と、同一分子内に活性水素と3級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量1,000~200,000の分散樹脂等が挙げられる。これらをベンジルクロリド等の四級化剤で処理することで、3級アミノ基の全部又は一部を4級アンモニウム塩基にすることができる。
これらは1種を単独で用いてもよく、2種以上を併用してもよい。
ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら2種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン-プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの2種以上の混合物が挙げられる。
これらは1種を単独で用いてもよく、2種以上を併用してもよい。
活性水素、即ち、酸素原子、窒素原子又は硫黄原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に1級のアミノ基の水素原子が好ましい。
このような同一分子内に活性水素と3級アミノ基を有する化合物を例示するならば、N,N-ジメチル-1,3-プロパンジアミン、N,N-ジエチル-1,3-プロパンジアミン、N,N-ジプロピル-1,3-プロパンジアミン、N,N-ジブチル-1,3-プロパンジアミン、N,N-ジメチルエチレンジアミン、N,N-ジエチルエチレンジアミン、N,N-ジプロピルエチレンジアミン、N,N-ジブチルエチレンジアミン、N,N-ジメチル-1,4-ブタンジアミン、N,N-ジエチル-1,4-ブタンジアミン、N,N-ジプロピル-1,4-ブタンジアミン、N,N-ジブチル-1,4-ブタンジアミン等が挙げられる。
これらは1種を単独で用いてもよく、2種以上を併用してもよい。
ウレタン系高分子分散剤の重量平均分子量(Mw)は通常1,000~200,000、好ましくは2,000~100,000、より好ましくは3,000~50,000の範囲である。前記下限値以上とすることで分散性及び分散安定性が良化する傾向があり、前記上限値以下とすることで溶解性が向上し分散性が良化する傾向がある。
該A-B又はB-A-Bブロック共重合体は、例えば、以下に示すリビング重合法にて調製される。
リビング重合法には、アニオンリビング重合法、カチオンリビング重合法、ラジカルリビング重合法があり、このうち、アニオンリビング重合法は、重合活性種がアニオンであり、例えば下記スキームで表される。
また、本発明で用いることができるA-Bブロック共重合体、B-A-Bブロック共重合体1g中の4級アンモニウム塩基の量は、通常0.1~10mmolであることが好ましく、この範囲内にすることで良好な分散性を確保できる傾向がある。
ここで、これらのブロック共重合体等の分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分1gあたりの塩基量と当量のKOHの質量で表し、次の方法により測定する。
100mLのビーカーに分散剤試料の0.5~1.5gを精秤し、50mLの酢酸で溶解する。pH電極を備えた自動滴定装置を使って、この溶液を0.1mol/LのHClO4酢酸溶液にて中和滴定する。滴定pH曲線の変曲点を滴定終点とし次式によりアミン価を求める。
また、このブロック共重合体の酸価は、該酸価の元となる酸性基の有無及び種類にもよるが、一般に低い方が好ましく、通常10mgKOH/g以下であり、その重量平均分子量(Mw)は、1000~100,000の範囲が好ましい。前記範囲内とすることで良好な分散性を確保できる傾向がある。
R31~R33のうち2つ以上が互いに結合して環状構造を形成してもよく;
R34は水素原子又はメチル基であり;
Xは2価の連結基であり;
Y-は対アニオンである。
R35及びR36が互いに結合して環状構造を形成してもよく;
R37は水素原子又はメチル基であり;
Zは2価の連結基である。
上記式(ii)のR35及びR36における、置換基を有していてもよいアリール基としては、上記式(i)のR31~R33として例示したものを好ましく採用することができる。
上記式(ii)のR35及びR36における、置換基を有していてもよいアラルキル基としては、上記式(i)のR31~R33として例示したものを好ましく採用することができる。
また、上記式(i)において、対アニオンのY-としては、Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 -等が挙げられる。
R42は水素原子又はメチル基であり;
nは1~20の整数である。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分枝状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。
R38における、アルキル基が有していてもよい置換基としては、ハロゲン原子、アルコキシ基等が挙げられる。また、アリール基又はアラルキル基が有していてもよい置換基としては、鎖状のアルキル基、ハロゲン原子、アルコキシ基等が挙げられる。また、R38で示される鎖状のアルキル基には、直鎖状及び分岐鎖状のいずれも含まれる。
本発明の感光性着色組成物には、上述の成分の他、シランカップリング剤等の密着向上剤、界面活性剤(塗布性向上剤)、顔料誘導体、光酸発生剤、架橋剤、メルカプト化合物、現像改良剤、紫外線吸収剤、酸化防止剤等を適宜配合することができる。
本発明の感光性着色組成物には、基板との密着性を改善するため、密着向上剤を含有させてもよい。密着向上剤としては、シランカップリング剤、燐酸基含有化合物等が好ましい。
シランカップリング剤の種類としては、エポキシ系、(メタ)アクリル系、アミノ系等種々のものを、1種を単独で、あるいは2種以上を混合して使用できる。
燐酸基含有化合物としては、(メタ)アクリロイル基含有ホスフェート類が好ましく、下記一般式(g1)、(g2)又は(g3)で表されるものが好ましい。
l及びl’は1~10の整数を表し;
mは1、2又は3を表す。
これらの燐酸基含有化合物は、1種類を単独で用いても、2種以上を組み合わせて使用してもよい。
本発明の感光性着色組成物には、塗布性向上ため、界面活性剤を含有させてもよい。
このような界面活性剤としては、例えば、TSF4460(ジーイー東芝シリコーン社製)、DFX-18(ネオス社製)、BYK-300、BYK-325、BYK-330(ビックケミー社製)、KP340(信越シリコーン社製)、メガファック F-470、F-475、F-478、F-559(DIC社製)、SH7PA(トーレシリコーン社製)、DS-401(ダイキン社製)、L-77(日本ユニカー社製)、FC4430(住友3M社製)等が挙げられる。
なお、界面活性剤は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
本発明の感光性着色組成物には、分散性、保存性向上のため、分散助剤として顔料誘導体を含有させてもよい。
顔料誘導体としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系等の誘導体が挙げられるが、中でもフタロシアニン系、キノフタロン系が好ましい。
顔料誘導体の置換基としてはスルホン酸基、スルホンアミド基及びその4級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシル基、アミド基等が顔料骨格に直接又はアルキル基、アリール基、複素環基等を介して結合したものが挙げられ、好ましくはスルホン酸基である。またこれら置換基は一つの顔料骨格に複数置換していてもよい。
光酸発生剤とは、紫外線により酸を発生することができる化合物であり、露光を行った際に発生する酸の作用により、例えばメラミン化合物等架橋剤があることで架橋反応を進行させることとなる。係る光酸発生剤の中でも、溶剤に対する溶解性、特に感光性着色組成物に使われる溶剤に対する溶解性が大きいものが好ましいものであり、例えば、ジフェニルヨードニウム、ジトリルヨードニウム、フェニル(p-アニシル)ヨードニウム、ビス(m-ニトロフェニル)ヨードニウム、ビス(p-tert-ブチルフェニル)ヨードニウム、ビス(p-クロロフェニル)ヨードニウム、ビス(n-ドデシル)ヨードニウム、p-イソブチルフェニル(p-トリル)ヨードニウム、p-イソプロピルフェニル(p-トリル)ヨードニウムなどのジアリールヨードニウム、あるいはトリフェニルスルホニウムなどのトリアリールスルホニウムのクロリド、ブロミド、あるいはホウフッ化塩、ヘキサフルオロフォスフェート塩、ヘキサフルオロアルセネート塩、芳香族スルホン酸塩、テトラキス(ペンタフルオロフェニル)ボレート塩等や、ジフェニルフェナシルスルホニウム(n-ブチル)トリフェニルボレート等のスルホニウム有機ホウ素錯体類、あるいは、2-メチル-4,6-ビストリクロロメチルトリアジン、2-(4-メトキシフェニル)-4,6-ビストリクロロメチルトリアジンなどのトリアジン化合物等を挙げることができるがこの限りではない。
本発明の感光性着色組成物には、さらに架橋剤を加えることができ、例えばメラミン又はグアナミン系の化合物を用いることができる。これら架橋剤としては、例えば、下記一般式(6)で示されるメラミン又はグアナミン系の化合物を挙げることができる。
R61が-NR66R67基の場合、R62、R63、R64、R65、R66及びR67の一つが-CH2OR68基を表し;
R61が炭素数6~12のアリール基の場合、R62、R63、R64及びR65の一つが-CH2OR68基を表し;
R62、R63、R64、R65、R66及びR67の残りは各々独立に、水素又は-CH2OR68基を表し;
R68は水素原子又は炭素数1~4のアルキル基を表す。
R61における、炭素数6~12のアリール基は典型的にはフェニル基、1-ナフチル基又は2-ナフチル基であり、これらのフェニル基やナフチル基には、アルキル基、アルコキシ基、ハロゲン原子などの置換基が結合していてもよい。アルキル基及びアルコキシ基は、それぞれ炭素数1~6程度であることができる。R68で表されるアルキル基は、上記のなかでも、メチル基又はエチル基、とりわけメチル基であるのが好ましい。
R62、R63、R64、R65、R66及びR67の残りは各々独立に、水素原子又は-CH2OR68基を表し;
R68は水素原子又はアルキル基を表す。
架橋剤を用いる際の量は、感光性着色組成物の全固形分に対して0.1~15質量%が好ましく、特に好ましくは0.5~10質量%である。
重合促進剤として、また、基板への密着性の向上のため、メルカプト化合物を添加することも可能である。
これらは種々のものを、1種を単独で、あるいは2種以上を組み合わせて使用できる。
本発明の感光性着色組成物において、感光性着色組成物の全固形分に占める(a)着色剤の含有割合は20質量%以上であり、30質量%以上であることが好ましく、35質量%以上であることがさらに好ましく、40質量%以上であることが特に好ましく、また、通常60質量%以下であることが好ましく、50質量%以下であることがより好ましい。(a)着色剤の含有割合を前記下限値以上とすることで、十分な光学濃度(OD)が得られる傾向があり、また、前記上限値以下とすることで十分な製版特性や耐溶剤性、機械的特性の確保ができる傾向がある。上限と下限の組み合わせとしては、20~60質量%が好ましく、30~50質量%がより好ましく、35~50質量%がさらに好ましく、40~50質量%が特に好ましく挙げられる。
また、本発明の感光性着色組成物中に占める増感色素の配合割合は感度の観点から感光性着色組成物中の全固形分中、通常20質量%以下、好ましくは15質量%以下、さらに好ましくは10質量%以下である。
また、(a)着色剤100質量部に対する(f)分散剤の含有割合は、通常5質量部以上、10質量部以上が特に好ましく、通常50質量部以下、特に30質量部以下であることが好ましい。上限と下限の組み合わせとしては、5~50質量部が好ましく、10~30質量部がより好ましく挙げられる。(f)分散剤の含有割合を前記下限値以上とすることで、十分な分散性が得られやすい傾向があり、前記上限値以下とすることで相対的に他の成分の割合が減ることで感度、製版性等が低下するのを抑制できる傾向がある。
本発明の感光性着色組成物は、着色スペーサー形成用に好適に使用することができ、着色スペーサーとして用いるとの観点からは黒色を呈していることが好ましい。また、その硬化した塗膜の膜厚1μm当たりの光学濃度(OD)が1.0以上であることが好ましく、1.2以上であることがより好ましく、1.5以上であることがさらに好ましく、1.8以上であることが特に好ましく、通常4.0以下であり、3.0以下であることがより好ましい。上限と下限の組み合わせとしては、1.0~4.0が好ましく、1.2~4.0がより好ましく、1.5~3.0がさらに好ましく、1.8~3.0が特に好ましく挙げられる。
本発明の感光性着色組成物(以下、「レジスト」と称することがある。)は、常法に従って製造される。
通常、(a)着色剤は、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理するのが好ましい。分散処理により(a)着色剤が微粒子化されるため、レジストの塗布特性が向上する。
このように、レジストを製造する工程において、(a)着色剤、(e)溶剤、及び(f)分散剤を少なくとも含有する着色剤分散液を製造することが好ましい。着色剤分散液に用いることができる(a)着色剤、(e)有機溶剤、及び(f)分散剤としては、それぞれ感光性着色組成物に用いることができるものとして記載したものを好ましく採用することができる。
サンドグラインダーで(a)着色剤を分散させる場合には、0.1~8mm程度の粒子径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は通常0℃から100℃であり、好ましくは室温から80℃の範囲である。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。レジストの20度鏡面光沢度(JIS Z8741)が50~300の範囲となるように、インキの光沢を制御するのが分散の目安である。レジストの光沢度が低い場合には、分散処理が十分でなく荒い顔料(色材)粒子が残っていることが多く、現像性、密着性、解像性等が不十分となる可能性がある。また、光沢値が上記範囲を超えるまで分散処理を行うと、顔料が破砕して超微粒子が多数生じるため、却って分散安定性が損なわれる傾向がある。
次に、上記分散処理により得られたインキと、レジスト中に含まれる、上記の他の成分を混合し、均一な混合液とする。レジストの製造工程においては、微細なゴミが液中に混じることが多いため、得られたレジストはフィルター等により濾過処理するのが望ましい。
本発明の感光性着色組成物を硬化させることで、硬化物を得ることができる。感光性着色組成物を硬化して得られる硬化物は、着色スペーサーとして好適に用いることができる。
次に、本発明の感光性着色組成物を用いた着色スペーサーについて、その製造方法に従って説明する。
着色スペーサーを形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。主に透明基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォンなどの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ(メタ)アクリル系樹脂などの熱硬化性樹脂シート、又は各種ガラスなどが挙げられる。この中でも、耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にITO、IZO等の透明電極が成膜されている場合もある。透明基板以外では、TFTアレイ上に形成することも可能である。
透明基板の厚さは、通常0.05~10mm、好ましくは0.1~7mmの範囲とされる。また各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常0.01~10μm、好ましくは0.05~5μmの範囲である。
本発明の感光性着色組成物は、公知のカラーフィルター用感光性着色組成物と同様の用途に使用されるが、以下、着色スペーサー(ブラックフォトスペーサー)として使用される場合について、本発明の感光性着色組成物を用いたブラックフォトスペーサーの形成方法の具体例に従って説明する。
[1]基板への供給方法
本発明の感光性着色組成物は、通常、溶剤に溶解あるいは分散された状態で、基板上へ供給される。その供給方法としては、従来公知の方法、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法などによって行うことができる。また、インクジェット法や印刷法などにより、パターン状に供給されてもよい。中でも、ダイコート法によれば、塗布液の使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くない、異物発生が抑制されるなど、総合的な観点から好ましい。
基板上に感光性着色組成物を供給した後の乾燥は、ホットプレート、IRオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。また、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせてもよい。
露光は、感光性着色組成物の塗布膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。露光マスクを用いて露光を行う場合には、露光マスクを感光性着色組成物の塗布膜に近接させる方法や、露光マスクを感光性着色組成物の塗布膜から離れた位置に配置し、該露光マスクを介した露光光を投影する方法によってもよい。また、マスクパターンを用いないレーザー光による走査露光方式によってもよい。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、脱酸素雰囲気下で行ったり、光重合性層上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ったりしてもよい。
中間透過開口部は、例えば、微小な多角形の遮光ユニットを有するマトリックス状遮光パターンによって作成する方法等が知られている。また吸収体として、クロム系、モリブデン系、タングステン系、シリコン系などの材料の膜によって、光透過率を制御し作成する方法等が知られている。
また、近接露光方式の場合には、露光対象とマスクパターンとの距離としては、通常10μm以上、好ましくは50μm以上、より好ましくは75μm以上であり、通常500μm以下、好ましくは400μm以下、より好ましくは300μm以下である。
上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。この水溶液には、さらに界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。
これらのアルカリ性化合物は、2種以上の混合物であってもよい。
現像の後の基板には、必要により上記の露光方法と同様な方法により追露光を行っても良く、また熱硬化処理を行ってもよい。この際の熱硬化処理条件は、温度は100℃~280℃の範囲、好ましくは150℃~250℃の範囲で選ばれ、時間は5分間~60分間の範囲で選ばれる。
また、本発明の着色スペーサーの1μm当たりの光学濃度(OD)は、遮光性の観点から、1.2以上が好ましく、1.5以上がより好ましく、1.8以上がさらに好ましく、通常4.0以下であり、3.0以下であることが好ましい。ここで光学濃度(OD)は後述する方法にて測定した値である。
本発明のカラーフィルターは、上述のような本発明の着色スペーサーを備えるものであり、例えば透明基板としてのガラス基板上に、ブラックマトリクスと、赤色、緑色、青色の画素着色層と、オーバーコート層とが積層されて、着色スペーサーを形成した後、配向膜を形成して製造される。画素着色層及び着色スペーサーは液晶駆動側基板上に形成される場合もあり、あるいは透明基板上と液晶駆動側基板上に別々に形成される場合もある。
このような本発明の着色スペーサーを有するカラーフィルターと液晶駆動側基板とを貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入することで、本発明の着色スペーサーを備えた、液晶表示装置等の画像表示装置を製造することができる。画素着色層及び着色スペーサーが液晶駆動側基板上に形成される場合についても同様に製造することができる。
以下の実施例及び比較例で用いた感光性着色組成物の構成成分は次の通りである。
プロピレングリコールモノメチルエーテルアセテート145質量部を窒素置換しながら攪拌し、120℃に昇温した。ここにスチレン10質量部、グリシジルメタクリレート85.2質量部及びトリシクロデカン骨格を有するモノメタクリレート(日立化成社製FA-513M)66質量部を滴下し、及び2,2’-アゾビス-2-メチルブチロニトリル8.47質量部を3時間かけて滴下し、さらに90℃で2時間攪拌し続けた。次に反応容器内を空気置換に変え、アクリル酸43.2質量部にトリスジメチルアミノメチルフェノール0.7質量部及びハイドロキノン0.12質量部を投入し、100℃で12時間反応を続けた。その後、テトラヒドロ無水フタル酸(THPA)56.2質量部、トリエチルアミン0.7質量部を加え、100℃3.5時間反応させた。こうして得られたアルカリ可溶性樹脂-IのGPCにより測定した重量平均分子量Mwは約8400、酸価は80mgKOH/g、二重結合当量は480g/molであった。
日本化薬(株)製「ZCR-1642H」(Mw=6500、酸価=98mgKOH/g、二重結合当量=560g/mol)
上記エポキシアクリレート溶液25質量部及び、トリメチロールプロパン(TMP)0.76質量部、ビフェニルテトラカルボン酸二無水物(BPDA)3.3質量部、テトラヒドロフタル酸無水物(THPA)3.5質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら105℃までゆっくり昇温し反応させた。
樹脂溶液が透明になったところで、メトキシブチルアセテートで希釈し、固形分50質量%となるよう調製し、酸価113mgKOH/g、GPCで測定したポリスチレン換算の重量平均分子量(Mw)2600、二重結合当量520g/molのカルボキシル基含有エポキシアクリレート樹脂(アルカリ可溶性樹脂-III)を得た。
無水コハク酸17質量部と市販のジペンタエリスリトールポリアクリレート(新中村化学社製A-9550)350質量部を、トリエチルアミン1.8質量部、及び4-メトキシフェノール0.12質量部、プロピレングリコールモノメチルエーテルアセテート91.8質量部の存在下に85℃で6時間反応させることにより、1分子中に1個のカルボキシル基と5個のアクリロイル基を有する多官能アクリレートを含む混合物(a-1)を得た。
続いて、ビスフェノールA型エポキシ樹脂(三菱ケミカル社製jER828、エポキシ当量186)32.7g、前記混合物(a-1)460.7g、2,2,6,6-テトラメチルピぺリジン1-オキシル0.2g、トリフェニルホスフィン8.0g、プロピレングリコールモノメチルエーテルアセテート18.9gを80℃で酸価が2mgKOH/g以下になるまで撹拌した。引き続いて、得られた反応生成物520.5gにプロピレングリコールモノメチルエーテルアセテート161.6gを加えて溶解させた後、1,2,3,6-テトラヒドロ無水フタル酸24.2gを加え、90℃で4時間反応させることにより、アルカリ可溶性樹脂-IVを得た。得られたアルカリ可溶性樹脂-IVは、酸価23mgKOH/g、GPCで測定したポリスチレン換算の重量平均分子量(Mw)が3000、二重結合当量は120g/molのものであった。なお、アルカリ可溶性樹脂-IVには以下の構造のアルカリ可溶性樹脂が含まれ、その二重結合当量は189g/molであった。
無水コハク酸120質量部と市販のペンタエリスリトールトリアクリレート596質量部を、トリエチルアミン2.5質量部、及びハイドロキノン0.25質量部の存在下に100℃で5時間反応させることにより、1分子中に1個のカルボキシル基と3個のアクリロイル基を有する多官能アクリレート67質量%とペンタエリスリトールトリアクリレート33質量%とからなる酸価94mgKOH/gの多官能アクリレート混合物(a-2)を得た。
次に9,9-ビス(4’-ヒドロキシフェニル)フルオレンのジエポキシ化物(エポキシ当量231)231質量部、前記多官能アクリレート混合物(a-2)597質量部、トリエチルベンジルアンモニウムクロライド17.08質量部、及びp-メトキシフェノール0.25質量部、プロピレングリコールモノメチルエーテルアセテート219質量部を仕込み、25mL/分の速度で空気を吹き込みながら88~90℃で加熱溶解させ、酸価が0.8mgKOH/gに達するまで溶液を8時間加熱攪拌し続け、無色透明の反応生成物を得た。引き続いて、得られた反応生成物に1,2,3,6-テトラヒドロ無水フタル酸137質量部を加えて88~90℃で4時間反応させることにより、アルカリ可溶性樹脂-Vを得た。得られたアルカリ可溶性樹脂-Vは、酸価54mgKOH/g、GPCで測定したポリスチレン換算の重量平均分子量(Mw)が2500、二重結合当量は219g/molのものであった。なお、アルカリ可溶性樹脂-Vには以下の構造のアルカリ可溶性樹脂が含まれ、その二重結合当量は261g/molであった。
BASF社製、Irgaphor(登録商標) Black S 0100 CF(下記式(I-1)で表される化学構造を有する)
ビックケミー社製「BYK-LPN21116」(側鎖に4級アンモニウム塩基及び3級アミノ基を有するAブロックと、4級アンモニウム塩基及び3級アミノ基を有さないBブロックからなる、アクリル系A-Bブロック共重合体。アミン価は70mgKOH/g。酸価は1mgKOH/g以下。)
分散剤-IのAブロック中には、下記式(1a)及び(2a)の繰り返し単位が含まれ、Bブロック中には下記式(3a)の繰り返し単位が含まれる。分散剤-Iの全繰り返し単位に占める下記式(1a)、(2a)、及び(3a)の繰り返し単位の含有割合はそれぞれ11.1モル%、22.2モル%、6.7モル%である。
ビックケミー社製「DISPERBYK-167」(ウレタン系高分子分散剤)
ルーブリゾール社製「Solsperse12000」
<溶剤-I>
PGMEA:プロピレングリコールモノメチルエーテルアセテート
<溶剤-II>
MB:3-メトキシブタノール
<光重合開始剤-I>
Irgacure OXE03(BASF社製)
DPHA:日本化薬社製 ジペンタエリスリトールヘキサアクリレート
<添加剤-I>
日本化薬社製、KAYAMER PM-21(メタクリロイル基含有ホスフェート)
<添加剤-II>
東レ・ダウコーニング社製 SH6040
<界面活性剤>
DIC社製 メガファック F-559
単位膜厚当たりの光学濃度は以下の手順にて測定した。
後述のパターン2及びパターン2’を有するガラス基板の光学濃度(OD)を透過濃度計グレタグマクベスD200-IIによって測定し、膜厚を菱化システム社製非接触表面・層断面形状計測システム VertScan(R)2.0により測定した。光学濃度(OD)及び膜厚から、単位膜厚当たりの光学濃度(単位OD値)を算出した。表2及び3中、「単位OD」と表記する。なお、OD値は遮光能力を示す数値であり、数値が大きいほど高遮光性であることを示す。
N-メチルピロリドン(NMP)溶出試験は以下の手順にて行った。
後述のパターン2及びパターン2’を有するガラス基板から測定用基板(2.5cm×1.0cm角)2枚を切り出してN-メチルピロリドン(NMP)8mL入りの10mL容バイアル瓶に浸漬した。そして、その測定用基板入りのバイアル瓶を80℃の熱浴に、40分間静置した状態でNMP溶出試験を実施した。その後に熱浴からバイアル瓶を取り出して、そのNMP溶出溶液(試料溶液)を用いて分光光度計(島津製作所社製「UV-3100PC」)により300~800nmの波長範囲で1nmおきに吸光度を測定した。光源には、ハロゲンランプ及び重水素ランプ(切り替え波長360nm)を使用して、検出器には、フォトマルを使用して、スリット幅2nmを測定条件とした。また、試料溶液は1cm角の石英セルに入れて測定した。吸光度とは、分光法において、ある物体を光が通過した際に光強度がどの程度減衰するかを示す無次元量であり、以下の式で定義される。
したがって、上式の(I/I0)は光透過率を表しており、吸光度Aは、透過率の逆数を対数表現した値ということになる。吸光度Aは、試料溶液に含有する物質の濃度などを算出する際に用いられる表記である。吸光度A=0の場合は、全く光を吸収しない状態(透過率100%)を示しており、吸光度A=∞の場合は、全く光を透過しない状態(透過率0%)を示していることになる。つまり、吸光度が強いほど、レジスト塗膜成分が多くNMPへ溶出しており、NMP耐性が悪いことを示している。測定した吸光度のスペクトル面積(nm)を算出して、面積値30(nm)未満をA、30(nm)以上をBとしてNMP耐性を評価した。表2及び3中、「NMP耐性」と表記し、上段にNMP耐性の評価結果を、下段に実際の面積値を示す。吸光度のスペクトル面積は、各波長における吸光度の和で表すことができ、溶出したレジスト成分の総和を意味していることになる。
NMP溶出溶液の吸収スペクトルの面積値による判定(波長300~800nm)
A:30(nm)未満
B:30(nm)以上
後述のパターン1及びパターン1’を有するガラス基板について、以下の手順にて弾性復元率を測定した。
負荷-除荷試験の微小硬度計として、島津製作所社製(島津ダイナミック超微小硬度計DUH-W201S)を用い、測定温度23℃、直径50μmの平面圧子を使用し、一定速度(3.06gf/sec)でスペーサーに荷重を加え、荷重が30.6gfに達したところで5秒間保持し、続いて同速度にて除荷を行い、荷重-変位曲線を得た。この荷重-変位曲線より、最大変位(μm)及び最終変位(μm)を測定し、下記式により弾性復元率(%)を算出し、以下の評価基準にて圧縮特性を評価した。
A:弾性復元率85%以上
B:弾性復元率85%未満
得られた感光性着色組成物を35℃で9日間保存し、保存後の粘度上昇率で相溶性を評価した。粘度は東機産業株式会社製 RC80L型粘度計(測定条件:23℃、50rpm)により測定した。保存後の粘度上昇率は下記式により算出し、以下の評価基準にて相溶性を評価した。
粘度上昇率(%)=(保存後の粘度-保存前の粘度)/保存前の粘度
A:粘度上昇率10%以下
B:粘度上昇率10%超過
現像形態の評価は以下の手順にて行った。
調製した感光性着色組成物を最終的な膜厚が2.3μmとなるようにスピンコーターにてガラス基板に塗布し、1分間減圧乾燥した後にホットプレートで80℃にて70秒間乾燥した。その後、露光及び現像工程を行い、現像時の非画線部(未露光部)の溶解のしかたを目視観察した。非画線部が現像液に均一に溶解するタイプと非画線部が膜状に剥離されるタイプに大別し、以下の評価基準にて現像性の善し悪しを判定した。剥離するタイプは現像液にレジストの剥離片が残り、パーティクルとして汚染する可能性があり、着色スペーサー製造時の歩留りが低下する場合がある。
AA:非画線部が均一に溶解する
A:わずかに剥離がみられるが、それ以外はほぼ均一に溶解する。
B:膜状の剥離が見られる。
C:現像できない。
表面平滑性及び下記の表面粗度の評価は以下の手順にて行った。
まず、調製した感光性着色組成物を最終的な膜厚が2.3μmとなるようにスピンコーターにてガラス基板に塗布し、1分間減圧乾燥した後にホットプレートで80℃にて70秒間乾燥した。露光及び現像工程を経てからオーブンで230℃にて20分間加熱してレジスト塗工基板を得た。作製したレジスト塗工基板について、前記加熱後の表面におけるシワの発生有無を光学顕微鏡にて70μm×70μmの視野で観察し、以下の評価基準にて評価した。
A:パターンの表面にミクロンオーダーのシワが観察されない
B:パターンの表面にミクロンオーダーのシワが僅かに観察される
C:パターンの表面にミクロンオーダーのシワが著しく目立つ
上記<表面平滑性の評価>にて作製したレジスト塗工基板について、菱化システム社製三次元非接触表面形状計測システム Micromapにて、50倍の光学レンズを用い、Focusモードで70μm×70μmの視野において表面粗度Sa(算術平均粗さ、μm)を測定した。
表1に記載の着色剤、分散剤、アルカリ可溶性樹脂、及び溶剤を、表1に記載の質量比となるように混合した。
この混合物をペイントシェーカーにより25~45℃の範囲で3時間分散処理を行った。ビーズとしては、0.5mmφのジルコニアビーズを用い、分散液の2.5倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して、着色剤分散液1及び着色剤分散液3を調製した。
着色剤としてのカーボンブラック(ビルラー社製、RAVEN1060U)、分散剤、分散助剤及び溶剤を、表1に記載の質量比となるように混合した。
この混合物を攪拌機により十分に攪拌し、プレミキシングを行った。次に、ペイントシェーカーにより25~45℃の範囲で6時間分散処理を行った。ビーズとしては、0.5mmφのジルコニアビーズを用い、分散液と同じ質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して着色剤分散液2を調製した。
Or64:C.I.ピグメントオレンジ64、
V29:C.I.ピグメントバイオレット29、
B60:C.I.ピグメントブルー60、
CB:カーボンブラック。
また、表1中の配合割合はいずれも質量部で表されており、溶剤以外は固形分換算した値である。
上記で調製した着色剤分散液1~3を用いて、固形分中の比率が表2~3の配合割合となるように各成分を加え、さらに全固形分の含有割合が19質量%となるようにPGMEAを加え、攪拌、溶解させて、感光性着色組成物を調製した。得られた感光性着色組成物を用いて、後述する方法でパターンを作成し、前述の方法にて評価を行った。
ガラス基板(旭硝子社製「AN100」)上にスピンコーターを用いて実施例1~4、比較例1及び2の各感光性着色組成物を塗布した。次いで、100℃にて70秒間、ホットプレート上で加熱乾燥して膜厚が2.7μmの塗布膜を形成した。
得られた塗布膜に対し、直径5~50μm(5~20μm:1μmおき、25μm~50μm:5μmおき)の各種直径の円形パターンの完全透過開口部を有する露光マスクを用いて露光処理を施した。露光ギャップ(マスクと塗布面間の距離)は、300μmであった。照射光としては、波長365nmでの強度が32mW/cm2である紫外線を用い、露光量は60mJ/cm2とした。また、紫外線照射は空気下で行った。
これらの操作により、不要部分を除去したパターンを得た。当該パターンの形成された基板をオーブン中、230℃で20分間加熱してパターンを硬化させ、高さが2.3μm、底面の直径が30±2μmの略円柱状のスペーサーパターン(パターン1)を得た。また、露光マスクを使わなかった以外は同様の手順で膜厚が2.3μmの全面被覆パターン(パターン2)も作成した。なお、スペーサーパターンの底面の直径は、(株)キーエンス社製超深度カラー3D形状測定顕微鏡「VK-9500」を用いて測定した。実施例5~9についても同様に膜厚が2.7μmの塗布膜を形成し、同一の露光、現像、及び加熱条件にて、底面の直径が30±2μmの略円柱状のスペーサーパターン(パターン1’)と全面被覆のパターン(パターン2’)を作成した。
これに対して、比較例1の感光性着色組成物を用いた塗布基板は、NMP溶出及び機械的特性が良いが、単位ODが低く遮光性が不足である。また、比較例2は単位ODの値は実施例と同等であるものの、NMP溶出及び機械的特性が悪いことが確認された。
比較例1のように、顔料濃度が低い場合には、エチレン性二重結合が少ない樹脂のみを使用した場合でもNMP溶出や機械的特性は十分なものとなるが、樹脂種はそのままにして、単に顔料濃度を高くするだけでは、比較例2のようにNMP溶出や機械的特性が不十分なものとなる。
また、実施例1と2との比較から、エポキシ(メタ)アクリレート樹脂(b-2)の中でも前記式(ii)で表される部分構造を有するものを採用することで、相溶性が良化することがわかった。これは前記式(ii)で表される部分構造を有するエポキシ(メタ)アクリレート樹脂(b-2)と分散液との相溶性が良好であるためと考えられる。相溶性が良好な場合には、感光性着色組成物の保存安定性が良化する傾向がある。
さらに、実施例1と3との比較から、アルカリ可溶性樹脂中のアルカリ可溶性樹脂(b-1)の含有割合を高くすることでNMP溶出と圧縮特性がさらに良化することがわかった。
実施例1と9の比較から、着色剤として有機黒色顔料を用いた場合でも、NMP溶出及び圧縮特性が良好であることがわかった。
Claims (16)
- (a)着色剤、(b)アルカリ可溶性樹脂、(c)光重合開始剤、(d)エチレン性不飽和化合物、(e)溶剤、及び(f)分散剤を含有する感光性着色組成物であって、
前記感光性着色組成物の全固形分に占める前記(a)着色剤の含有割合が20質量%以上であり、
前記(b)アルカリ可溶性樹脂が、下記式(I)で表される部分構造(1)を有するアルカリ可溶性樹脂(b-1)を含有することを特徴とする感光性着色組成物。
(式(I)中、R1は水素原子又はメチル基を表し;
R2、R3、R5及びR6は各々独立に、置換基を有していてもよいアルキレン基を表し;
R4はn+1価の連結基を表し;
R7は置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基又は置換基を有していてもよい芳香族環基を表し;
l及びmは各々独立に、0~12の整数を表し;
nは3以上の整数を表し;
*は結合手を表す。) - (a)着色剤、(b)アルカリ可溶性樹脂、(c)光重合開始剤、(d)エチレン性不飽和化合物、(e)溶剤、及び(f)分散剤を含有する感光性着色組成物であって、
前記感光性着色組成物の全固形分に占める前記(a)着色剤の含有割合が20質量%以上であり、
前記(b)アルカリ可溶性樹脂が、二重結合当量が400以下であるアルカリ可溶性樹脂(b-1)を含有することを特徴とする感光性着色組成物。 - 前記アルカリ可溶性樹脂(b-1)の、ゲルパーミエーションクロマトグラフィーで測定したポリスチレン換算の重量平均分子量が1000以上である、請求項1又は2に記載の感光性着色組成物。
- 前記感光性着色組成物の全固形分に占める前記アルカリ可溶性樹脂(b-1)の含有割合が1質量%以上である、請求項1~3のいずれか1項に記載の感光性着色組成物。
- 前記(b)アルカリ可溶性樹脂が、さらにエポキシ(メタ)アクリレート樹脂(b-2)を含有する、請求項1~4のいずれか1項に記載の感光性着色組成物。
- 前記(a)着色剤が、有機着色顔料を含有する、請求項1~6のいずれか1項に記載の感光性着色組成物。
- 前記有機着色顔料が、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも1種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも1種とを含有する、請求項7に記載の感光性着色組成物。
- 前記(a)着色剤が、黒色顔料を含有する、請求項1~8のいずれか1項に記載の感光性着色組成物。
- 前記黒色顔料が、カーボンブラック及び有機黒色顔料の一方又は両方を含有する、請求項9に記載の感光性着色組成物。
- 前記有機黒色顔料が、下記一般式(1)で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料である、請求項10に記載の感光性着色組成物。
(式(1)中、R11及びR16は各々独立に、水素原子、CH3、CF3、フッ素原子又は塩素原子を表し;
R12、R13、R14、R15、R17、R18、R19及びR20は各々独立に、水素原子、ハロゲン原子、R21、COOH、COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22、N=CH2、N=CHR21、N=CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21又はSO2NR21R22を表し;
かつ、R12とR13、R13とR14、R14とR15、R17とR18、R18とR19、及びR19とR20からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合し、又は酸素原子、硫黄原子、NH若しくはNR21ブリッジによって互いに結合することもでき;
R21及びR22は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基である。) - 硬化した塗膜の膜厚1μm当たりの光学濃度が1.0以上である、請求項1~11のいずれか1項に記載の感光性着色組成物。
- 着色スペーサー形成用である、請求項1~12のいずれか1項に記載の感光性着色組成物。
- 請求項1~13のいずれか1項に記載の感光性着色組成物を硬化して得られる硬化物。
- 請求項14の硬化物から形成される着色スペーサー。
- 請求項15の着色スペーサーを備える画像表示装置。
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CN111133344A (zh) * | 2017-09-26 | 2020-05-08 | 大阪有机化学工业株式会社 | 光间隔体形成用感光性树脂组合物、光间隔体的形成方法、带光间隔体的基板、及滤色器 |
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