WO2019087985A1 - ネガ型感光性樹脂組成物、硬化膜、並びに有機elディスプレイ及びその製造方法 - Google Patents
ネガ型感光性樹脂組成物、硬化膜、並びに有機elディスプレイ及びその製造方法 Download PDFInfo
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- WO2019087985A1 WO2019087985A1 PCT/JP2018/039958 JP2018039958W WO2019087985A1 WO 2019087985 A1 WO2019087985 A1 WO 2019087985A1 JP 2018039958 W JP2018039958 W JP 2018039958W WO 2019087985 A1 WO2019087985 A1 WO 2019087985A1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- 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
- G02F1/133509—Filters, e.g. light shielding masks
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- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
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- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
- H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
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- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
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- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
- H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers
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- H10K71/10—Deposition of organic active material
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Definitions
- the present invention relates to a negative photosensitive resin composition, a cured film, an organic EL display, and a method of manufacturing the same.
- EL organic electroluminescence
- the organic EL display has a transparent electrode such as indium tin oxide (hereinafter referred to as "ITO") on the light extraction side of the light emitting element, and a metal electrode such as an alloy of magnesium and silver on the light extraction side of the light emitting element.
- ITO indium tin oxide
- metal electrode such as an alloy of magnesium and silver
- an insulating layer called a pixel division layer is formed between the transparent electrode and the metal electrode.
- a light emitting material is deposited by vapor deposition through a vapor deposition mask in a region corresponding to the pixel region, in which the pixel division layer is opened and the underlying transparent electrode or metal electrode is exposed.
- a layer is formed.
- the transparent electrode and the metal electrode are generally formed by sputtering, but in order to prevent disconnection of the formed transparent electrode or metal electrode, a pattern shape with a low taper is required for the pixel division layer Be done.
- the organic EL display has a thin film transistor (hereinafter, “TFT”) for controlling a light emitting element, and a driving TFT, a switching TFT, and the like are formed.
- TFTs are formed as a laminated structure located below the transparent electrode or metal electrode which is the base of the above-mentioned pixel division layer.
- the step due to the TFT formed with these TFTs or the metal wiring connecting the TFTs with each other deteriorates the uniformity etc. in the film formation of the transparent electrode, the metal electrode, the pixel division layer and the light emitting layer formed later. It causes the deterioration of the display characteristics and the reliability of the organic EL display. Therefore, after forming a TFT array, it is general to form a TFT planarizing layer and / or a TFT protective layer to reduce or smooth a step due to the TFT array.
- the organic EL display has a self light emitting element that emits light using energy due to recombination of electrons injected from the cathode and holes injected from the anode. Therefore, if there is a substance that inhibits the movement of electrons or holes, or a substance that forms an energy level that inhibits the recombination of electrons and holes, the light emission efficiency of the light emitting element decreases or the light emitting material deactivates. As a result, the lifetime of the light emitting element is reduced. Since the pixel division layer is formed at a position adjacent to the light emitting element, outgassing from the pixel division layer and the outflow of ionic components can contribute to the reduction of the life of the organic EL display.
- a photosensitive resin composition having high heat resistance a negative photosensitive resin composition using a highly heat resistant polyimide and an oxime ester photopolymerization initiator is known (see, for example, Patent Document 1). .
- the organic EL display has a self light emitting element, when external light such as sunlight is incident outdoors, visibility and contrast are reduced due to the reflection of the external light. Therefore, a technique for reducing external light reflection is required.
- a photosensitive resin composition containing an alkali-soluble polyimide and a colorant is known (see, for example, Patent Document 2). That is, it is a method of reducing external light reflection by forming the pixel division layer which has high heat resistance and light-shielding property using the photosensitive resin composition containing polyimide and coloring agents, such as a pigment.
- the TFT planarization layer and the TFT protective layer are also formed on the light emitting layer through the pixel division layer.
- high heat resistance is required because they are formed at close positions.
- a coloring agent such as a pigment is added to the photosensitive resin composition to impart light shielding properties
- the ultraviolet light etc. at the time of pattern exposure is also blocked as the content of the coloring agent is increased. The sensitivity is reduced.
- any photosensitive resin composition containing a colorant known in the prior art has characteristics for use as a material for forming a pixel division layer, a TFT planarization layer, or a TFT protective layer of an organic EL display. It was inadequate. Specifically, any of the sensitivity, the light shielding property, or the pattern processability of the low taper shape was insufficient.
- the curing of the film deep portion is insufficient at the time of pattern exposure, so the film deep portion is side-etched at the time of development. Therefore, it becomes reverse taper shape after development, and becomes a factor which obstructs pattern formation of low taper shape.
- it is necessary to increase the exposure amount at the time of pattern exposure to accelerate UV curing.
- the exposure amount becomes high, the film is excessively crosslinked at the time of UV curing, and the reflow property at the time of heat curing is reduced, so that a pattern of a highly tapered shape is formed.
- the pattern skirt is also reflowed at the time of heat curing. Therefore, since the pattern opening size width after thermosetting is smaller than the pattern opening size width after development, an error occurs in the pixel design of a display device such as an organic EL display. Further, the variation in the dimension of the pattern opening due to the reflow at the time of heat curing causes the decrease in the panel manufacturing yield. Accordingly, there is also a problem that it is difficult to simultaneously form the low taper pattern and to suppress the change in the dimension opening width of the pattern before and after the thermosetting. In order to achieve both characteristics, it is necessary to form a low-tapered pattern after development, to suppress reflow during heat curing, and to suppress changes in the dimension opening width of the pattern.
- the present invention has been made in view of the above, and an object thereof is to provide a high sensitivity, to form a low-tapered pattern after development, and to suppress a change in dimension opening width of the pattern before and after thermosetting.
- An object of the present invention is to obtain a negative photosensitive resin composition capable of obtaining a cured film excellent in light shielding property.
- a further object of the present invention is that it has high sensitivity, can form a low-tapered pattern after development, can suppress changes in the dimension opening width of the pattern before and after heat curing, and has light shielding properties It is an object of the present invention to provide an excellent cured film and an organic EL display.
- a negative photosensitive resin composition comprises (A) an alkali-soluble resin, (C1) a photopolymerization initiator, and (Da) A negative photosensitive resin composition comprising a blackening agent, wherein the (A) alkali-soluble resin is (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, And (A1-4) a first resin containing at least one selected from the group consisting of polybenzoxazole precursors, and (A1) a first resin, the (A1-1) polyimide, and the (A1-2) polyimide precursor And one or more types selected from the group consisting of the (A1-3) polybenzoxazole and the (A1-4) polybenzoxazole precursor represent structural units having a fluorine atom as the total structural units of 10 (C1)
- the photopolymerization initiator contains (C1-1) an oxime ester photopoly
- X 7 is a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or .
- X 7 which represents an arylene group having 6 to 15 carbon atoms is, In the case of a direct bond, an alkylene group having 1 to 10 carbon atoms, or a cycloal
- the optical density per 1 ⁇ m of the cured film according to the above-mentioned invention is 0.3 to 5.0
- the cured film is a pixel division layer, an electrode insulation Layer, wiring insulating layer, interlayer insulating layer, TFT planarization layer, electrode planarization layer, wiring planarization layer, TFT protective layer, electrode protective layer, wiring protective layer, and gate insulating layer Prepare as.
- the method of manufacturing an organic EL display according to one aspect of the present invention is a method of manufacturing an organic EL display according to the above invention, and the negative photosensitive resin composition according to the above invention is formed on a substrate.
- the negative photosensitive resin composition according to the present invention it is possible to form a pattern having a high sensitivity, a low taper shape after development, and to suppress a change in the dimension opening width of the pattern before and after thermosetting. It is possible to obtain a cured film excellent in the light shielding property.
- the cured film according to the present invention and the organic EL display and the method of manufacturing the same, it is possible to form a pattern with high sensitivity and low taper shape after development, and change in the pattern opening dimension width before and after heat curing. It is possible to obtain a cured film that can be suppressed and has excellent light shielding properties, and to obtain an organic EL display provided with this cured film.
- FIG. 1 is a process diagram schematically illustrating the production process of steps 1 to 7 in an organic EL display using a cured film of the negative photosensitive resin composition of the present invention.
- FIG. 2 is a process diagram schematically illustrating the production process of Steps 1 to 13 in a liquid crystal display using a cured film of the negative photosensitive resin composition of the present invention.
- FIG. 3 is a cross-sectional view showing an example of a cross section of a cured pattern having a step shape.
- FIG. 4 is a schematic view illustrating the manufacturing process of Steps 1 to 4 in the substrate of the organic EL display used for light emission characteristic evaluation in a plan view.
- FIG. 5 is a schematic view illustrating a schematic cross section of the organic EL display having no polarizing layer.
- FIG. 6 is a schematic view illustrating the arrangement and dimensions of the light transmitting portion, the light shielding portion, and the semi-light transmitting portion in the halftone photomask used for halftone characteristic evaluation.
- the negative photosensitive resin composition of the present invention is a negative photosensitive resin composition comprising (A) an alkali-soluble resin, (C1) a photopolymerization initiator, and (Da) a blackening agent, which is characterized in that 1) One type selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor as the alkali-soluble resin (A1) The first resin containing the above, containing (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor One or more types selected from the group consisting of a body have a structural unit having a fluorine atom in 10 to 100 mol% of the total structural unit, and the (C1) photopolymerization initiator is a (C1-1) oxime A stell-based photopolymerization initiator is contained,
- X 7 is a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or .
- X 7 which represents an arylene group having 6 to 15 carbon atoms is,
- R 29 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, .
- X 7 representing the acyl group, or a nitro group having 2 to 10 carbon atoms, 6 carbon atoms
- R 29 is hydrogen, an alkyl group having
- the negative photosensitive resin composition of the present invention contains at least the (A1) first resin as the (A) alkali-soluble resin.
- (A1) One kind of resin selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor as the first resin Contains the above.
- the (A1-1) polyimide, the (A1-2) polyimide precursor, the (A1-3) polybenzoxazole, and the (A1-4) polybenzoxazole precursor may be a single resin or a co-polymer thereof. It may be any of polymers.
- alkali-soluble resin (A1) polyimide (A1) as a first resin from the viewpoint of improving halftone characteristics, improving the heat resistance of a cured film, and improving the reliability of a light emitting element A1-2) It is preferable to contain one or more types selected from the group consisting of a polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, (A1-1) polyimide It is more preferable to contain the (A1-3) polybenzoxazole, and / or to contain the (A1-1) polyimide.
- the polyimide precursor for example, tetracarboxylic acid, corresponding tetracarboxylic acid dianhydride, or tetracarboxylic acid diester dichloride, etc., and diamine, corresponding diisocyanate compound, or trimethylsilylated diamine, etc. And a tetracarboxylic acid residue and / or a derivative residue thereof and a diamine residue and / or a derivative residue thereof.
- the (A1-2) polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.
- polyimide for example, those obtained by subjecting the above-described polyamide acid, polyamide acid ester, polyamide acid amide, or polyisoimide to dehydration and ring closure by heating or reaction using an acid or a base or the like It has a tetracarboxylic acid residue and / or its derivative residue and a diamine residue and / or its derivative residue.
- the polyimide precursor (A1-2) is a thermosetting resin, and is thermally cured at a high temperature for dehydration ring closure to form a highly heat resistant imide bond, thereby obtaining a polyimide (A1-1). Therefore, the heat resistance of the cured film obtained can be remarkably improved by incorporating the polyimide (A1-1) having a highly heat resistant imide bond into the negative photosensitive resin composition. Therefore, it is suitable when using a cured film for the use by which high heat resistance is requested
- (A1-2) polyimide precursor is a resin whose heat resistance improves after dehydration and ring closure, it is used in applications where it is desired to achieve both the characteristics of the precursor structure before dehydration and ring closure and the heat resistance of the cured film. It is suitable.
- the (A1-1) polyimide and the (A1-2) polyimide precursor have an imide bond and / or an amide bond as a bond having polarity. Therefore, when (D1) pigment is contained as (D) coloring agent to be described later, the bond having such polarity interacts strongly with (D1) pigment, and thus the dispersion stability of (D1) pigment is improved. be able to.
- the polyimide (A1-1) used in the present invention preferably contains a structural unit represented by the following general formula (1), from the viewpoint of improving the heat resistance of the cured film.
- R 1 represents a 4- to 10-valent organic group
- R 2 represents a 2- to 10-valent organic group
- R 3 and R 4 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the general formula (5) or the general formula (6).
- p represents an integer of 0 to 6
- q represents an integer of 0 to 8.
- R 1 in the general formula (1) represents a tetracarboxylic acid residue and / or a derivative residue thereof
- R 2 represents a diamine residue and / or a derivative residue thereof.
- the tetracarboxylic acid derivative include tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride, and tetracarboxylic acid active diesters.
- a diamine derivative a diisocyanate compound or trimethylsilylated diamine is mentioned.
- R 1 has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms
- a 4- to 10-valent organic group is preferred.
- R 2 is a divalent to decavalent one having one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms Organic groups are preferred.
- q is preferably 1 to 8.
- the aliphatic structure, alicyclic structure and aromatic structure described above may have a hetero atom, and may be either unsubstituted or substituted.
- R 19 to R 21 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 to 15 carbon atoms. Represents an aryl group.
- R 19 to R 21 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or 6 to 10 carbon atoms An aryl group is preferred.
- the above-mentioned alkyl group, acyl group and aryl group may be either unsubstituted or substituted.
- the polyimide (A1-1) preferably contains the structural unit represented by the general formula (1) as a main component, and the general formula (1) accounts for all the structural units in the polyimide (A1-1).
- the content ratio of the structural unit to be represented is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%.
- the heat resistance of a cured film can be improved as the content ratio is 50 to 100 mol%.
- the (A1-2) polyimide precursor used in the present invention preferably contains a structural unit represented by the following general formula (3), from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development. .
- R 9 represents a 4- to 10-valent organic group
- R 10 represents a 2- to 10-valent organic group
- R 11 represents a substituent represented by the general formula (5) or the general formula (6) described above
- R 12 represents a phenolic hydroxyl group, a sulfonic acid group or a mercapto group
- R 13 represents a phenolic It represents a substituent represented by a hydroxyl group, a sulfonic acid group, a mercapto group, or the above-described formula (5) or formula (6).
- t represents an integer of 2 to 8
- u represents an integer of 0 to 6
- v represents an integer of 0 to 8
- R 9 in the general formula (3) represents a tetracarboxylic acid residue and / or a derivative residue thereof
- R 10 represents a diamine residue and / or a derivative residue thereof.
- the tetracarboxylic acid derivative include tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride, and tetracarboxylic acid active diesters.
- a diamine derivative a diisocyanate compound or trimethylsilylated diamine is mentioned.
- R 9 has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms
- a 4- to 10-valent organic group is preferred.
- R 10 is a divalent to decavalent one having one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms Organic groups are preferred.
- v is preferably 1 to 8.
- the aliphatic structure, alicyclic structure and aromatic structure described above may have a hetero atom, and may be either unsubstituted or substituted.
- the polyimide precursor (A1-2) preferably contains the structural unit represented by the general formula (3) as a main component, and (A1-2) a general formula occupied in all structural units in the polyimide precursor
- the content ratio of the structural unit represented by (3) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol%, the resolution can be improved.
- the amic acid structural unit in the polyimide precursor has a carboxy group as a tetracarboxylic acid residue and / or a derivative residue thereof.
- R 11 in the general formula (3) structural unit represented by the general formula (5) substituents only consists represented by, R 19 is hydrogen (A1-2) a polyimide precursor, ( A1-2a) It is called a polyamic acid.
- R 11 in the structural unit represented by the general formula (3) is a substituent represented by the general formula (5) as the polyimide precursor (A1-2)
- R 19 has 1 to 6 carbon atoms Structural units that are 10 alkyl groups, acyl groups having 2 to 6 carbon atoms, or aryl groups having 6 to 15 carbon atoms are referred to as amic acid ester structural units.
- the amic acid ester structural unit in the polyimide precursor has a carboxylic acid ester group as a group obtained by esterifying a tetracarboxylic acid residue and / or its derivative residue.
- R 11 in the structural unit represented by the general formula (3) is composed of only the substituent represented by the general formula (5), and R 19 is an alkyl group having 1 to 10 carbon atoms, 2 to 6 carbon atoms
- the polyimide precursor (A1-2) which is an acyl group of the above or an aryl group having a carbon number of 6 to 15 is referred to as (A1-2b) polyamic acid ester.
- the amic acid amide structural unit in the polyimide precursor has a carboxylic acid amide group as a group in which a tetracarboxylic acid residue and / or a derivative residue thereof is amidated.
- the (A1-2) polyimide precursor the amic acid structural unit, and the amic acid ester structural unit and / or the amic acid It is preferred to contain an amide structural unit.
- the (A1-2) polyimide precursor containing an amic acid structural unit and an amic acid ester structural unit is referred to as (A1-2-1) polyamic acid partial ester.
- the (A1-2) polyimide precursor containing an amic acid structural unit and an amic acid amide structural unit is referred to as (A1-2-2) polyamic acid partial amide.
- the (A1-2) polyimide precursor containing an amic acid structural unit, an amic acid ester structural unit and an amic acid amide structural unit is referred to as (A1-2-3) polyamic acid partial ester amide.
- These polyimide precursors containing an amic acid structural unit and an amic acid ester structural unit and / or an amic acid amide structural unit have a carboxy group as a tetracarboxylic acid residue and / or a derivative residue thereof (A1- 2a) It can be synthesized from a polyamic acid by esterification of a part of carboxy group and / or amidization of a part of carboxy group.
- the content ratio of the polyamic acid unit in the total structural units in the polyimide precursor (A1-2) is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more.
- the content ratio is 10 mol% or more, the resolution after development can be improved.
- 60 mol% or less is preferable, as for the content rate of a polyamic acid unit, 50 mol% or less is more preferable, and 40 mol% or less is more preferable.
- the content ratio is 60 mol% or less, a pattern with a low taper shape can be formed after development.
- (A1-2) 40 mol% or more is preferable, 50 mol% or more is more preferable, and 60 mol% or more is more preferable as the total of the content ratio of the polyamic acid ester unit and the polyamic acid amide unit in the total structural units in the polyimide precursor .
- the total content ratio is 40 mol% or more, a pattern with a low taper shape can be formed after development.
- 90 mol% or less is preferable, as for the sum total of the content ratio of a polyamic-acid ester unit and a polyamic-acid amide unit, 80 mol% or less is more preferable, and 70 mol% is further more preferable.
- the total content ratio is 90 mol% or less, the resolution after development can be improved.
- the polybenzoxazole precursor can be obtained, for example, by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid active diester with a bisaminophenol compound as a diamine. And have a dicarboxylic acid residue and / or a derivative residue thereof and a bisaminophenol compound residue and / or a derivative residue thereof.
- Examples of (A1-4) polybenzoxazole precursors include polyhydroxyamides.
- polybenzoxazole for example, those obtained by dehydration ring closure of a dicarboxylic acid and a bisaminophenol compound as a diamine by using a polyphosphoric acid, and the polyhydroxyamide described above Include those obtained by cyclodehydration ring closure by heating, or reaction with phosphoric anhydride, a base, or a carbodiimide compound, etc., and dicarboxylic acid residue and / or its derivative residue, and a bisaminophenol compound residue And / or have a derivative residue thereof.
- the (A1-4) polybenzoxazole precursor is a thermosetting resin, and is thermally cured at a high temperature to form a highly heat-resistant and rigid benzoxazole ring by dehydration ring closure, (A1-3) polybenzo An oxazole is obtained. Therefore, the heat resistance of the cured film obtained can be remarkably improved by incorporating the (A1-3) polybenzoxazole having a highly heat resistant and rigid benzoxazole ring into the negative photosensitive resin composition. Therefore, it is suitable when using a cured film for the use by which high heat resistance is requested
- the (A1-4) polybenzoxazole precursor is a resin whose heat resistance improves after dehydration and ring closure, when it is used for applications where the characteristics of the precursor structure before dehydration and ring closure and the heat resistance of the cured film are desired to be compatible And so on.
- the (A1-3) polybenzoxazole and the (A1-4) polybenzoxazole precursor have an oxazole bond and / or an amide bond as a bond having polarity. Therefore, when (D1) pigment is contained as (D) coloring agent to be described later, the bond having such polarity interacts strongly with (D1) pigment, and thus the dispersion stability of (D1) pigment is improved. be able to.
- the (A1-3) polybenzoxazole used in the present invention preferably contains a structural unit represented by the general formula (2) from the viewpoint of improving the heat resistance of the cured film.
- R 5 represents a di- to 10-valent organic group
- R 6 represents a 4- to 10-valent organic group having an aromatic structure
- R 7 and R 8 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above-mentioned general formula (5) or general formula (6).
- r represents an integer of 0 to 8
- s represents an integer of 0 to 6.
- R 5 in the general formula (2) represents a dicarboxylic acid residue and / or a derivative residue thereof
- R 6 represents a bisaminophenol compound residue and / or a derivative residue thereof.
- dicarboxylic acid derivatives include dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.
- R 5 has at least one selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms
- a di- to 10-valent organic group is preferred.
- R 6 is preferably a tetra- to deca-valent organic group having a C 6-30 aromatic structure.
- s is preferably 1 to 8.
- the aliphatic structure, alicyclic structure and aromatic structure described above may have a hetero atom, and may be either unsubstituted or substituted.
- the polybenzoxazole preferably contains the structural unit represented by the general formula (2) as a main component, and the general formula occupied by all structural units in the (A1-3) polybenzoxazole
- the content ratio of the structural unit represented by (2) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%.
- the heat resistance of a cured film can be improved as the content ratio is 50 to 100 mol%.
- the (A1-4) polybenzoxazole precursor used in the present invention may contain the structural unit represented by the general formula (4) from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development. preferable.
- R 14 represents a di- to 10-valent organic group
- R 15 represents a 4- to 10-valent organic group having an aromatic structure
- R 16 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the general formula (5) or the general formula (6) described above
- R 17 represents a phenolic hydroxyl group
- R 18 Represents a sulfonic acid group, a mercapto group, or a substituent represented by the general formula (5) or the general formula (6) described above.
- w represents an integer of 0 to 8
- x represents an integer of 2 to 8
- y represents an integer of 0 to 6, and 2 ⁇ x + y ⁇ 8.
- R 14 in the general formula (4) represents a dicarboxylic acid residue and / or a derivative residue thereof
- R 15 represents a bisaminophenol compound residue and / or a derivative residue thereof.
- dicarboxylic acid derivatives include dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.
- R 14 has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms A di- to 10-valent organic group is preferred.
- R 15 is preferably a tetra- to deca-valent organic group having a C 6-30 aromatic structure.
- the aliphatic structure, alicyclic structure and aromatic structure described above may have a hetero atom, and may be either unsubstituted or substituted.
- the (A1-4) polybenzoxazole precursor preferably contains a structural unit represented by the general formula (4) as a main component, and (A1-4) all structural units in the polybenzoxazole precursor
- the content ratio of the structural unit represented by the general formula (4) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol%, the resolution can be improved.
- tetracarboxylic acids and dicarboxylic acids and their derivatives examples include aromatic tetracarboxylic acids, alicyclic tetracarboxylic acids, and aliphatic tetracarboxylic acids. These tetracarboxylic acids may have a heteroatom other than the oxygen atom of the carboxy group.
- dicarboxylic acid and its derivative in the (A1-3) polybenzoxazole and (A1-4) polybenzoxazole precursor a tricarboxylic acid and / or a derivative thereof may be used.
- dicarboxylic acids and tricarboxylic acids include aromatic dicarboxylic acids, aromatic tricarboxylic acids, alicyclic dicarboxylic acids, alicyclic tricarboxylic acids, aliphatic dicarboxylic acids, and aliphatic tricarboxylic acids. These dicarboxylic acids and tricarboxylic acids may have heteroatoms other than oxygen atom in addition to oxygen atom of carboxy group.
- tetracarboxylic acids examples include the compounds described in WO 2017/057281.
- a diamine and its derivative As a diamine and its derivative (s), an aromatic diamine, a bisamino phenol compound, an alicyclic diamine, an alicyclic dihydroxy diamine, an aliphatic diamine, or an aliphatic dihydroxy diamine is mentioned, for example. These diamines and their derivatives may have hetero atoms in addition to the nitrogen atom and the oxygen atom possessed by the amino group and its derivatives.
- ⁇ Structural unit having a fluorine atom> One or more selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is a structural unit having a fluorine atom Is contained in 10 to 100 mol% of the total structural units.
- a structural unit in which one or more selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor have a fluorine atom By containing these, the transparency can be improved, the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development.
- halftone characteristics can be improved. It is presumed that this is because radical hardening is possible in the deep part of the film by the improvement of the transparency of the film.
- the compatibility between the resin and the initiator can be enhanced, and exposure is performed even in the deep part of the film. It is thought that the UV curing at the time advances efficiently.
- the water repellency can be imparted to the film surface by the fluorine atoms, so that the penetration of the developer into the film surface during alkali development can be suppressed, and the side etching by the developer can be suppressed.
- exposure refers to irradiation with actinic radiation (radiation), and examples include irradiation with visible light, ultraviolet light, electron beam, or X-ray.
- an ultra-high pressure mercury lamp light source capable of irradiating visible light and ultraviolet light is preferable, and j-ray (wavelength 313 nm), i-ray (wavelength 365 nm), h-ray (wavelength) Irradiation with 405 nm) or g-line (wavelength 436 nm) is more preferable.
- exposure means irradiation of actinic radiation (radiation).
- One or more types selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor have a structural unit having a fluorine atom
- the solubility with respect to a solvent can be improved. Therefore, the content of the high polar solvent described above can be reduced, or these resins can be dissolved without using the high polar solvent, and the dispersion stability of the (D1) pigment can be improved.
- a structural unit which has a fluorine atom which (A1-1) polyimide and / or (A1-2) polyimide precursor contains it originates in a structural unit acid derived from tetracarbon which has a fluorine atom, and / or its derivative.
- a structural unit or a structural unit derived from a diamine having a fluorine atom and / or a structural unit derived from a derivative thereof can be mentioned.
- the content ratio of structural units having a fluorine atom is preferably 30 to 100 mol%.
- the content rate of the structural unit which has a fluorine atom 50 mol% or more is more preferable, and 70 mol% or more is further more preferable.
- the content ratio is 30 to 100 mol%, the sensitivity at the time of exposure can be improved.
- carboxylic acids in one or more resins selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor From a tetracarboxylic acid having a fluorine atom, a tetracarboxylic acid derivative having a fluorine atom, a dicarboxylic acid having a fluorine atom, and a dicarboxylic acid derivative having a fluorine atom occupying in the total of structural units derived from the structural unit and its derivative
- the content ratio of structural units derived from one or more selected species is preferably 30 to 100 mol%.
- the content rate of the structural unit which has a fluorine atom 50 mol% or more is more preferable, and 70 mol% or more is further more preferable.
- the content ratio is 30 to 100 mol%, the sensitivity at the time of exposure can be improved.
- the content rate of the structural unit which has a fluorine atom 50 mol% or more is more preferable, and 70 mol% or more is further more preferable.
- the content ratio is 30 to 100 mol%, the sensitivity at the time of exposure can be improved.
- the (A1-1) polyimide and / or the (A1-2) polyimide precursor preferably contains a structural unit derived from an aromatic carboxylic acid and / or a structural unit derived from a derivative thereof.
- the polyimide precursor contains a structural unit derived from an aromatic carboxylic acid and / or a structural unit derived from a derivative thereof, whereby the heat resistance of the aromatic group is obtained. Thus, the heat resistance of the cured film can be improved.
- aromatic carboxylic acid and its derivative aromatic tetracarboxylic acid and / or its derivative are preferable.
- the content ratio of structural units derived from a derivative thereof is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%.
- the heat resistance of a cured film can be improved as the content ratio is 50 to 100 mol%.
- the (A1-3) polybenzoxazole and / or the (A1-4) polybenzoxazole precursor preferably contains a structural unit derived from an aromatic carboxylic acid and / or a structural unit derived from a derivative thereof.
- the polybenzoxazole precursor contains an aromatic carboxylic acid-derived structural unit and / or a structural unit derived from a derivative thereof.
- the heat resistance of the base can improve the heat resistance of the cured film.
- aromatic carboxylic acid and its derivative aromatic dicarboxylic acid or aromatic tricarboxylic acid and / or their derivative are preferable, and aromatic dicarboxylic acid and / or its derivative are more preferable.
- the content ratio of the structural unit derived from the structural unit and / or the derivative thereof is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%.
- the heat resistance of a cured film can be improved as the content ratio is 50 to 100 mol%.
- One or more types selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are derived from aromatic amines It is preferable to contain a structural unit derived from a structural unit and / or a derivative thereof.
- At least one selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is derived from an aromatic amine
- aromatic diamines, bisaminophenol compounds, aromatic triamines, or trisaminophenol compounds, and / or their derivatives are preferable, and aromatic diamines or bisaminophenol compounds, and / or those The derivatives of are more preferred.
- the content ratio of the structural unit derived from the aromatic amine and / or the structural unit derived from the derivative thereof in the total of the structural units derived from the structural unit and the derivative thereof is preferably 50 to 100 mol%, and 60 to 100 mol% Is more preferable, and 70 to 100 mol% is more preferable.
- the heat resistance of a cured film can be improved as the content ratio is 50 to 100 mol%.
- One or more selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor have a silyl group or a siloxane bond It is preferable to contain the structural unit derived from the diamine which it has, and / or the structural unit derived from its derivative (s).
- One or more selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor have a silyl group or a siloxane bond
- the interaction at the interface between the cured film of the negative photosensitive resin composition and the substrate at the base is increased, and the base substrate and And the chemical resistance of the cured film can be improved.
- One or more selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is an amine having an oxyalkylene structure It is preferable to contain a structural unit derived from a structural unit derived from and / or a derivative thereof.
- One or more selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is an amine having an oxyalkylene structure
- a cured film having a low taper pattern shape can be obtained by containing a structural unit derived from a structural unit derived from and / or a derivative thereof, and mechanical properties of the cured film and pattern processability with an alkaline developer Can be improved.
- ⁇ Terminal blocking agent> One or more types selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor have monoamine terminal of resin. It may be capped with an end capping agent such as dicarboxylic acid anhydride, monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester.
- the terminal of the resin is sealed with a terminal blocking agent, whereby (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzo. It is possible to improve the storage stability of the coating solution of the resin composition containing one or more kinds selected from oxazole precursors.
- the content ratio of structural units derived from a derivative can be determined by combining 1 H-NMR, 13 C-NMR, 15 N-NMR, IR, TOF-MS, elemental analysis, ash measurement and the like.
- One or more kinds selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are ethylenically unsaturated double It is preferred to have a linking group. What introduce
- transduced the ethylenically unsaturated double bond group into the side chain of these resin is also preferable by reaction which introduce
- One or more kinds selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are a part of them. What is obtained by reacting a phenolic hydroxyl group and / or a carboxy group with a compound having an ethylenically unsaturated double bond group is also preferable. The reaction described above makes it possible to introduce an ethylenically unsaturated double bond group into the side chain of the resin.
- the compound having an ethylenically unsaturated double bond group is preferably an electrophilic compound having an ethylenically unsaturated double bond group from the viewpoint of reactivity.
- the electrophilic compound for example, isocyanate compound, isothiocyanate compound, epoxy compound, aldehyde compound, thioaldehyde compound, ketone compound, thioketone compound, acetate compound, carboxylic acid chloride, carboxylic acid anhydride, carboxylic acid active ester compound And carboxylic acid compounds, halogenated alkyl compounds, azide alkyl compounds, triflate alkyl compounds, mesylate alkyl compounds, tosylate alkyl compounds, or cyanide alkyl compounds, but from the viewpoint of reactivity and availability of compounds, An isocyanate compound, an epoxy compound, an aldehyde compound, a ketone compound, or a carboxylic acid anhydride is preferable, and an isocyanate compound or an epoxy compound
- Mw 500,000 or less is preferable, 300,000 or less is more preferable, 100,000 or less is more preferable.
- Mw is 500,000 or less, the leveling property at the time of coating and the pattern processability with an alkali developer can be improved.
- Mn number average molecular weight
- 1,000 or more are preferable in polystyrene conversion measured by GPC
- 3,000 or more are more preferable, and 5,000 or more are more preferable.
- the resolution after development can be improved as Mn is 1,000 or more.
- Mn 500,000 or less is preferable, 300,000 or less is more preferable, 100,000 or less is more preferable.
- coating and the pattern processability in alkaline developing solution can be improved as Mn is 500,000 or less.
- Mw and Mn of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are GPC, light scattering method, or X It can be easily measured as a polystyrene conversion value by a small angle scattering method or the like.
- the number n of repeating structural units in the (A1-1) polyimide, the (A1-2) polyimide precursor (A1-3) polybenzoxazole, and the (A1-4) polybenzoxazole precursor is equal to the molecular weight of the structural unit.
- the (A1-1) polyimide and the (A1-2) polyimide precursor can be synthesized by a known method. For example, a method of reacting tetracarboxylic acid dianhydride and diamine (partially replaced with monoamine which is an end capping agent) at 80 to 200 ° C. in a polar solvent such as N-methyl-2-pyrrolidone, or Tetracarboxylic acid dianhydride (partially replaced with a capping agent dicarboxylic acid anhydride, monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester) and diamine at 80 to 200 ° C.
- a polar solvent such as N-methyl-2-pyrrolidone, or Tetracarboxylic acid dianhydride
- dicarboxylic acid anhydride monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester
- the (A1-3) polybenzoxazole and the (A1-4) polybenzoxazole precursor can be synthesized by known methods. For example, a method of reacting a dicarboxylic acid active diester and a bisaminophenol compound (partially replaced with a terminal capping agent monoamine) at 80 to 250 ° C. in a polar solvent such as N-methyl-2-pyrrolidone Or a dicarboxylic acid active diester (partly substituted with a capping agent dicarboxylic acid anhydride, monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester) and a bisaminophenol compound 80
- a polar solvent such as N-methyl-2-pyrrolidone
- a dicarboxylic acid active diester partially substituted with a capping agent dicarboxylic acid anhydride, monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester
- the reaction
- the negative photosensitive resin composition of this invention contains (A2) 2nd resin as (A) alkali-soluble resin.
- (A2) As the second resin from the viewpoint of improvement in sensitivity at the time of exposure and reduction in taper by pattern shape control after development, (A2-1) polysiloxane, (A2-2) polycyclic side chain containing resin, (A2) A2-3) It is preferable to contain one or more types selected from an acid-modified epoxy resin and (A2-4) an acrylic resin.
- (A2-1) polysiloxane, (A2-2) polycyclic side chain-containing resin, (A2-3) acid-modified epoxy resin, and (A2-4) acrylic resin are single resins or those It may be any of the copolymers of
- (A) As the alkali-soluble resin, from the viewpoint of improvement in halftone characteristics, sensitivity improvement at the time of exposure, and reduction in taper by pattern shape control after development, (A2) polysiloxane as the second resin (A2-1) And (A2-2) polycyclic side chain-containing resin, (A2-3) acid-modified epoxy resin, and (A2-4) acrylic resin, preferably containing one or more selected from the group consisting of (A2- 1) It is more preferable to contain one or more selected from the group consisting of polysiloxane, (A2-2) polycyclic side chain-containing resin, and (A2-3) acid-modified epoxy resin, (A2-1) poly It is more preferable to contain a siloxane and / or (A2-2) polycyclic side chain-containing resin, and it is particularly preferable to contain (A2-1) a polysiloxane. Further, by including the (A2-1) polysiloxane, it is possible to form a low taper shape pattern after heat curing, and to suppress a
- (A2-1) Polysiloxane As (A2-1) polysiloxane used for this invention, 1 or more types chosen from trifunctional organosilane, tetrafunctional organosilane, bifunctional organosilane, and monofunctional organosilane are hydrolyzed, for example, and dehydration condensation is carried out. And polysiloxanes obtained by
- (A2-1) Polysiloxane is a thermosetting resin, which is thermally cured at a high temperature for dehydration condensation to form a highly heat-resistant siloxane bond (Si—O). Therefore, the heat resistance of the resulting cured film can be improved by incorporating the (A2-1) polysiloxane having a highly heat resistant siloxane bond into the negative photosensitive resin composition. Moreover, since it is resin which heat resistance improves after dehydration condensation, it is suitable when using for the use which wants to make the characteristic before dehydration condensation and the heat resistance of a cured film make compatible.
- the (A2-1) polysiloxane has a silanol group as a reactive group. Therefore, when the pigment (D1) is contained as a colorant (D) described later, the silanol group can interact and / or bind to the surface of the pigment (D1), and the pigment (D1) It is possible to interact and / or bind to surface modifying groups. Therefore, the dispersion stability of the (D1) pigment can be improved.
- the polysiloxane (A2-1) used in the present invention preferably contains a trifunctional organosilane unit and / or a tetrafunctional organosilane unit from the viewpoint of improving the heat resistance of the cured film and the resolution after development.
- a trifunctional organosilane the organosilane unit represented by General formula (7) is preferable.
- an organosilane unit represented by the general formula (8) is preferable.
- a bifunctional organosilane unit may be contained.
- the organosilane unit represented by General formula (9) is preferable.
- the organosilane unit represented by General formula (10) is preferable.
- R 22 to R 27 each independently represent hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
- R 22 to R 27 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2 to 10 carbon atoms
- An alkenyl group or an aryl group having 6 to 15 carbon atoms is preferable.
- the above-mentioned alkyl group, cycloalkyl group, alkenyl group and aryl group may have a hetero atom and may be either unsubstituted or substituted.
- organosilane which has an organosilane unit represented by General formula (7), General formula (8), General formula (9), or General formula (10), it is described, for example, in WO 2017/057281. Compounds are mentioned.
- the content ratio of the organosilane unit represented by the general formula (7) in the polysiloxane (A2-1) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and more preferably 70 to 100 mol in terms of the Si atom mol ratio. % Is more preferred.
- the heat resistance of a cured film can be improved as the content ratio is 50 to 100 mol%.
- the organosilane unit which has an epoxy group is preferable.
- the content ratio of the organosilane unit represented by the general formula (8) to the polysiloxane (A2-1) is preferably 0 to 40 mol%, more preferably 0 to 30 mol%, and more preferably 0 to 20 mol in terms of a Si atom mol ratio. % Is more preferred.
- the content ratio is 0 to 40 mol%, it is possible to improve pattern processability at the time of alkali development, sensitivity at the time of exposure, and heat resistance of the cured film.
- a pattern with a low taper shape can be formed after development, and changes in the dimension opening width of the pattern before and after heat curing can be suppressed.
- the content ratio of the organosilane unit represented by the general formula (9) in the polysiloxane (A2-1) is preferably 0 to 60 mol%, more preferably 0 to 50 mol%, and more preferably 0 to 40 mol in terms of a Si atom mol ratio. % Is more preferred. When the content ratio is 0 to 60 mol%, the heat resistance of the cured film and the resolution after development can be improved.
- the content ratio of the organosilane unit represented by the general formula (10) in the polysiloxane (A2-1) is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and still more preferably 0 to 5 mol in terms of a Si atom mol ratio. % Is more preferred. When the content ratio is 0 to 20 mol%, the heat resistance of the cured film can be improved.
- an organosilane represented by the general formula (7a), an organosilane represented by the general formula (8a), an organosilane represented by the general formula (9a) And one or more selected from organosilanes represented by the general formula (10a), which are obtained by hydrolyzing and dehydrating condensation are preferable (A2-1) polysiloxanes.
- R 22 to R 27 each independently represent hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group
- R 115 to R 124 are each independently And represents hydrogen, an alkyl group, an acyl group or an aryl group.
- R 22 to R 27 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2 to 10 carbon atoms
- An alkenyl group or an aryl group having 6 to 15 carbon atoms is preferable.
- Each of R 115 to R 124 is preferably independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- the alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, and the acyl group described above may have a hetero atom, and may be either unsubstituted or substituted.
- the organosilane unit represented by the general formula (7), the organosilane unit represented by the general formula (8), the organosilane unit represented by the general formula (9), and the like may be either regular arrangement or irregular arrangement.
- the regular arrangement includes, for example, alternating copolymerization, periodic copolymerization, block copolymerization, graft copolymerization and the like.
- irregular arrangement random copolymerization etc. are mentioned, for example.
- the organosilane unit represented by the general formula (10) may be either a two-dimensional arrangement or a three-dimensional arrangement.
- sequence linear form is mentioned, for example.
- a three-dimensional arrangement for example, a ladder-like shape, a scaly shape, or a mesh shape may be mentioned.
- the (A2-1) polysiloxane used in the present invention preferably contains an organosilane unit having an aromatic group.
- Such (A2-1) polysiloxane is an organosilane having an aromatic group as an organosilane having an organosilane unit represented by the general formula (7), the general formula (9), or the general formula (10) It is preferable that it is obtained using (A2-1)
- the heat resistance of the cured film can be improved by the heat resistance of the aromatic group.
- the (A2-1) polysiloxane contains an organosilane unit having an aromatic group, which causes steric hindrance of the aromatic group. And (D1) the dispersion stability of the pigment can be improved. Furthermore, in the case where the (D1) pigment is the (D1-1) organic pigment, the aromatic group in the (A2-1) polysiloxane interacts with the aromatic group of the (D1-1) organic pigment, so (D1) -1) It is possible to improve the dispersion stability of the organic pigment.
- the content ratio of the organosilane unit having an aromatic group in the polysiloxane (A2-1) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more, in terms of the Si atom mol ratio.
- the heat resistance of a cured film can be improved as a content rate is 5 mol% or more.
- the content ratio is preferably 80 mol% or less, more preferably 75 mol% or less, and still more preferably 70 mol% or less.
- the pattern processability in alkaline developing solution can be improved as a content ratio is 80 mol% or less.
- the Si atom molar ratio represented by the general formula (7), the general formula (9), or the general formula (10) and derived from the organosilane unit having an aromatic group is 5 mol% or more and 80 mol% or less Is preferred.
- the content ratio of various organosilane units in the polysiloxane (A2-1) is a combination of 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, and ash measurement. Can be asked.
- Mw of (A2-1) polysiloxane used for this invention 500 or more are preferable in polystyrene conversion measured by GPC, 700 or more are more preferable, and 1,000 or more are more preferable.
- the resolution after development can be improved as Mw is 500 or more.
- Mw 100,000 or less is preferable, 50,000 or less is more preferable, 20,000 or less is more preferable.
- coating and the pattern processability in alkaline developing solution can be improved as Mw is 100,000 or less.
- the (A2-1) polysiloxane can be synthesized by a known method.
- a method of hydrolyzing organosilane in a reaction solvent and dehydration condensation may be mentioned.
- a method of hydrolyzing organosilane and dehydrating condensation for example, a reaction solvent and water, and, if necessary, a catalyst are added to a mixture containing organosilane, and the reaction is carried out at 50 to 150 ° C, preferably 90 to 130 ° C.
- a method of heating and stirring for about 0.5 to 100 hours may, for example, be mentioned.
- hydrolysis byproducts alcohols such as methanol
- condensation byproducts water
- Examples of the (A2-2) polycyclic side chain-containing resin used in the present invention include the following (I) to (IV) polycyclic side chain-containing resins.
- the polycyclic side chain-containing resin is a thermosetting resin, has a structure in which the main chain and a bulky side chain are connected by one atom, and as a bulky side chain, it has high heat resistance and rigidity. Ring structure such as a fluorene ring. Therefore, the heat resistance of the cured film obtained is improved by containing the resin having a cyclic side chain such as a highly heat resistant and rigid fluorene ring (A2-2) polycyclic side chain containing resin in the negative photosensitive resin composition. It can be done. Therefore, it is suitable when using a cured film for the use which heat resistance is requested
- the (A2-2) polycyclic side chain-containing resin used in the present invention preferably has an ethylenically unsaturated double bond group.
- the sensitivity at the time of exposure can be improved by incorporating the (A2-2) polycyclic side chain-containing resin having an ethylenically unsaturated double bond group into the negative photosensitive resin composition.
- the formed three-dimensional crosslinked structure is mainly composed of an alicyclic structure or an aliphatic structure, it is possible to suppress the increase in temperature of the softening point of the resin and obtain a low-tapered pattern shape.
- Mechanical properties of the cured film can be improved. Therefore, it is suitable when using a cured film for the use which a mechanical characteristic is requested
- the (A2-2) polycyclic side chain-containing resin used in the present invention is a structural unit represented by the general formula (47) or a general formula (48) from the viewpoint of improving the heat resistance of the cured film It is preferable to contain one or more types selected from the structural unit, the structural unit represented by the general formula (49), and the structural unit represented by the general formula (50).
- any one of a main chain, a side chain, and an end from the viewpoint of improving sensitivity at the time of exposure and mechanical properties of a cured film. It is preferable to contain an ethylenically unsaturated double bond group as described above.
- X 69 , X 70 , X 72 , X 73 , X 75 , X 76 , X 78 and X 79 each independently represent a monocyclic or fused polycyclic ring Represents a hydrocarbon ring of
- Each of X 71 , X 74 , X 77 and X 80 independently represents a divalent to ten-valent organic group of a carboxylic acid residue and / or a derivative residue thereof.
- Each of W 1 to W 4 independently represents an organic group having two or more aromatic groups.
- R 160 to R 167 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms
- R 170 to R 175 , R 177 , and R 178 each independently represent hydrogen or ethylenically unsaturated Represents an organic group having a double bond group
- R 176 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- a, b, c, d, e, f, g and h each independently represent an integer of 0 to 10, and ⁇ , ⁇ , ⁇ and ⁇ each independently represent 0 or 1 Represent.
- X 69 , X 70 , X 72 , X 73 , X 75 , X 76 , X 78 and X 79 each independently have 6 to 15 carbon atoms and 2 to 6 carbon atoms
- a 10-valent, monocyclic or fused polycyclic hydrocarbon ring is preferred.
- X 71 , X 74 , X 77 and X 80 each independently represent an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic having 6 to 30 carbon atoms
- the organic group is preferably a di- to deca-valent organic group having one or more kinds selected from group structures.
- W 1 to W 4 are preferably each independently a substituent represented by any one of the general formulas (51) to (56).
- R 170 to R 175 , R 177 and R 178 are preferably each independently a substituent represented by General Formula (57).
- the above-described alkyl group, aliphatic structure, alicyclic structure, aromatic structure, monocyclic or fused polycyclic aromatic hydrocarbon ring, and organic group having an ethylenically unsaturated double bond group are hetero compounds. It may have an atom, and may be either unsubstituted or substituted.
- R 179 to R 182 , R 185 and R 188 each independently represent an alkyl group having 1 to 10 carbon atoms.
- R 183 , R 184 , R 186 , R 187 , R 189 , R 191 and R 193 to R 196 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 4 to 10 carbon atoms Represents a group or an aryl group having 6 to 15 carbon atoms.
- R 190 and R 192 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R 190 and R 192 And may form a ring.
- the ring formed by R 190 and R 192 includes, for example, a benzene ring or a cyclohexane ring.
- At least one of R 183 and R 184 is an aryl group having 6 to 15 carbon atoms.
- At least one of R 186 and R 187 is an aryl group having 6 to 15 carbon atoms.
- At least one of R 189 and R 190 is an aryl group having 6 to 15 carbon atoms
- at least one of R 191 and R 192 is an aryl group having 6 to 15 carbon atoms
- R 190 and R 192 are You may form a ring.
- At least one of R 193 and R 194 is an aryl group having 6 to 15 carbon atoms
- at least one of R 195 and R 196 is an aryl group having 6 to 15 carbon atoms.
- i, j, k, l, m and n each independently represent an integer of 0 to 4.
- R 190 and R 192 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or 6 to 10 carbon atoms And the ring formed by R 190 and R 192 is preferably a benzene ring.
- the above-mentioned alkyl group, cycloalkyl group and aryl group may be either unsubstituted or substituted.
- X 81 is a direct bond, represents an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain of carbon atoms 6 ⁇
- X 82 is a direct It represents a bond or an arylene chain having 6 to 15 carbon atoms.
- R 197 represents a vinyl group, an aryl group or a (meth) acrylic group.
- X 81 is preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms.
- X 82 is preferably a direct bond or an arylene chain having 6 to 10 carbon atoms.
- the above-mentioned alkylene chain, cycloalkylene chain, arylene chain, vinyl group, aryl group, and (meth) acryl group may be either unsubstituted or substituted.
- the (A2-2) polycyclic side chain-containing resin used in the present invention preferably contains a structural unit derived from an aromatic group carboxylic acid and a derivative thereof.
- the heat resistance of the cured film can be improved by the heat resistance of the aromatic group .
- the aromatic carboxylic acid and derivatives thereof are selected from tetracarboxylic acids having an aromatic group, tetracarboxylic acid dianhydrides having an aromatic group, tricarboxylic acids having an aromatic group, and dicarboxylic acids having an aromatic group
- tetracarboxylic acids having an aromatic group tetracarboxylic acid dianhydrides having an aromatic group
- tricarboxylic acids having an aromatic group tricarboxylic acids having an aromatic group
- dicarboxylic acids having an aromatic group One or more types are preferable.
- (D1) pigment when (D1) pigment is especially contained as a (D) coloring agent mentioned later, (A2-2)
- the polycyclic side chain containing resin contains a structural unit derived from aromatic carboxylic acid and its derivative. The steric hindrance of the aromatic group can improve the dispersion stability of the (D1) pigment.
- the aromatic group in the (A2-2) polycyclic side chain-containing resin interacts with the aromatic group of the (D1-1) organic pigment Therefore, the dispersion stability of the (D1-1) organic pigment can be improved.
- aromatic group carboxylic acid and its derivative the compounds contained in the above-mentioned aromatic tetracarboxylic acid and / or its derivative, aromatic tricarboxylic acid and / or its derivative, or aromatic dicarboxylic acid and / or its derivative Can be mentioned.
- the ratio is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and still more preferably 30 to 100 mol%.
- the content ratio is 10 to 100 mol%, the heat resistance of the cured film can be improved.
- the (A2-2) polycyclic side chain-containing resin used in the present invention contains a structural unit derived from a carboxylic acid and a derivative thereof, and (A2-2) the polycyclic side chain-containing resin has an acidic group Is preferred. (A2-2) When the polycyclic side chain-containing resin has an acidic group, pattern processability with an alkali developer and resolution after development can be improved.
- the acidic group a group exhibiting an acidity of less than pH 6 is preferred.
- a carboxy group, a carboxylic anhydride group, a sulfonic acid group, phenolic hydroxyl group, or a hydroxy imide group is mentioned, for example.
- a carboxy group, a carboxylic acid anhydride group, or a phenolic hydroxyl group is preferable, and a carboxy group or a carboxylic acid anhydride group is more preferable, from the viewpoint of pattern processability improvement with an alkaline developer and resolution improvement after development.
- the content ratio of structural units derived from various monomer components in the polycyclic side chain-containing resin is 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis It can be determined by combining the method and the ash content measurement.
- Examples of the (A2-2) polycyclic side chain-containing resin used in the present invention include “ADEKA ARKLS” (registered trademark) WR-101 or WR-301 (all of which are made by ADEKA), OGSOL (registered trademark) Trademarks CR-1030, CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6, CR-TR7, CR-TR8, CR-TR9 Or CR-TR10 (all from Osaka Gas Chemical Co., Ltd.), or TR-B201 or TR-B202 (all from TRONLY).
- ADKA ARKLS registered trademark
- OGSOL registered trademark
- CR-1030 CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6, CR-TR7, CR-TR8, CR-TR9 Or CR-TR10
- TR-B201 or TR-B202 all from TRONLY
- Mw of (A2-2) polycyclic side chain containing resin used for this invention 500 or more are preferable in polystyrene conversion measured by GPC, 1,000 or more are more preferable, and 1,500 or more are more preferable. .
- the resolution after development can be improved as Mw is 500 or more.
- Mw 100,000 or less is preferable, 50,000 or less is more preferable, 20,000 or less is more preferable.
- coating and the pattern processability in alkaline developing solution can be improved as Mw is 100,000 or less.
- Examples of the acid-modified epoxy resin (A2-3) used in the present invention include the following acid-modified epoxy resins (I) to (VI).
- III An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional alcohol compound and a polyfunctional carboxylic acid anhydride.
- the acid-modified epoxy resin is a thermosetting resin, and has a highly heat-resistant aromatic cyclic structure in the epoxy resin skeleton of the main chain. Therefore, the heat resistance of the cured film obtained can be improved by containing the (A2-3) acid-modified epoxy resin in the resin composition. Therefore, it is suitable when using a cured film for the use which heat resistance is requested
- the acid-modified epoxy resin (A2-3) used in the present invention preferably has an ethylenically unsaturated double bond group.
- an acid-modified epoxy resin (A2-3) having an ethylenically unsaturated double bond group into the resin composition, the sensitivity at the time of exposure can be improved.
- the formed three-dimensional crosslinked structure is mainly composed of an alicyclic structure or an aliphatic structure, it is possible to suppress the increase in temperature of the softening point of the resin and obtain a low-tapered pattern shape.
- Mechanical properties of the cured film can be improved. Therefore, it is suitable when using a cured film for the use which a mechanical characteristic is requested
- the acid-modified epoxy resin (A2-3) used in the present invention has a carboxy group and / or a carboxylic anhydride group as an alkali-soluble group.
- a carboxy group and / or a carboxylic acid anhydride group By having a carboxy group and / or a carboxylic acid anhydride group, the resolution after development can be improved.
- the acid-modified epoxy resin (A2-3) used in the present invention a structural unit represented by the general formula (35) or a structural unit represented by the general formula (36) from the viewpoint of improving the heat resistance of the cured film
- the acid-modified epoxy resin (A2-3) used in the present invention may be added to any one or more of the main chain, side chain, and terminal from the viewpoint of improving sensitivity at the time of exposure and mechanical properties of the cured film. It is preferred to have an ethylenically unsaturated double bond group.
- X 51 to X 54 each independently represent an aliphatic structure having 1 to 6 carbon atoms.
- Z 53 represents an aromatic structure having 10 to 25 and 3 to 16 carbon atoms.
- R 71 to R 75 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and
- R 76 and R 77 each represent Each independently represents an alkyl group having 1 to 10 carbon atoms
- R 78 to R 82 each independently represent a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or R represents an aryl group having 6 to 15 carbon atoms
- R 83 to R 88 each independently represent a substituent represented by General Formula (39).
- a, b, c, d and e each independently represent an integer of 0 to 10
- f represents an integer of 0 to 8
- g represents an integer of 0 to 6
- h i
- J and k each independently represent an integer of 0 to 3
- l represents an integer of 0 to 4.
- the alkyl group, the cycloalkyl group, the aryl group, the aliphatic structure, and the aromatic structure described above may have a hetero atom, and may be either unsubstituted or substituted.
- the aromatic structure of Z 53 in the general formula (38) contains one or more kinds selected from the group consisting of a terphenyl structure, a naphthalene structure, an anthracene structure and a fluorene structure. Further, as other aromatic structures of Z 53 in the general formula (38), for example, 1,2,3,4-tetrahydronaphthalene structure, 2,2-diphenylpropane structure, diphenyl ether structure, diphenyl ketone structure or diphenyl sulfone The structure is mentioned.
- X 55 represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms.
- R 89 to R 91 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- R 92 represents hydrogen or a substituent represented by the general formula (40).
- each of R 89 and R 90 independently is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen.
- R 91 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen or a methyl group.
- X56 represents a C1-C6 alkylene chain or a C4-C10 cycloalkylene chain.
- X 56 is preferably an alkylene chain of 1 to 4 carbon atoms or a cycloalkylene chain of 4 to 7 carbon atoms.
- the above-mentioned alkylene chain, cycloalkylene chain, alkyl group and aryl group may be either unsubstituted or substituted.
- X 57 to X 61 each independently represent an aliphatic structure having 1 to 6 carbon atoms
- X 62 and X 63 each independently have 1 carbon atom And an alkylene chain of to 6 or a cycloalkylene chain having 4 to 10 carbon atoms.
- R 93 to R 97 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms
- R 98 to R 104 represent Each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms
- R 105 represents hydrogen or 1 to 6 carbon atoms
- R 106 and R 107 each independently represent a substituent represented by General Formula (39)
- R 108 represents hydrogen, a substituent represented by General Formula (39), or This represents a substituent represented by the general formula (40).
- n, o, p and q each independently represent an integer of 0 to 10
- r and s each independently represent an integer of 0 to 3
- t, u, v, w And x each independently represent an integer of 0 to 4.
- the above-mentioned alkylene chain, cycloalkylene chain, alkyl group, cycloalkyl group, aryl group, and aliphatic structure may have a hetero atom, and may be either unsubstituted or substituted.
- the terminal of the acid-modified epoxy resin having a structural unit represented by the general formula (43) (A2-3) has a general formula (44) It is preferable to have a substituent represented by and / or a substituent represented by General Formula (45).
- R 109 represents a substituent represented by Formula (39).
- X 64 represents an aliphatic structure having 1 to 6 carbon atoms.
- R 110 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R 111 and R 112 each independently represent halogen or carbon And an alkyl group of 1 to 10, a cycloalkyl group of 4 to 10 carbon atoms, or an aryl group of 6 to 15 carbon atoms.
- R 113 represents a substituent represented by General Formula (39).
- ⁇ represents an integer of 0 to 10.
- X 64 is preferably an aliphatic structure having 1 to 4 carbon atoms.
- R 110 is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 111 and R 112 each independently represent a halogen or carbon An alkyl group of 1 to 6 carbons, a cycloalkyl group of 4 to 7 carbons, or an aryl group of 6 to 10 carbons is preferable.
- the acid-modified epoxy resin (A2-3) used in the present invention preferably contains a structural unit derived from an aromatic carboxylic acid and a derivative thereof.
- A2-3) When the acid-modified epoxy resin contains a structural unit derived from an aromatic carboxylic acid and a derivative thereof, the heat resistance of the cured film can be improved by the heat resistance of the aromatic group.
- aromatic carboxylic acids and derivatives thereof include tetracarboxylic acids having aromatic groups, tricarboxylic acids having aromatic groups, tricarboxylic acid anhydrides having aromatic groups, dicarboxylic acids having aromatic groups, and aromatic groups.
- One or more types selected from the dicarboxylic acid anhydrides possessed are preferable.
- the (A2-3) acid-modified epoxy resin contains an aromatic carboxylic acid and a structural unit derived from a derivative thereof, so that the aromatic The steric hindrance of the group group can improve the dispersion stability of the (D1) pigment.
- the aromatic group in the (A2-3) acid-modified epoxy resin interacts with the aromatic group of the (D1-1) organic pigment, (D1-1) It is possible to improve the dispersion stability of the organic pigment.
- Aromatic carboxylic acids and derivatives thereof include the compounds contained in the aromatic tetracarboxylic acids and / or derivatives thereof, aromatic tricarboxylic acids and / or derivatives thereof and aromatic dicarboxylic acids and / or derivatives thereof described above. .
- the content ratio of the structural unit derived from the aromatic carboxylic acid and / or the derivative thereof in the structural units derived from all the carboxylic acid and the derivative thereof in the acid-modified epoxy resin is 10 to 100 mol% Preferably, 20 to 100 mol% is more preferable, and 30 to 100 mol% is more preferable. When the content ratio is 10 to 100 mol%, the heat resistance of the cured film can be improved.
- the acid-modified epoxy resin (A2-3) used in the present invention preferably contains a structural unit derived from a carboxylic acid and a derivative thereof, and the acid-modified epoxy resin (A2-3) preferably has an acidic group.
- the acid-modified epoxy resin having an acid group can improve the pattern processability with an alkali developer and the resolution after development.
- the acidic group a group exhibiting an acidity of less than pH 6 is preferred.
- a carboxy group, a carboxylic anhydride group, a sulfonic acid group, phenolic hydroxyl group, or a hydroxy imide group is mentioned, for example.
- a carboxy group, a carboxylic acid anhydride group, or a phenolic hydroxyl group is preferable, and a carboxy group or a carboxylic acid anhydride group is more preferable, from the viewpoint of pattern processability improvement with an alkaline developer and resolution improvement after development.
- the content ratio of structural units derived from various monomer components in the acid-modified epoxy resin is 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, And ash content measurement can be determined in combination.
- Examples of the acid-modified epoxy resin (A2-3) used in the present invention include “KAYARAD” (registered trademark) PCR-1222H, CCR-1171H, TCR-1348H, ZAR-1494H, and ZFR-1401H. ZCR-1798H, ZXR-1807H, ZCR-6002H, or ZCR-8001H (all are manufactured by Nippon Kayaku Co., Ltd.), or "NK OLIGO” (registered trademark) EA-6340, EA-7140, Or the same EA-7340 (all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the Mw of the acid-modified epoxy resin (A2-3) used in the present invention is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, in terms of polystyrene measured by GPC.
- the resolution after development can be improved as Mw is in the range mentioned above.
- Mw 100,000 or less is preferable, 50,000 or less is more preferable, 20,000 or less is more preferable.
- coating and the pattern processability in alkaline developing solution can be improved as Mw is in the range mentioned above.
- (A2-4) Acrylic resin for example, one or more kinds selected from a copolymerization component having an acidic group, a copolymerization component derived from (meth) acrylic acid ester, and other copolymerization components
- the acrylic resin obtained by radically copolymerizing the copolymerization component of these is mentioned.
- copolymerization component which has an acidic group a copolymerization component derived from (meth) acrylic acid ester, and the other copolymerization component, the compound of international publication 2017/057281 is mentioned, for example.
- the (A2-4) acrylic resin used in the present invention preferably has an ethylenically unsaturated double bond group.
- the (A2-4) acrylic resin having an ethylenically unsaturated double bond group into the negative photosensitive resin composition, it is possible to improve the sensitivity at the time of exposure.
- the formed three-dimensional crosslinked structure is mainly composed of an alicyclic structure or an aliphatic structure, it is possible to suppress the increase in temperature of the softening point of the resin and obtain a low-tapered pattern shape.
- Mechanical properties of the cured film can be improved. Therefore, it is suitable when using a cured film for the use which a mechanical characteristic is requested
- the (A2-4) acrylic resin used in the present invention is a structural unit represented by the general formula (61) and / or a general formula (62) from the viewpoint of improving sensitivity at the time of exposure and mechanical properties of the cured film. It is preferable to contain the structural unit represented by
- Rd 1 and Rd 2 each independently represent an alkyl group having 1 to 10 carbons and a cyclocarbon having 4 to 15 carbons, each having an ethylenically unsaturated double bond group. It represents an alkyl group or an aryl group having 6 to 15 carbon atoms.
- R 200 to R 205 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- Each of X 90 and X 91 independently represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms.
- Rd 1 and Rd 2 each independently represent an alkyl group having 1 to 6 carbon atoms and a cyclocarbon having 4 to 10 carbon atoms, each having an ethylenically unsaturated double bond group.
- An alkyl group or an aryl group having 6 to 10 carbon atoms is preferred.
- Each of R 200 to R 205 is preferably independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- each of X 90 and X 91 is preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms.
- the alkyl group, the cycloalkyl group, the aryl group, the alkylene chain, the cycloalkylene chain and the arylene chain described above may have a hetero atom and may be either unsubstituted or substituted.
- the (A2-4) acrylic resin used in the present invention is preferably an (A2-4) acrylic resin obtained by radical copolymerization of a copolymerization component having an acidic group or another copolymerization component.
- a copolymerization component having an aromatic group or a copolymerization component having an alicyclic group is preferable.
- the (A2-4) acrylic resin used in the present invention preferably contains a structural unit derived from a copolymerization component having an acidic group, and the (A2-4) acrylic resin preferably has an acidic group. (A2-4) Since the acrylic resin has an acidic group, the pattern processability with an alkali developer and the resolution after development can be improved.
- the acidic group a group exhibiting an acidity of less than pH 6 is preferred.
- a carboxy group, a carboxylic anhydride group, a sulfonic acid group, phenolic hydroxyl group, or a hydroxy imide group is mentioned, for example.
- a carboxy group, a carboxylic acid anhydride group, or a phenolic hydroxyl group is preferable, and a carboxy group or a carboxylic acid anhydride group is more preferable, from the viewpoint of pattern processability improvement with an alkaline developer and resolution improvement after development.
- the (A2-4) acrylic resin used in the present invention when the (A2-4) acrylic resin has a carboxy group, the (A2-4) acrylic resin having no epoxy group is preferable.
- the acrylic resin has both a carboxy group and an epoxy group, there is a possibility that the carboxy group and the epoxy group react during storage of the coating liquid of the negative photosensitive resin composition. Therefore, the storage stability of the coating liquid of the resin composition may be reduced.
- the (A2-4) acrylic resin having no epoxy group a copolymerization component having a carboxy group or a carboxylic acid anhydride group and another copolymerization component having no epoxy group were radically copolymerized (A2) -4) Acrylic resin is preferred.
- the (A2-4) acrylic resin used in the present invention preferably contains a structural unit derived from a copolymerization component having an aromatic group.
- the acrylic resin contains a structural unit derived from a copolymer component having an aromatic group, the heat resistance of the cured film can be improved by the heat resistance of the aromatic group.
- (D1) pigment is especially contained as a (D) coloring agent mentioned later
- (A2-4) an acrylic resin contains an aromatic group by containing the structural unit derived from the copolymerization component which has an aromatic group. The steric hindrance of the group can improve the dispersion stability of the (D1) pigment.
- the aromatic group in the (A2-4) acrylic resin interacts with the aromatic group of the (D1-1) organic pigment; -1) It is possible to improve the dispersion stability of the organic pigment.
- the content ratio of structural units derived from the copolymerization component having an aromatic group in the structural units derived from all the copolymerization components in the acrylic resin is preferably 10 mol% or more, and more preferably 20 mol% or more Preferably, 30 mol% or more is more preferable.
- the heat resistance of a cured film can be improved as a content rate is 10 mol% or more.
- the content ratio is preferably 80 mol% or less, more preferably 75 mol% or less, and still more preferably 70 mol% or less. When the content ratio is 80 mol% or less, the sensitivity at the time of exposure can be improved.
- the (A2-4) acrylic resin used in the present invention preferably contains a structural unit derived from a copolymerization component having an alicyclic group.
- the acrylic resin By containing a structural unit derived from a copolymer component having an alicyclic group, the acrylic resin improves the heat resistance and the transparency of the cured film by the heat resistance and the transparency of the alicyclic group. It can be done.
- the content ratio of structural units derived from the copolymerization component having an alicyclic group in the structural units derived from all the copolymerization components in the acrylic resin is preferably 5 mol% or more, and 10 mol% or more More preferably, 15 mol% or more is more preferable.
- the heat resistance and transparency of a cured film can be improved as a content rate is 5 mol% or more.
- 90 mol% or less is preferable, 85 mol% or less is more preferable, and 75 mol% or less is more preferable.
- the mechanical property of a cured film can be improved as a content rate is 90 mol% or less.
- an ethylenic unsaturated double bond group is further added to a resin obtained by radical copolymerization of a copolymerization component having an acidic group or another copolymerization component. And resins obtained by ring-opening addition reaction of unsaturated compounds having an epoxy group are preferable.
- An ethylenically unsaturated double bond group can be introduced into the side chain of the (A2-4) acrylic resin by subjecting an unsaturated compound having an ethylenically unsaturated double bond group and an epoxy group to a ring-opening addition reaction. .
- the content ratio of structural units derived from various copolymerization components in the acrylic resin (A2-4) is 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, and It can be determined by combining ash content measurement and the like.
- the Mw of the (A2-4) acrylic resin used in the present invention is preferably 1,000 or more, more preferably 3,000 or more, and still more preferably 5,000 or more, in terms of polystyrene measured by GPC.
- the resolution after development can be improved as Mw is 1,000 or more.
- Mw 100,000 or less is preferable, 70,000 or less is more preferable, 50,000 or less is more preferable.
- coating and the pattern processability in alkaline developing solution can be improved as Mw is 100,000 or less.
- the (A2-4) acrylic resin can be synthesized by a known method.
- the method of radically copolymerizing a copolymerization component under air or under nitrogen and in the presence of a radical polymerization initiator can be mentioned.
- a method of radical copolymerization for example, after sufficiently substituting the inside of the reaction vessel with nitrogen in the air or by bubbling or reduced pressure degassing, a copolymerization component and a radical polymerization initiator are added to the reaction solvent, The reaction may be carried out at 110 ° C. for 30 to 500 minutes. Further, if necessary, a chain transfer agent such as a thiol compound and / or a polymerization inhibitor such as a phenol compound may be used.
- the content ratio of the (A1) first resin to the total 100 mass% of (A1) the first resin and (A2) the second resin is 25 mass% or more Is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
- the heat resistance of a cured film and the reliability of a light emitting element can be improved as a content rate is 25 mass% or more.
- the content ratio of the (A1) first resin is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 97% by mass or less, still more preferably 95% by mass or less, and 90% by mass or less Is particularly preferred. While the sensitivity at the time of exposure can be improved as a content ratio is 99 mass% or less, the pattern of low taper shape can be formed after image development. In addition, halftone characteristics can be improved.
- the heat resistance of the cured film is improved when the content ratio of the (A1) first resin and the (A2) second resin in the negative photosensitive resin composition of the present invention is within the above-described preferable range. It is possible to obtain a low taper pattern shape. Therefore, the cured film obtained from the negative photosensitive resin composition of the present invention has a pattern of high heat resistance and low taper such as an insulating layer such as a pixel division layer of an organic EL display, a TFT planarization layer, or a TFT protective layer. It is suitable for the application where the shape is required.
- the negative photosensitive resin composition of the present invention contains (D) a colorant to be described later, visualization of electrode wiring can be prevented or external light reflection can be reduced, and contrast in image display can be improved.
- the negative photosensitive resin composition of the present invention preferably further contains (B) a radically polymerizable compound.
- the radically polymerizable compound (B) refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule.
- radical polymerization of the (B) radically polymerizable compound proceeds by radicals generated from the (C1) photopolymerization initiator described later, and the exposed part of the film of the resin composition becomes insolubilized in an alkali developer.
- a negative pattern can be formed.
- UV curing at the time of exposure is promoted, and the sensitivity at the time of exposure can be improved.
- crosslink density after heat curing can be improved, and the hardness of the cured film can be improved.
- radically polymerizable compound (B) a compound having a (meth) acrylic group which facilitates the progress of radical polymerization is preferable. From the viewpoint of sensitivity improvement at the time of exposure and hardness improvement of a cured film, a compound having two or more (meth) acrylic groups in the molecule is more preferable.
- the double bond equivalent of the radically polymerizable compound (B) is preferably 80 to 800 g / mol from the viewpoint of sensitivity improvement at the time of exposure and formation of a low tapered pattern.
- (B) As the radically polymerizable compound, in addition to the (B1) fluorene skeleton-containing radically polymerizable compound and the (B2) indane skeleton-containing radically polymerizable compound described later, for example, diethylene glycol di (meth) acrylate, triethylene glycol di ( Meta) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,1,6-hexanediol di
- the compound obtained by subjecting a compound having two or more glycidoxy groups to a ring-opening addition reaction with an unsaturated carboxylic acid having an ethylenically unsaturated double bond group in a molecule is also preferred.
- a compound obtained by reacting a polybasic acid carboxylic acid or a polybasic carboxylic acid anhydride is also preferred.
- the content of the (B) radically polymerizable compound in the negative photosensitive resin composition of the present invention is 15 in the case where the total of (A) alkali soluble resin and (B) radically polymerizable compound is 100 parts by mass. More than 20 mass parts are more preferable, 25 mass parts or more are more preferable, and 30 mass parts or more are especially preferable. While being able to improve the sensitivity at the time of exposure as content is 15 mass parts or more, the cured film of the low taper pattern shape can be obtained. On the other hand, 65 mass parts or less are preferable, as for content of a radically polymerizable compound (B), 60 mass parts or less are more preferable, 55 mass parts or less are more preferable, 50 mass parts or less are especially preferable. While the heat resistance of a cured film can be improved as content is 65 mass parts or less, a low taper pattern shape can be obtained.
- the negative photosensitive resin composition of the present invention is further selected from the group consisting of (B1) a fluorene skeleton-containing radical polymerizable compound and (B2) an indane skeleton-containing radical polymerizable compound as the (B) radically polymerizable compound It is preferable to contain one or more kinds.
- the (B1) fluorene skeleton-containing radically polymerizable compound refers to a compound having a plurality of ethylenic unsaturated double bond groups and a fluorene skeleton in the molecule.
- Indane skeleton-containing radically polymerizable compound means a compound having a plurality of ethylenically unsaturated double bond groups and indane skeleton in the molecule.
- the (D1a-1a) benzofuranone-based black pigment is particularly contained as the (Da) blackening agent described later, a pigment-derived developing residue may be generated due to the insufficient alkali resistance of the pigment described above.
- the soft chain-containing aliphatic radical polymerizable compound to be described later and the (B1) fluorene skeleton-containing radical polymerizable compound or the (B2) indane skeleton-containing radical polymerizable compound are contained as described above. It is possible to suppress the generation of development residues derived from pigments.
- a compound having a (meth) acrylic group which is easily progressed by radical polymerization is preferable. From the viewpoint of sensitivity improvement at the time of exposure and suppression of residues after development, compounds having two or more (meth) acryl groups in the molecule are more preferable.
- Examples of the (B1) fluorene skeleton-containing radically polymerizable compound include 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis [4- (3- (meth) ) Acryloxypropoxy) phenyl] fluorene, 9,9-bis (4- (meth) acryloxyphenyl) fluorene, 9,9-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] Fluorene, or 9,9-bis [3,4-bis (2- (meth) acryloxyethoxy) phenyl] fluorene, or OGSOL (registered trademark) EA-50P, EA-0200, EA-0250P, EA -0300, EA-500, EA-1000, EA-F 5510, or GA-5000 (or more, Re may also be mentioned is manufactured by Osaka Gas Chemicals Co., Ltd.).
- Indane skeleton-containing radically polymerizable compounds include, for example, 1,1-bis [4- (2- (meth) acryloxyethoxy) phenyl] indane, 1,1-bis (4- (meth) acryloxy) Phenyl) indane, 1,1-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] indane, 1,1-bis [3,4-bis (2- (meth) acryloxyethoxy) And R) phenyl] indane, 2,2-bis [4- (2- (meth) acryloxyethoxy) phenyl] indane, or 2,2-bis (4- (meth) acryloxyphenyl) indane.
- the (B1) fluorene skeleton-containing radically polymerizable compound and the (B2) indane skeleton-containing radically polymerizable compound can be synthesized by a known method.
- the synthesis method described in WO 2008/139924 can be mentioned.
- the total content of the (B1) fluorene skeleton-containing radically polymerizable compound and the (B2) indane skeleton-containing radically polymerizable compound in the negative photosensitive resin composition of the present invention is (A) alkali-soluble resin and (B)
- the total amount of radically polymerizable compounds is 100 parts by mass, 0.5 parts by mass or more is preferable, 1 part by mass or more is more preferable, 2 parts by mass or more is more preferable, 3 parts by mass or more is further more preferable, 5 Particularly preferred is part by weight or more. While the sensitivity at the time of exposure can be improved as content is 0.5 mass parts or more, a pattern of low taper shape can be formed after thermosetting.
- the total content of the (B1) fluorene skeleton-containing radically polymerizable compound and the (B2) indane skeleton-containing radically polymerizable compound is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less It is more preferable, 18 parts by mass or less is still more preferable, and 15 parts by mass or less is particularly preferable. While the change of the pattern opening dimension width
- the negative photosensitive resin composition of the present invention preferably further contains (B3) a flexible chain-containing aliphatic radically polymerizable compound as the (B) radically polymerizable compound.
- B3) A flexible chain-containing aliphatic radically polymerizable compound means a compound having a plurality of ethylenic unsaturated double bond groups and a flexible skeleton such as an aliphatic chain or an oxyalkylene chain in the molecule.
- (B3) By containing a flexible chain-containing aliphatic radically polymerizable compound, UV curing at the time of exposure can proceed efficiently, and sensitivity at the time of exposure can be improved.
- (D1) pigment is contained as a (D) coloring agent to be described later, the (D1) pigment is fixed to a cured portion by crosslinking at the time of UV curing of the (B3) flexible chain-containing aliphatic radically polymerizable compound.
- the (D1a-1a) benzofuranone-based black pigment is specifically contained as the (Da) blackening agent described later, as described above, there may be a case where a pigment-derived developing residue is generated due to insufficient alkali resistance of this pigment. is there. Even in such a case, the generation of the above-described development residue derived from the pigment can be suppressed by containing the (B3) flexible chain-containing aliphatic radically polymerizable compound.
- the flexible chain-containing aliphatic radically polymerizable compound (B3) a compound having a group represented by the general formula (24) and a group represented by three or more general formulas (25) in a molecule is preferable.
- R 125 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- Z 17 represents a group represented by General Formula (29) or a group represented by General Formula (30).
- a represents an integer of 1 to 10
- b represents an integer of 1 to 4
- c represents 0 or 1
- d represents an integer of 1 to 4
- e represents 0 or 1 .
- c 0, d is 1.
- each of R 126 to R 128 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- R 129 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- c is preferably 1 and e is preferably 1.
- R 126 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen or a methyl group.
- Each of R 127 and R 128 independently is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen.
- R 129 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen or a methyl group.
- the flexible chain-containing aliphatic radical polymerizable compound (B3) preferably has at least one lactone modified chain and / or at least one lactam modified chain.
- the generation of a residue after development can be suppressed by the soft chain-containing aliphatic radically polymerizable compound having at least one lactone modified chain and / or at least one lactam modified chain.
- the flexible chain-containing aliphatic radically polymerizable compound has at least one lactone modified chain and / or at least one. Have two lactam modified chains.
- the number of ethylenic unsaturated double bond groups that the flexible chain-containing aliphatic radical polymerizable compound has in the molecule is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
- the number of ethylenically unsaturated double bond groups is 2 or more, the sensitivity at the time of exposure can be improved.
- the number of ethylenically unsaturated double bond groups that the (B3) flexible chain-containing aliphatic radical polymerizable compound has in the molecule is preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. Particularly preferred is not more than one.
- the number of ethylenically unsaturated double bond groups is 12 or less, it is possible to form a low-tapered pattern after heat curing, and to suppress changes in the dimension opening width of the pattern before and after heat curing.
- (B3) As a flexible chain-containing aliphatic radical polymerizable compound, as a compound having 3 or more ethylenic unsaturated double bond groups in the molecule, for example, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylation Dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactone modified dipentaerythritol hexa (meth) acrylate, ⁇ -valerolactone modified dipentaerythritol hexa (meth) acrylate, ⁇ -butyrolactone modified dipentaerythritol hexa (meth) acrylate, ⁇ -Propiolactone modified dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactam modified dipentaerythritol hexa (meth) acrylate, ⁇ -caprol
- Examples of the compound having two ethylenically unsaturated double bond groups in the molecule include ⁇ -caprolactone modified hydroxypivalate neopentyl glycol di (meth) acrylate, ⁇ -caprolactone modified trimethylolpropane di (meth) acrylate, ⁇ -caprolactone modified ditrimethylolpropane di (meth) acrylate, ⁇ -caprolactone modified glycerin di (meth) acrylate, ⁇ -caprolactone modified pentaerythritol di (meth) acrylate, ⁇ -caprolactone modified dimethylol-tricyclodecane di (meth) acrylate ⁇ -caprolactone modified 1,3-bis ((meth) acryloxyethyl) isocyanuric acid, or ⁇ -caprolactone modified 1,3-bis ((meth) acryloxyethyl) isocyanuric acid, or “ KAYARAD "(registere
- the flexible chain-containing aliphatic radically polymerizable compound (B3) can be synthesized by a known method.
- the content of the (B3) flexible chain-containing aliphatic radically polymerizable compound in the negative photosensitive resin composition of the present invention is 100 parts by mass of the total of (A) alkali soluble resin and (B) radically polymerizable compound. In this case, 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is more preferable, and 20 parts by mass or more is particularly preferable. While the sensitivity at the time of exposure can be improved as content is 5 mass parts or more, residue generation after development can be controlled. In addition, it is possible to suppress the change in the pattern opening dimension width before and after heat curing.
- the content of the (B3) soft chain-containing aliphatic radical polymerizable compound is 45 parts by mass or less, 40 parts by mass or less is more preferable, 35 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable as the content of the (B3) soft chain-containing aliphatic radical polymerizable compound. If the content is 45 parts by mass or less, a cured film having a low taper pattern shape can be obtained.
- the negative photosensitive resin composition of the present invention preferably further contains (B4) an alicyclic group-containing radically polymerizable compound as the (B) radically polymerizable compound.
- the alicyclic group-containing radically polymerizable compound (B4) refers to a compound having a plurality of ethylenic unsaturated double bond groups and an alicyclic group in the molecule.
- the negative photosensitive resin composition of the present invention preferably contains (B4) an alicyclic group-containing radically polymerizable compound and a (F) polyfunctional thiol compound described later.
- (B4) alicyclic group-containing radically polymerizable compound and the (F) polyfunctional thiol compound in combination, it is possible to suppress a change in the dimension opening width of the pattern before and after heat curing, and to form a low taper shape after development. Can form a pattern of This is considered to be because UV inhibition of the (B4) alicyclic group-containing radically polymerizable compound at the time of exposure was promoted by the inhibition of oxygen inhibition on the film surface by the (F) polyfunctional thiol compound.
- the (B4) alicyclic group-containing radically polymerizable compound is susceptible to inhibition of UV curing due to steric hindrance of the alicyclic group in addition to oxygen inhibition on the film surface. Is considered to have been significantly promoted.
- the number of ethylenic unsaturated double bond groups that the alicyclic group-containing radically polymerizable compound has in the molecule is preferably 2 or more, and more preferably 3 or more. When the number of ethylenically unsaturated double bond groups is 2 or more, the sensitivity at the time of exposure can be improved. On the other hand, the number of ethylenic unsaturated double bond groups that the (B4) alicyclic group-containing radically polymerizable compound has in the molecule is preferably 10 or less, more preferably 6 or less. When the number of ethylenically unsaturated double bond groups is 10 or less, a pattern with a low taper shape can be formed after heat curing.
- the alicyclic group contained in the molecule of the (B4) alicyclic group-containing radically polymerizable compound is preferably a fused polycyclic alicyclic skeleton.
- a fused polycyclic alicyclic skeleton By having the fused polycyclic alicyclic skeleton, it is possible to suppress the change in the dimension opening width of the pattern before and after heat curing. In addition, it becomes possible to make a forward taper by pattern shape control after development and to form a low taper shape pattern after heat curing.
- fused polycyclic alicyclic skeleton for example, bicyclo [4.3.0] nonane skeleton, bicyclo [5.4.0] undecane skeleton, bicyclo [2.2.2] octane skeleton, tricyclo [5.2 .1.0 2,6 ] decane skeleton, pentacyclopentadecane skeleton, adamantane skeleton or hydroxyadamantane skeleton.
- Examples of the alicyclic group-containing radically polymerizable compound include dimethylol-bicyclo [4.3.0] nonanedi (meth) acrylate, dimethylol-bicyclo [5.4.0] undecanedi (meth) acrylate, and dimethylol.
- octane di (meth) acrylate dimethylol-tricyclo [5.2.1.0 2,6 ] decanedi (meth) acrylate, dimethylol-pentacyclopentadecane di (meth) acrylate, 1,1 Examples include 3-adamantane di (meth) acrylate, 1,3,5-adamantane tri (meth) acrylate or 5-hydroxy-1,3-adamantane di (meth) acrylate.
- the alicyclic group-containing radically polymerizable compound (B4) can be synthesized by a known method.
- the content of the (B4) alicyclic group-containing radically polymerizable compound in the negative photosensitive resin composition of the present invention is 100 parts by mass of the total of (A) alkali-soluble resin and (B) radically polymerizable compound. In such a case, 1 part by mass or more is preferable, 2 parts by mass or more is more preferable, 3 parts by mass or more is more preferable, 5 parts by mass or more is still more preferable, and 10 parts by mass or more is particularly preferable.
- the content is 1 part by mass or more, the change in the dimension opening width of the pattern before and after heat curing can be suppressed. In addition, it becomes possible to make a forward taper by pattern shape control after development, and to form a low-tapered pattern after heat curing.
- the content of the (B4) alicyclic group-containing radically polymerizable compound is preferably 30 parts by mass or less, more preferably 27 parts by mass or less, further preferably 25 parts by mass or less, still more preferably 22 parts by mass or less 20 parts by mass or less is particularly preferable. While the change of the pattern opening dimension width
- the negative photosensitive resin composition of the present invention further contains (C1) a photopolymerization initiator as (C) a photosensitizer.
- the photopolymerization initiator refers to a compound which generates a radical by bond cleavage and / or reaction upon exposure to light.
- C1 By containing a photopolymerization initiator, radical polymerization of the above-mentioned (B) radically polymerizable compound proceeds, and the exposed part of the film of the resin composition becomes insoluble in an alkali developer, thereby making it negative. A pattern of molds can be formed. In addition, UV curing at the time of exposure is promoted, and sensitivity can be improved.
- variety before and behind thermosetting can be suppressed by containing (C1) photoinitiator as a specific amount or more. This is considered to be due to the increase in the amount of radicals generated from the (C1) photopolymerization initiator at the time of exposure. That is, by increasing the radical generation amount at the time of exposure, the collision probability between the generated radical and the ethylenically unsaturated double bond group in the above-mentioned (B) radical polymerizable compound becomes high, and the UV curing is accelerated. It is presumed that, by improving the crosslink density, it is possible to suppress a change in the dimension opening width of the pattern before and after heat curing by suppressing the reflow of the tapered portion and pattern foot of the pattern at the time of heat curing.
- (C1) As the photopolymerization initiator, for example, benzyl ketal photopolymerization initiator, ⁇ -hydroxy ketone photopolymerization initiator, ⁇ -amino ketone photopolymerization initiator, acyl phosphine oxide photopolymerization initiator, biimidazole Photopolymerization initiator, oxime ester photopolymerization initiator, acridine photopolymerization initiator, titanocene photopolymerization initiator, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, aromatic keto ester photopolymerization initiator Or benzoic acid ester photopolymerization initiators are preferred, and from the viewpoint of improving sensitivity at the time of exposure, ⁇ -hydroxy ketone photopolymerization initiator, ⁇ -amino ketone photopolymerization initiator, acyl phosphine oxide photopolymerization initiator, Biimidazole photo
- benzyl ketal photopolymerization initiators examples include 2,2-dimethoxy-1,2-diphenylethane-1-one.
- Examples of ⁇ -hydroxy ketone photopolymerization initiators include 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, or 2-hydroxy-1- [4- [4- [4- [4 (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2-methylpropan-1-one.
- Examples of ⁇ -amino ketone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4) -Morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one, or 3,6-bis (2-methyl) -2-morpholinopropionyl) -9-octyl-9H-carbazole.
- acyl phosphine oxide type photoinitiator For example, 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6 trimethyl trimethyl)-phenyl phosphine oxide, or bis (2, 6- dimethoxy) And benzoyl)-(2,4,4-trimethylpentyl) phosphine oxide.
- biimidazole photopolymerization initiator for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′, 5-tris (2-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-1,2′-biimidazole, 2,2 ′, 5-tris (2-fluorophenyl) -4- (3,4-Dimethoxyphenyl) -4 ', 5'-diphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5 Examples include '-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2-methoxyphenyl) -4,4', 5,5'-tetraphenyl-1,2
- oxime ester photopolymerization initiators include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime, 1-phenylbutane-1,2-dione-2- (O-methoxy) Carbonyl) oxime, 1,3-diphenylpropane-1,2,3-trione-2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- ( O-Benzoyl) oxime, 1- [4- [4-carboxyphenylthio] phenyl] propane-1,2-dione-2- (O-acetyl) oxime, 1- [4- [4- (2-hydroxyethoxy) oxime ) Phenylthio] phenyl] propane-1,2-dione-2- (O-acetyl) oxime, 1- [4- (phenylthio)
- acridine photopolymerization initiators examples include 1,7-bis (acridin-9-yl) -n-heptane.
- titanocene photopolymerization initiator for example, bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium (IV) or bis ( ⁇ 5 -3-methyl-2,4-cyclopentadien-1-yl) -bis (2,6-difluorophenyl) titanium (IV).
- benzophenone-based photopolymerization initiators include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4- There may be mentioned hydroxybenzophenone, alkylated benzophenone, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone, 4-methylbenzophenone, dibenzyl ketone or fluorenone.
- acetophenone photopolymerization initiators examples include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone.
- aromatic ketoester photopolymerization initiators examples include methyl 2-phenyl-2-oxyacetate.
- benzoate-based photopolymerization initiators include ethyl 4-dimethylaminobenzoate, (2-ethyl) hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, or methyl 2-benzoylbenzoate.
- the content of the (C1) photopolymerization initiator in the negative photosensitive resin composition of the present invention is 0 in the case where the total of (A) alkali soluble resin and (B) radically polymerizable compound is 100 parts by mass. 1 part by mass or more is preferable, 0.5 part by mass or more is more preferable, 0.7 part by mass or more is more preferable, and 1 part by mass or more is particularly preferable.
- the sensitivity at the time of exposure can be improved as content is 0.1 mass part or more.
- the content of the (C1) photopolymerization initiator is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, still more preferably 14 parts by mass or more, and 15 parts by mass from the viewpoint of controlling the pattern opening size width.
- the above is particularly preferable.
- the content is 10 parts by mass or more, a change in dimension opening width of the pattern before and after heat curing can be suppressed.
- 30 parts by mass or less is preferable, 25 parts by mass or less is more preferable, 22 parts by mass or less is more preferable, and 20 parts by mass or less is particularly preferable.
- the content is 30 parts by mass or less, the resolution after development can be improved, and a cured film having a low taper shape pattern can be obtained.
- the negative photosensitive resin composition of the present invention has one or more kinds of structures selected from the group consisting of (I), (II), and (III) as the (C1) photopolymerization initiator (C1-1) 2.)
- An oxime ester photopolymerization initiator hereinafter, "(C1-1) specific oxime ester photopolymerization initiator" is contained.
- X 7 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms.
- R 29 is hydrogen, an alkyl group having 1 to 10 carbon atoms, or 4 to 10 carbon atoms
- a cycloalkyl group an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group.
- R 29 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, carbon A haloalkyl group of 1 to 10, a haloalkoxy group of 1 to 10 carbon atoms, a heterocyclic group of 4 to 10 carbon atoms, a heterocyclic oxy group of 4 to 10 carbon atoms, an acyl group of 2 to 10 carbon atoms, or nitro Represents a group.
- R 30 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- a represents 0 or 1
- b represents an integer of 0 to 10.
- X 7 is preferably an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving the solubility in a solvent, or an arylene group having 6 to 15 carbon atoms from the viewpoint of improving the sensitivity during exposure.
- R 29 is preferably a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms from the viewpoint of improving the solubility in a solvent.
- R 29 is a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or 4 to 10 carbon atoms from the viewpoint of improving sensitivity at the time of exposure and forming a low taper shape pattern after development.
- a heterocyclic group, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group is preferable.
- R 30 is preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably methyl, from the viewpoint of improving sensitivity at the time of exposure.
- a is preferably 0 from the viewpoint of improving sensitivity at the time of exposure.
- the group represented by the general formula (11) is a group having an oxime ester structure, and is a group having a structure which generates a radical by bond cleavage and / or reaction by UV upon exposure.
- the fluorene structure, carbazole structure, dibenzofuran structure, dibenzothiophene structure, naphthalene structure, diphenylmethane structure, diphenylamine structure, diphenyl ether structure, or diphenyl sulfide structure in (II) or (III) described above is the oxime ester structure described above Represents a mother skeleton to which a group having In the above-mentioned (I), (II), or (III), the naphthalenecarbonyl structure, the trimethylbenzoyl structure, the thiophenecarbonyl structure, the furan carbonyl structure, and the nitro group are bonded by a group having the oxime ester structure described above Represents a structure to be bonded or
- a specific oxime ester-based photopolymerization initiator increases the absorbance in the ultraviolet region in the molecule, radical cures at the deep part of the film at the time of exposure, and radical cure due to an increase in the amount of radicals generated at the time of exposure
- (C1-1) By containing a specific oxime ester photopolymerization initiator, the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics can be improved. It is presumed that this is because radical curing in the deep part of the film at the time of exposure is possible.
- the specific conjugated structure possessed by the (C1-1) specific oxime ester-based photopolymerization initiator interacts with the aromatic group possessed by the (A1) first resin and the (A2) second resin.
- the film is compatibilized with the entire film, and the penetration of the developer into the cured film during alkali development is suppressed by promoting radical curing to the deep part of the film due to the increase of radical generation amount at the time of exposure, side etching by developer Is considered to be able to suppress
- the (C1-1) specific oxime ester-based photopolymerization initiator it is possible to suppress a change in the dimension opening width of the pattern before and after heat curing. This suppresses the side etching by the developing solution at the time of alkali development as described above, and in addition to the formation of a low taper shape pattern after the development, UV curing at the time of exposure is accelerated and thus curing is achieved. It is presumed that the film has a high molecular weight, and the reflow of the pattern at the time of heat curing is suppressed.
- the initiator contains one or more selected from the group consisting of a compound represented by the general formula (12), a compound represented by the general formula (13), and a compound represented by the general formula (14)
- the compound represented by General formula (13) is more preferable.
- X 1 to X 6 each independently represent a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or 6 to 6 carbon atoms 15 represents an arylene group.
- Y 1 to Y 3 each independently represent carbon, nitrogen, oxygen or sulfur.
- R 31 to R 36 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or It represents a C 1-10 hydroxyalkyl group.
- R 37 to R 39 each independently represent a group represented by General Formula (15), a group represented by General Formula (16), a group represented by General Formula (17), a general formula (18) Or a nitro group.
- R 40 to R 45 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or 4 to 10 carbon atoms Represents a group forming a ring.
- R 46 to R 48 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms And an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms.
- R 49 to R 51 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms
- R 52 to R 54 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- a represents an integer of 0 to 3
- b represents 0 or 1
- c represents an integer of 0 to 5
- d represents 0 or 1
- e represents an integer of 0 to 4.
- F represents an integer of 0 to 2
- g, h and i each independently represent an integer of 0 to 2
- j, k and l each independently represent 0 or 1
- m, n and o each independently represent an integer of 0 to 10.
- R 37 is a nitro group
- X 4 is an arylene group having 6 to 15 carbon atoms
- R 49 is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 4 to 10 carbon atoms Group, aryl group having 6 to 15 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 10 carbon atoms, heterocyclic group having 4 to 10 carbon atoms, heterocyclic oxy group having 4 to 10 carbon atoms , An acyl group having 2 to 10 carbon atoms, or a nitro group.
- each of X 1 to X 6 is preferably independently an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving the solubility in a solvent. From the viewpoint, an arylene group having 6 to 15 carbon atoms is preferable.
- Examples of the ring having 4 to 10 carbon atoms formed in R 40 to R 45 include a benzene ring and a cyclohexane ring.
- Each of R 46 to R 48 independently represents an alkyl group having 1 to 10 carbons, a cycloalkyl group having 4 to 10 carbons, a haloalkyl group having 1 to 10 carbons, or the like from the viewpoint of improving the solubility in a solvent
- a C 1-10 haloalkoxy group is preferable, and a C 1-10 fluoroalkyl group or a C 1-10 fluoroalkoxy group is more preferable.
- R 46 to R 48 each independently represent a haloalkyl group having 1 to 10 carbon atoms or a haloalkoxy having 1 to 10 carbon atoms from the viewpoint of sensitivity improvement at the time of exposure and formation of a low taper shape pattern after development.
- a group or an acyl group having 2 to 10 carbon atoms is preferable, and a fluoroalkyl group having 1 to 10 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms is more preferable.
- R 49 to R 51 each independently represent a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving the solubility in a solvent Is preferable, and a fluoroalkyl group having 1 to 10 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms is more preferable.
- R 49 to R 51 each independently represent a haloalkyl group having 1 to 10 carbon atoms or a haloalkoxy having 1 to 10 carbon atoms, from the viewpoint of sensitivity improvement at the time of exposure and formation of a low tapered shape pattern after development.
- a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group is preferable, and a fluoroalkyl group having 1 to 10 carbon atoms or The number of fluoroalkoxy groups of 1-10 is more preferred.
- R 52 to R 54 are each independently preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, from the viewpoint of improving sensitivity at the time of exposure; More preferable.
- Each of j, k and l is preferably 0 independently from the viewpoint of improving sensitivity at the time of exposure.
- (C1-1) As a photoinitiator, it is preferable to contain the compound represented by the compound represented by General formula (12), and / or General formula (13).
- Y 1 and Y 2 are preferably carbon or nitrogen.
- R 46 and R 47 preferably contain at least an alkenyl group having 1 to 10 carbon atoms, and more preferably contain an alkenyl group having 1 to 6 carbon atoms.
- R 49 and R 50 preferably contain at least an alkenyl group having 1 to 10 carbon atoms, and more preferably contain an alkenyl group having 1 to 6 carbon atoms. This is considered to be because the compatibility between the resin and the initiator can be further improved by containing the alkenyl group, and UV curing at the time of exposure efficiently proceeds even in the deep part of the film.
- alkenyl group for example, a vinyl group, 1-methylethenyl group, allyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, 3-butenyl group, or cinnamyl group .
- R 55 to R 58 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. And an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or a group forming a ring.
- Examples of the ring formed by a plurality of R 55 to R 58 include a benzene ring, a naphthalene ring, an anthracene ring, a cyclopentane ring or a cyclohexane ring.
- a is an integer of 0 to 7
- b is an integer of 0 to 2
- c and d are each independently an integer of 0 to 3.
- the ring formed by a plurality of R 55 to R 58 is preferably a benzene ring or a naphthalene ring.
- (C1-1) As the specific oxime ester photopolymerization initiator, it is preferable to have a group substituted with a halogen.
- (C1-1) When the specific oxime ester photopolymerization initiator has a halogen-substituted group, the solubility in a solvent is improved.
- the compatibility with the (A1) first resin and the (A2) second resin can be improved, and the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development. it can.
- halogen fluorine is preferred.
- At least one selected from a polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor contains a structural unit having a fluorine atom, and thus a resin and an initiator It is thought that the UV curing at the time of exposure can proceed efficiently even in the deep part of the film.
- halogen-substituted group examples include fluoromethyl group, fluoroethyl group, chloroethyl group, bromoethyl group, iodoethyl group trifluoromethyl group, trifluoropropyl group, trichloropropyl group, tetrafluoropropyl group and trifluoropentyl group.
- Tetrafluoropentyl group pentafluoropentyl group, heptafluoropentyl group, heptafluorodecyl group, fluorocyclopentyl group, tetrafluorocyclopentyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethoxy group, trifluoropropoxy group, tetra And fluoropropoxy, trifluoropentyloxy, pentafluoropentyloxy, tetrafluorocyclopentyloxy or pentafluorophenoxy groups.
- Examples of the (C1-1) specific oxime ester photopolymerization initiator include compounds (OXL-1 to OXL-102) having the structures shown below.
- the specific oxime ester photopolymerization initiator can be synthesized by a known method. For example, the synthesis methods described in JP-A-2013-190459, JP-A-2016-191905, and WO 2014/500852 can be mentioned.
- the maximum absorption wavelength of the specific oxime ester photopolymerization initiator is preferably 330 nm or more, more preferably 340 nm or more, and still more preferably 350 nm or more.
- the maximum absorption wavelength is 330 nm or more, the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development.
- the maximum absorption wavelength of the (C1-1) specific oxime ester photopolymerization initiator is preferably 410 nm or less, more preferably 400 nm or less, still more preferably 390 nm or less, and particularly preferably 380 nm or less.
- the sensitivity at the time of exposure can be improved as the maximum absorption wavelength is 410 nm or less, and a pattern with a low taper shape can be formed after development.
- the maximum transmission wavelength of the (Da) blackening agent described later is 330 to 410 nm
- exposure is performed such that the maximum absorption wavelength of the (C1-1) specific oxime ester photopolymerization initiator is 330 to 410 nm.
- the sensitivity can be improved, and a pattern with a low taper shape can be formed after development.
- the maximum absorption wavelength and the maximum transmission wavelength mean a wavelength showing maximum absorption and a wavelength showing maximum transmission in the absorption spectrum and the transmission spectrum within the wavelength range of 300 to 800 nm.
- the absorbance at a wavelength of 360 nm in a 0.01 g / L propylene glycol monomethyl ether acetate solution of a specific oxime ester photopolymerization initiator is preferably 0.20 or more, more preferably 0.25 or more, 0.30 or more is further preferable, 0.35 or more is further more preferable, 0.40 or more is particularly preferable, and 0.45 or more is most preferable.
- the sensitivity at the time of exposure can be improved as the absorbance is 0.20 or more, and a pattern with a low taper shape can be formed after development. In addition, it is possible to suppress a change in the dimension opening width of the pattern before and after heat curing, and to improve halftone characteristics.
- the absorbance at a wavelength of 360 nm in a 0.01 g / L propylene glycol monomethyl ether acetate solution of the (C1-1) specific oxime ester-based photopolymerization initiator is preferably 1.00 or less. While generation
- the content of the (C1-1) specific oxime ester photopolymerization initiator in the negative photosensitive resin composition of the present invention is 100 mass of the total of (A) alkali soluble resin and (B) radically polymerizable compound.
- 0.1 parts by mass or more is preferable, 0.5 parts by mass or more is more preferable, 0.7 parts by mass or more is more preferable, and 1 part by mass or more is particularly preferable.
- the content is 0.5 parts by mass or more, the sensitivity at the time of exposure can be improved.
- the content of the (C1-1) specific oxime ester-based photopolymerization initiator is preferably 3 parts by mass or more, and more preferably 4 parts by mass or more, from the viewpoint of control of the pattern shape after development and thermosetting. 5 parts by mass or more is more preferable, and 7 parts by mass or more is particularly preferable.
- the content is 3 parts by mass or more, a pattern with a low taper shape can be formed after development, and a change in the dimension opening width of the pattern before and after thermosetting can be suppressed. In addition, halftone characteristics can be improved.
- the content of the (C1-1) specific oxime ester-based photopolymerization initiator is preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and 15 parts by mass or less from the viewpoint of pattern shape control after development. Is more preferable, and 13 parts by mass or less is particularly preferable.
- the content is 20 parts by mass or less, a pattern with a low taper shape can be formed after development, and a change in the dimension opening width of the pattern before and after thermosetting can be suppressed.
- the negative photosensitive resin composition of the present invention further comprises (C1-2) an ⁇ -amino ketone photopolymerization initiator as a (C1) photopolymerization initiator and a (C1-3) acyl phosphine oxide photopolymerization initiator It is preferable to contain one or more kinds selected from the group consisting of (C1-4) biimidazole photopolymerization initiators.
- (C1-2) at least one selected from the group consisting of (C1-2) ⁇ -amino ketone photopolymerization initiators, (C1-3) acyl phosphine oxide photopolymerization initiators, and (C1-4) biimidazole photopolymerization initiators
- the sensitivity at the time of exposure can be improved. Since these photopolymerization initiators have an absorption wavelength in a wavelength range different from the absorption wavelength of the (C1-1) specific oxime ester photopolymerization initiator described above, UV light at the time of exposure is more efficiently radicalized It is believed that it can be used for curing. Further, in addition to the above, it is possible to suppress the change in the dimension opening width of the pattern before and after the thermosetting.
- the (C1-2) ⁇ -amino ketone photopolymerization initiator, the (C1-3) acyl phosphine oxide photopolymerization initiator and the (C1-4) biimidazole photopolymerization initiator contain nitrogen or phosphorus in the molecule Therefore, it is considered that amine or phosphine is generated by photolysis at the time of exposure and / or thermal decomposition at the time of thermal curing, and these act as a crosslinking catalyst at the time of thermal curing to suppress the reflow in the pattern foot.
- the content ratio of the (C1-1) specific oxime ester-based photopolymerization initiator in the (C1) photopolymerization initiator is preferably 55% by mass or more, and 60% by mass. % Or more is more preferable, 65 mass% or more is further preferable, 70 mass% or more is further more preferable, and 75 mass% or more is particularly preferable. While the sensitivity at the time of exposure can be improved as a content ratio is 55 mass% or more, the change of the pattern opening dimension width
- 95 mass% or less is preferable, as for the content ratio of (C1-1) specific oxime ester type photoinitiator, 93 mass% or less is more preferable, 90 mass% or less is more preferable, and 88 mass% or less is more preferable. More preferably, 85% by mass or less is particularly preferable. While the sensitivity at the time of exposure can be improved as a content ratio is 95 mass% or less, the change of the pattern opening dimension width
- the (C1-2) ⁇ -amino ketone photopolymerization initiator, the (C1-3) acyl phosphine oxide photopolymerization initiator, and the (C1) photopolymerization initiator in the photopolymerization initiator 5 mass% or more is preferable, as for the sum total of the content ratio of (C1-4) biimidazole type photoinitiator, 7 mass% or more is more preferable, 10 mass% or more is more preferable, 12 mass% or more is still more preferable 15 mass% or more is especially preferable.
- the sensitivity at the time of exposure can be improved as a content ratio is 5 mass% or more, the change of the pattern opening dimension width
- 45 mass% or less is preferable, as for the content ratio of (C1-1) specific oxime ester type photoinitiator, 40 mass% or less is more preferable, 35 mass% or less is more preferable, and 30 mass% or less is more preferable More preferably, 25% by mass or less is particularly preferable.
- the sensitivity at the time of exposure can be improved as a content ratio is 45 mass% or less, the change of the pattern opening dimension width
- the negative photosensitive resin composition of the present invention may further contain (C2) a photoacid generator as the (C) photosensitizer.
- C2) A photoacid generator is a compound which causes bond cleavage by exposure to generate an acid.
- C2) By containing a photo-acid generator UV curing at the time of exposure is promoted, and sensitivity can be improved. Moreover, the crosslinking density after thermosetting of a resin composition can be improved, and the chemical resistance of a cured film can be improved.
- C2 As a photo-acid generator, there exist an ionic compound and a nonionic compound.
- triorganosulfonium salt compounds include methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, or 4-toluenesulfonate of triphenylsulfonium; methanesulfonic acid of dimethyl-1-naphthylsulfonium Salts, trifluoromethanesulfonates, camphorsulfonates, or 4-toluenesulfonates; methanesulfonates, trifluoromethanesulfonates, camphorsulfonates of dimethyl (4-hydroxy-1-naphthyl) sulfonium, Or 4-toluenesulfonic acid salt; methanesulfonate, trifluoromethanesulfonate, camphorsulfonates of dimethyl (4-hydroxy-1-naphthyl) sulfonium, Or 4-toluenesulfonic acid salt;
- Examples of (C2) photoacid generators for nonionic compounds include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, sulfoneimide compounds, phosphoric acid ester compounds, or sulfone benzotriazoles Compounds are mentioned.
- nonionic compounds are preferable to ionic compounds from the viewpoints of solubility and insulating properties of the cured film. From the viewpoint of the strength of the generated acid, those generating benzenesulfonic acid, 4-toluenesulfonic acid, perfluoroalkylsulfonic acid or phosphoric acid are more preferable.
- the content of the (C2) photoacid generator in the negative photosensitive resin composition of the present invention is 0 when the total of (A) the alkali-soluble resin and the (B) radically polymerizable compound is 100 parts by mass. 1 part by mass or more is preferable, 0.5 part by mass or more is more preferable, 0.7 part by mass or more is more preferable, and 1 part by mass or more is particularly preferable.
- the sensitivity at the time of exposure can be improved as content is 0.1 mass part or more. On the other hand, 25 parts by mass or less is preferable, 20 parts by mass or less is more preferable, 17 parts by mass or less is more preferable, and 15 parts by mass or less is particularly preferable. When the content is 25 parts by mass or less, the resolution after development can be improved, and a low taper pattern shape can be obtained.
- the negative photosensitive resin composition of the present invention further contains (Da) a blackening agent as the (D) coloring agent.
- the colorant (D) is a compound which absorbs light of a specific wavelength, and particularly refers to a compound which absorbs light of the wavelength of visible light (380 to 780 nm) to color it.
- a film obtained from the negative photosensitive resin composition can be colored, and light transmitted through the film of the resin composition or light reflected from the film of the resin composition Can be colored to give the desired color.
- coloring agent the compound which absorbs the light of the wavelength of visible light, and colors red, orange, yellow, green, blue, or purple is mentioned. By combining these coloring agents in two or more colors, toning of light transmitted through the film of the resin composition or light reflected from the film of the resin composition to a desired color coordinate is improved. be able to.
- the negative photosensitive resin composition of the present invention contains (Da) a blackening agent as an essential component as the (D) coloring agent.
- the blackening agent refers to a compound that is colored black by absorbing light of the wavelength of visible light.
- a film of the resin composition is blackened by containing a blackening agent, a light shielding property that shields the light transmitted through the film of the resin composition or the light reflected from the film of the resin composition It can be improved.
- the pixel division layer, the electrode insulating layer, the wiring insulating layer, the interlayer insulating layer, the TFT planarization layer, the electrode planarization layer, the wiring planarization layer, the TFT protective layer, the electrode protective layer, the wiring protective layer, the gate insulating layer It is suitable for applications such as color filters, black matrices or black column spacers.
- a pixel division layer having a light shielding property of an organic EL display an electrode insulation layer, a wiring insulation layer, an interlayer insulation layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protection layer, a wiring
- a protective layer or a gate insulating layer and suitable for applications where high contrast is required by suppressing external light reflection, such as a pixel division layer having a light shielding property, an interlayer insulating layer, a TFT planarizing layer, or a TFT protective layer. is there.
- (D) Black in a coloring agent means that "BLACK" is contained in Color Index Generic Name (following, "CI number”).
- Two or more C.I. I. A mixture of (D) colorants whose number is not black, and C.I. I. The black color in the mixture of two or more colors of the (D) colorant containing at least one non-numbered (D) colorant means black when it is a cured film.
- black means the transmittance per 1.0 ⁇ m of film thickness at a wavelength of 550 nm in the transmission spectrum of the cured film of the resin composition containing (D) a colorant, based on the Lambert-Veil equation.
- the film thickness is converted in the range of 0.1 to 1.5 ⁇ m so that the transmittance at a wavelength of 550 nm is 10%, the transmittance at a wavelength of 450 to 650 nm in the transmission spectrum after conversion is 25 It says that it is less than%.
- the transmission spectrum of the cured film can be determined by the following method.
- the resin composition containing at least an optional binder resin and (D) colorant is prepared such that the content ratio of (D) colorant in the total solid content of the resin composition is 35% by mass.
- the film After applying a film of the resin composition on a Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.), the film is prebaked at 110 ° C. for 2 minutes to form a film to obtain a prebaked film.
- a high temperature inert gas oven IH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.
- a 1.0 ⁇ m cured film (hereinafter, "colorant-containing cured film") is prepared. Also, a resin composition containing the binder resin and (D) not containing a colorant is prepared, applied, prebaked and thermally cured on a Tempax glass substrate by the same method as described above, (D) coloring A cured film with a film thickness of 1.0 ⁇ m of a resin composition containing no agent (hereinafter, "cured film for blank”) is prepared.
- a UV-visible spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation), measure a Tempax glass substrate on which a blank cured film is formed with a film thickness of 1.0 ⁇ m, and use the UV-visible absorption spectrum as a blank Do.
- the tempax glass substrate on which the produced colorant-containing cured film is formed is measured by a single beam, and the transmittance per 1.0 ⁇ m film thickness at a wavelength of 450 to 650 nm is determined. Calculate the transmittance of the cured film.
- the blackening agent (Da) a compound which absorbs light of all wavelengths of visible light and is colored black is preferable from the viewpoint of light shielding. Also preferred is a mixture of two or more (D) colorants selected from red, orange, yellow, green, blue or violet colorants. By combining these (D) colorants in two or more colors, it can be pseudo-black, and the light shielding property can be improved.
- the maximum transmission wavelength of the blackening agent is preferably 330 nm or more, more preferably 340 nm or more, and still more preferably 350 nm or more.
- the maximum transmission wavelength is 330 nm or more, the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development. In addition, it is possible to suppress a change in the dimension opening width of the pattern before and after heat curing, and to improve halftone characteristics.
- the maximum transmission wavelength of the (Da) blackening agent is preferably 410 nm or less, more preferably 400 nm or less, still more preferably 390 nm or less, and particularly preferably 380 nm or less.
- the sensitivity at the time of exposure can be improved as the maximum transmission wavelength is 410 nm or less, and a pattern with a low taper shape can be formed after development.
- the maximum transmission wavelength of the (Da) blackening agent is 330 to 410 nm
- the maximum absorption wavelength of the (C1-1) specific oxime ester photopolymerization initiator described above is 330 to 410 nm. Is preferred.
- the maximum transmission wavelength of the colorant (D) is determined by measuring the transmittance per film thickness of 1.0 ⁇ m at a wavelength of 300 to 800 nm, as in the measurement method of the transmission spectrum of the cured film described above. It can be calculated by finding the wavelength that indicates the maximum transmission in the transmission spectrum.
- the (Da) blackening agent mentioned above is a mixture of (D1a) black pigment, (D2a-1) black dye and (D2a-2) two or more dye mixtures described later. It is preferable to contain one or more types to be selected, and it is more preferable to contain a (D1a) black pigment described later from the viewpoint of the light shielding property.
- a coloring agent other than black refers to a compound that is colored by absorbing light of the wavelength of visible light. That is, it is a coloring agent which colors red, orange, yellow, green, blue, or purple except black which was mentioned above.
- a blackening agent and (Db) a coloring agent other than black, it is possible to impart light shielding properties, coloring properties and / or toning properties to the film of the resin composition.
- the colorant other than (Db) black described above preferably contains a pigment other than (D1b) black and / or a dye other than (D2b) black described later. It is more preferable to contain pigments other than (D1b) black described later, from the viewpoints of light shielding property and heat resistance or weather resistance.
- the content ratio of the (D) colorant in the total 100% by mass of the (A) alkali-soluble resin, (D) colorant, and (E) dispersant described later is 15 mass% or more is preferable, 20 mass% or more is more preferable, 25 mass% or more is more preferable, 30 mass% or more is especially preferable.
- the content ratio is 15% by mass or more, light shielding properties, coloring properties, or toning properties can be improved.
- 80 mass% or less is preferable, as for the content ratio of (D) coloring agent, 75 mass% or less is more preferable, 70 mass% or less is more preferable, 65 mass% or less is especially preferable.
- the sensitivity at the time of exposure can be improved as a content ratio is 80 mass% or less.
- the content ratio of the (D) coloring agent which occupies for the total solid of the negative photosensitive resin composition of this invention except a solvent 10 mass% or more is more preferable, and 15 mass % Or more is more preferable, and 20% by mass or more is particularly preferable.
- the content ratio is 5% by mass or more, light shielding properties, coloring properties, or toning properties can be improved.
- 70 mass% or less is preferable, as for the content ratio of (D) coloring agent, 65 mass% or less is more preferable, 60 mass% or less is more preferable, 55 mass% or less is still more preferable, 50 mass% or less is especially preferable preferable.
- the sensitivity at the time of exposure can be improved as a content ratio is 70 mass% or less.
- the preferred content ratio of the (Da) blackening agent is as described above for the preferred content ratio of the (D) coloring agent.
- the (D) colorant described above contains a (D1) pigment.
- the (Da) black agent described above is necessarily contained, and a colorant other than (Db) black may optionally be contained.
- the (D1) pigment is a compound that causes the surface of the object to be physically adsorbed, or causes the surface of the object to interact with the (D1) pigment to color the object. Generally, it is insoluble in solvents and the like.
- the coloring by the (D1) pigment has high hiding ability and is hardly discolored by ultraviolet rays and the like.
- (D1) By containing a pigment, it can be colored to a color excellent in hiding property, and the light shielding property and the weather resistance of the film of the resin composition can be improved.
- the number average particle diameter of the (D1) pigment is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and still more preferably 10 to 200 nm.
- the number average particle diameter of the pigment (D1) is 1 to 1,000 nm, the light shielding property of the film of the resin composition and the dispersion stability of the pigment (D1) can be improved.
- the number average particle diameter of the (D1) pigment is a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter, Inc.) or a zeta potential / particle diameter / molecular weight measuring device (Zetasizer Nano ZS; Sysmex Corporation) (D1) pigment can be used to measure the laser scattering due to Brownian motion of the (D1) pigment in the solution (dynamic light scattering method). Further, the number average particle diameter of the (D1) pigment in the cured film obtained from the resin composition is measured using a scanning electron microscope (hereinafter, "SEM”) and a transmission electron microscope (hereinafter, "TEM"). You can ask for it by doing.
- SEM scanning electron microscope
- TEM transmission electron microscope
- the number average particle diameter of the (D1) pigment is directly measured with a magnification of 50,000 to 200,000.
- D1 When the pigment is a true sphere, the diameter of the true sphere is measured to obtain a number average particle diameter.
- D1 When the pigment is not a true sphere, the longest diameter (hereinafter, "major axis diameter”) and the longest diameter (hereinafter, “minor axis diameter”) in the direction orthogonal to the major axis diameter are measured. The minor axis diameter is averaged, and the biaxial average diameter is taken as the number average particle diameter.
- Examples of the (D1) pigment include (D1-1) an organic pigment or (D1-2) an inorganic pigment.
- (D1-1) As the organic pigment for example, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, surren pigments, indoline pigments, benzofuranone pigments And perylene pigments, aniline pigments, azo pigments, condensed azo pigments, and carbon black.
- the inorganic pigment for example, graphite or silver-tin alloy, or fine particles of metal such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver, oxide, And complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitrides.
- the preferred content ratio of the (D1) pigment, the (D1-1) organic pigment, and the (D1-2) inorganic pigment in the total solid content of the negative photosensitive resin composition of the present invention excluding the solvent is as described above. It is as the preferable content ratio of (D) coloring agent.
- the (D1) pigment described above preferably contains (D1a) black pigment or (D1a) black pigment and (D1b) a pigment other than black.
- the black pigment refers to a pigment that is colored black by absorbing light of the wavelength of visible light.
- D1a By containing a black pigment, the film of the resin composition turns black, and the shielding property is excellent, so the light shielding property of the film of the resin composition can be improved.
- the (Da) black agent described above is a (D1a) black pigment
- the (D1a) black pigment is a (D1a-1) black organic pigment described later (D1a).
- D1a-2) One or more selected from black inorganic pigments and (D1a-3) two or more color pigment mixtures are preferable.
- a pigment other than black refers to a pigment that colors purple, blue, green, yellow, orange or red except black by absorbing light of the wavelength of visible light.
- D1b By containing a pigment other than black, the film of the resin composition can be colored, and coloring or toning can be imparted.
- D1b By combining two or more pigments other than black, the film of the resin composition can be toned to a desired color coordinate, and the toning property can be improved. Examples of pigments other than black (D1b) include pigments described later, which are colored in red, orange, yellow, green, blue, or purple except black.
- the pigment other than (D1b) black described above is an organic pigment other than (D1b-1) black and / or an inorganic pigment other than (D1b-2) black described later. Is preferred.
- the above-mentioned (D1a) black pigment is (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) two or more colors It is preferable that it is 1 or more types chosen from a color pigment mixture.
- the black organic pigment refers to an organic pigment that is colored black by absorbing light of a wavelength of visible light.
- the black organic pigment By containing a black organic pigment, the film of the resin composition turns black and the shielding property is excellent, so the light shielding property of the film of the resin composition can be improved. Furthermore, since it is an organic substance, it adjusts the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or shielding light of a desired specific wavelength by chemical structural change or functional conversion, to improve the color matching property. Can.
- the film resistance value can be obtained by including the (D1a-1) black organic pigment. Can be improved.
- an insulating layer such as a pixel division layer of an organic EL display, a TFT planarization layer, or a TFT protective layer, it is possible to suppress light emission defects and the like and to improve reliability.
- Examples of the (D1a-1) black organic pigment include anthraquinone black pigments, benzofuranone black pigments, perylene black pigments, aniline black pigments, azo black pigments, azomethine black pigments, and carbon black.
- Examples of carbon black include channel black, furnace black, thermal black, acetylene black, and lamp black. Channel black is preferred from the viewpoint of light shielding.
- the black inorganic pigment refers to an inorganic pigment that is colored black by absorbing light of the wavelength of visible light.
- D1a-2 By containing a black inorganic pigment, the film of the resin composition turns black, and the shielding property is excellent, so the light shielding property of the film of the resin composition can be improved. Furthermore, since it is an inorganic substance and is excellent in heat resistance and weather resistance, the heat resistance and weather resistance of the film of the resin composition can be improved.
- black inorganic pigments include fine particles and oxides of graphite or silver-tin alloy, or metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver And complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitrides. From the viewpoint of light shielding property improvement, fine particles of titanium or silver, oxides, composite oxides, sulfides, nitrides, carbides, or oxynitrides are preferable as the (D1a-2) black inorganic pigment, and nitrides of titanium are preferable. Or the oxynitride is more preferable.
- the pigment mixture of two or more colors is a pigment that pseudo-blackens by combining two or more pigments selected from red, orange, yellow, green, blue, or purple pigments. I say a mixture.
- D1a-3 By containing a pigment mixture of two or more colors, the film of the resin composition becomes black and the shielding property is excellent, so that the light shielding property of the film of the resin composition can be improved. Furthermore, in order to mix two or more pigments, it is possible to adjust the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or blocking light of a desired specific wavelength, and to improve the color matching property.
- black organic pigment black inorganic pigment, red pigment, orange pigment, yellow pigment, green pigment, blue pigment and violet pigment, known pigments can be used.
- the pigment other than (D1b) black is an organic pigment other than (D1b-1) black and / or an inorganic pigment other than (D1b-2) black. Is preferred.
- An organic pigment other than black refers to an organic pigment that colors red, orange, yellow, green, blue, or purple except black by absorbing light of a wavelength of visible light.
- organic pigments other than black are organic substances, the transmission spectrum or absorption spectrum of the film of the resin composition is transmitted, for example, transmitting or shielding light of a desired specific wavelength by chemical structural change or functional conversion. Adjustment can be made to improve the toning property.
- An inorganic pigment other than black refers to an inorganic pigment which is colored in red, orange, yellow, green, blue or purple except black by absorbing light of wavelength of visible light.
- the inorganic pigment other than black is an inorganic substance and is excellent in heat resistance and weather resistance, so the heat resistance and weather resistance of the film of the resin composition can be improved.
- one organic pigment other than (D1b-1) black is selected from the group consisting of blue pigment, red pigment, yellow pigment, violet pigment, orange pigment and green pigment It is preferable that it is a kind or more. However, the color pigment mixture of (D1a-3) two or more colors as the above-mentioned (D1a) black pigment is excluded.
- the organic pigment other than black is at least one selected from the group consisting of a blue pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, and a green pigment
- the light shielding of the film of the resin composition Since the transmittance of the wavelength in the ultraviolet region can be increased while maintaining the property, the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics can be improved.
- pigments to be colored in blue examples include pigment blue 15, 15: 3, 15: 4, 15: 6, 22, 60, or 64 (the numerical values are all C.I. numbers).
- pigment red 9 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, or 250 (all numerical values are C.I. numbers).
- pigment yellow 12 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 120, 125, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 166, 168, 175, 180, 181, 185, 192, or 194 (all numerical values are C.I. numbers).
- pigment violet 19 23, 29, 30, 32, 37, 40, or 50 is mentioned, for example (all numerical values are CI numbers).
- pigment orange for example, pigment orange 12, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, or 72 can be mentioned (all numerical values are C.I. numbers).
- pigment green 7, 10, 36, or 58 is mentioned, for example (all numerical values are C.I. numbers).
- the above-mentioned blue pigments are C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and C.I. I. Pigment Blue 60 is preferably one or more selected from the group consisting of C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 177, C.I. I. Pigment red 179, and C.I. I. Pigment red 190 is preferably selected from the group consisting of C.I. I. Pigment yellow 120, C.I. I.
- Pigment yellow 151, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 192, and C.I. I. Pigment yellow 194 is preferably selected from the group consisting of C.I. I. Pigment violet 19, C.I. I. Pigment violet 29 and C.I. I. Pigment violet 37 is preferably selected from the group consisting of C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. It is preferable that it is 1 or more types selected from the group which consists of pigment orange 72.
- the organic pigment other than (D1b-1) black has the above-described configuration, the pigment is excellent in heat resistance, and the halogen content derived from the pigment in the resin composition can be reduced, and the insulating property and low dielectric property Since it is excellent, in particular, when used as an insulating layer such as a pixel division layer of an organic EL display, a TFT planarization layer, or a TFT protective layer, it is possible to suppress a light emission failure and the like and to improve reliability.
- 1 mass% or more is preferable, and, as for the content ratio of organic pigments other than (D1 b-1) black which occupy in the total solid of the negative photosensitive resin composition of this invention except a solvent, 3 mass% or more is more preferable. 5 mass% or more is further preferable, and 7 mass% or more is especially preferable. While the sensitivity at the time of exposure can be improved as a content rate is 1 mass% or more, a pattern of low taper shape can be formed after development. In addition, halftone characteristics can be improved.
- the content ratio of the organic pigment other than (D1b-1) black is preferably 25% by mass or less, more preferably 22% by mass or less, still more preferably 20% by mass or less, and still more preferably 17% by mass or less Particularly preferred is mass% or less.
- the content ratio is 25% by mass or less, the light shielding property and the toning property can be improved.
- (D1a-1a) A film of a resin composition by containing one or more kinds selected from the group consisting of (B1) benzofuranone black pigment, (D1a-1 b) perylene black pigment, and (D1a-1 c) azo black pigment Since it is blackened and it is excellent in concealability, the light-shielding property of the film
- the light shielding property per unit content ratio of the pigment in the resin composition is excellent as compared with a general organic pigment, the same light shielding performance can be provided with a small content ratio. Therefore, the light shielding property of the film can be improved, and the sensitivity at the time of exposure can be improved.
- the film of the resin composition since it is an organic substance, it adjusts the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or shielding light of a desired specific wavelength by chemical structural change or functional conversion, to improve the color matching property.
- it since it is possible to improve the transmittance of the near infrared region wavelength (for example, 700 nm or more), it has a light shielding property, and is suitable for applications using light of the near infrared region wavelength.
- the insulating property and the low dielectric property are excellent as compared with general organic pigments and inorganic pigments, the resistance value of the film can be improved.
- an insulating layer such as a pixel division layer of an organic EL display, a TFT planarization layer, or a TFT protective layer, it is possible to suppress light emission defects and the like and to improve reliability.
- (D1a-1a) benzofuranone-based black pigment absorbs light of the wavelength of visible light, while it has high transmittance in the wavelength of ultraviolet region (for example, 400 nm or less), so (D1a-1a) benzofuranone-based black pigment
- a development residue derived from the pigment may be generated due to the insufficient alkali resistance of the pigment. That is, when the surface of the (D1a-1a) benzofuranone-based black pigment described above is exposed to the alkali developing solution during development, a part of the surface is decomposed or dissolved, and remains on the substrate as a development residue derived from the pigment May.
- (D1a-1a) A benzofuranone-based black pigment is blackened by absorbing light of a visible light wavelength having a benzofuran-2 (3H) -one structure or a benzofuran-3 (2H) -one structure in the molecule It refers to a compound to be colored.
- a benzofuranone-based black pigment a benzofuranone compound represented by any one of the general formulas (63) to (68), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer thereof is preferable.
- R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent hydrogen, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Or an alkyl group having 1 to 10 carbon atoms having 1 to 20 fluorine atoms.
- a plurality of R 208 , R 209 , R 214 , R 215 , R 220 or R 221 may form a ring with a direct bond or an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 251 bridge Absent.
- Each of R 210 , R 211 , R 216 , R 217 , R 222 and R 223 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- Each of a, b, c, d, e and f independently represents an integer of 0 to 4.
- the alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the aryl group described above may have a hetero atom, and may be either unsubstituted or substituted.
- R 253 , R 254 , R 259 , R 260 , R 265 and R 266 are each independently hydrogen, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Or an alkyl group having 1 to 10 carbon atoms having 1 to 20 fluorine atoms.
- a plurality of R 255 , R 256 , R 261 , R 262 , R 267 or R 268 may form a ring with a direct bond or an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 271 bridge Absent.
- Each of R 257 , R 258 , R 263 , R 264 , R 269 and R 270 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
- Each of a, b, c, d, e and f independently represents an integer of 0 to 4.
- the alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the aryl group described above may have a hetero atom, and may be either unsubstituted or substituted.
- benzofuranone-based black pigments examples include “IRGAPHOR” (registered trademark) BLACK S 0100 CF (manufactured by BASF), black pigments described in WO 2010/081624, or WO 2010/081756 And black pigments of
- the (D1a-1b) perylene black pigment refers to a compound having a perylene structure in the molecule, which is colored in black by absorbing light of a wavelength of visible light.
- the (D1a-1b) perylene black pigment is preferably a perylene compound represented by any one of the general formulas (69) to (71), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.
- X 92 , X 93 , X 94 and X 95 each independently represent an alkylene chain having 1 to 10 carbon atoms.
- R 224 and R 225 each independently represent hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.
- R 249 , R 250 and R 251 each independently represent hydrogen, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having 1 to 20 fluorine atoms.
- R 273 and R 274 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms.
- Each of a and b independently represents an integer of 0 to 5.
- the above-mentioned alkylene chain, alkoxy group, acyl group, and alkyl group may have a hetero atom, and may be either unsubstituted or substituted.
- Examples of (D1a-1b) perylene black pigments include, for example, pigment black 31 or 32 (all figures are CI numbers).
- PALIOGEN registered trademark
- BLACK S0084, K0084, L0086, K0086, EH0788, or FK4281 can be mentioned.
- the (D1a-1c) azo black pigment refers to a compound having an azo group in the molecule, which is colored in black by absorbing light of a visible light wavelength.
- an azo compound represented by the general formula (72) is preferable.
- X 96 represents an arylene chain having 6 to 15 carbon atoms.
- Y 96 represents an arylene chain having 6 to 15 carbon atoms.
- R 275 , R 276 and R 277 each independently represent a halogen or an alkyl group having 1 to 10 carbon atoms.
- R 278 represents a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a nitro group.
- R 279 represents a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acylamino group having 2 to 10 carbon atoms, or a nitro group.
- R 280 , R 281 , R 282 and R 283 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms.
- a represents an integer of 0 to 4
- b represents an integer of 0 to 2
- c represents an integer of 0 to 4
- d and e each independently represent an integer of 0 to 8.
- n each represents an integer of 1 to 4.
- the arylene chain, the alkyl group, the alkoxy group, and the acylamino group described above may have a hetero atom and may be either unsubstituted or substituted.
- azo black pigment for example, “CHROMOFINE” (registered trademark) BLACK A1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.), a black pigment described in JP-A-01-170601, or JP-A-02 Black pigments described in Japanese Patent Application Laid-Open No. 03-34664 can be mentioned.
- CHROMOFINE registered trademark
- BLACK A1103 manufactured by Dainichi Seika Kogyo Co., Ltd.
- JP-A-02 Black pigments described in Japanese Patent Application Laid-Open No. 03-34664 can be mentioned.
- the content ratio of one or more selected from the group consisting of pigments is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. When the content ratio is 5% by mass or more, the light shielding property and the toning property can be improved.
- the content ratio of one or more selected from the group consisting of (D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) azo-based black pigment is 70% by mass or less Is preferable, 65 mass% or less is more preferable, 60 mass% or less is more preferable, 55 mass% or less is still more preferable, and 50 mass% or less is particularly preferable.
- the sensitivity at the time of exposure can be improved as a content ratio is 70 mass% or less.
- the above-mentioned (D1a-3) pigment mixture of two or more colors is (D1a-3a) a color pigment mixture containing a blue pigment, a red pigment and a yellow pigment, (D1a -3b) Color pigment mixture containing purple pigment and yellow pigment, (D1a-3c) color pigment mixture containing blue pigment, red pigment and orange pigment, or (D1a-3d) blue pigment, purple pigment and orange pigment It is preferable that it is a color pigment mixture containing
- the film of the resin composition turns black, and the shielding property of the film of the resin composition can be improved since the film has excellent concealability .
- the transmittance of the wavelength in the ultraviolet region can be increased, the sensitivity at the time of exposure can be improved, and a pattern with a low taper shape can be formed after development.
- permeability of the wavelength of a near infrared region can be improved, it has light-shielding property and it is suitable for the use which utilizes the light of the wavelength of a near infrared region.
- pigments to be colored in blue examples include pigment blue 15, 15: 3, 15: 4, 15: 6, 22, 60, or 64 (the numerical values are all C.I. numbers).
- pigment red 9 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, or 250 (all numerical values are C.I. numbers).
- pigment yellow 12 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 120, 125, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 166, 168, 175, 180, 181, 185, 192, or 194 (all numerical values are C.I. numbers).
- pigment violet 19 23, 29, 30, 32, 37, 40, or 50 is mentioned, for example (all numerical values are CI numbers).
- pigment orange for example, pigment orange 12, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, or 72 can be mentioned (all numerical values are C.I. numbers).
- pigment green 7, 10, 36, or 58 is mentioned, for example (all numerical values are C.I. numbers).
- the blue pigment described above is C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and C.I. I. Pigment Blue 60 is preferably one or more selected from the group consisting of C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 177, C.I. I. Pigment red 179, and C.I. I. Pigment red 190 is preferably selected from the group consisting of C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 151, C.I. I.
- Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 192, and C.I. I. Pigment yellow 194 is preferably selected from the group consisting of C.I. I. Pigment violet 19, C.I. I. Pigment violet 29 and C.I. I. Pigment violet 37 is preferably selected from the group consisting of C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. It is preferable that it is 1 or more types selected from the group which consists of pigment orange 72.
- the alkali resistance of the pigment is excellent, so the decomposition or dissolution of the pigment surface during alkali development is suppressed, and the development residue generation due to the pigment is suppressed. be able to.
- the halogen content derived from the pigment in a resin composition can be reduced, and since it is excellent in insulation and low dielectric property, the resistance value of a film
- membrane can be improved.
- an insulating layer such as a pixel division layer of an organic EL display, a TFT planarization layer, or a TFT protective layer, it is possible to suppress light emission defects and the like and to improve reliability.
- the (D1a-1) black organic pigment preferably further contains a (DC) coating layer.
- the coating layer (DC) covers the pigment surface, which is formed by, for example, surface treatment with a silane coupling agent, surface treatment with a silicate, surface treatment with a metal alkoxide, or coating treatment with a resin. I say a layer.
- Modifying the surface state of the particles such as acidifying, basifying, hydrophilizing or hydrophobizing the particle surface of the (D1a-1) black organic pigment, by including a (DC) coating layer It is possible to improve acid resistance, alkali resistance, solvent resistance, dispersion stability, heat resistance and the like. As a result, it is possible to suppress the generation of development residues derived from the pigment.
- the (D1a-1) black organic pigment particularly contains a (D1a-1a) benzofuranone-based black pigment
- the (D1a-1a) benzofuranone-based black pigment contains the (DC) -coated layer to obtain the pigment.
- the alkali resistance of the pigment can be improved, and the development residue derived from the pigment can be suppressed.
- the average coverage by the (DC) coating layer on the (D1a-1) black organic pigment is preferably 50% or more, preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.
- the average coverage by the (DC) coating layer is 80% or more, generation of a residue during development can be suppressed.
- the average coverage of the (D1a-1) black organic pigment by the (DC) coating layer is a magnification of 300 kV under conditions of an accelerating voltage using a transmission electron microscope (H 9500; manufactured by Hitachi High-Technologies Corporation)
- the cross section is observed with 50,000 to 200,000 times the area of each black pigment, and the coverage M (%) of each black pigment is determined by the following equation for 100 randomly selected black pigment particles, and the number average value is calculated
- the average coverage N (%) can be determined by calculation.
- Coverage M (%) ⁇ L1 / (L1 + L2) ⁇ ⁇ 100
- L1 The total length (nm) of the portion of the outer periphery of the particle covered by the covering layer
- L2 The total length (nm) of the part of the outer periphery of the particle not covered by the covering layer (the part where the interface and the embedding resin are in direct contact)
- L1 + L2 peripheral length of particle (nm).
- the (DC) coating layer contains one selected from the group consisting of (DC-1) silica coating layer, (DC-2) metal oxide coating layer, and (DC-3) metal hydroxide coating layer. Is preferred. Since silica, metal oxides and metal hydroxides have a function of imparting alkali resistance to the pigment, generation of development residues derived from the pigment can be suppressed.
- (DC-1) Silica contained in the silica coating layer is a generic term for silicon dioxide and its hydrate.
- DC-2 The metal oxide contained in the metal oxide coating layer is a generic term for metal oxides and their hydrates.
- An example of the metal oxide is alumina, and examples thereof include alumina (Al 2 O 3 ) or alumina hydrate (Al 2 O 3 .nH 2 O).
- Examples of the metal hydroxide contained in the (DC-3) metal hydroxide coating layer include aluminum hydroxide (Al (OH) 3 ). Since the dielectric constant of silica is low, an increase in the dielectric constant of the pixel division layer can be suppressed even when the content of the (DC) coating layer of the (D1a-1) black organic pigment is large.
- the (DC-1) silica coating layer, the (DC-2) metal oxide coating layer and the (DC-3) metal hydroxide coating layer of the (DC) coating layer are analyzed by, for example, X-ray diffraction method be able to.
- X-ray-diffraction apparatus a powder X-ray-diffraction apparatus (made by Mac Science) etc. are mentioned, for example.
- the mass of silicon atoms or metal atoms contained in the (DC-1) silica coating layer, the (DC-2) metal oxide coating layer, and the (DC-3) metal hydroxide coating layer is rounded off to two decimal places. And calculate the value to the first decimal place.
- the mass of pigment particles excluding the (DC) covering layer contained in the (D1a-1) black organic pigment having the (DC) covering layer can be determined, for example, by the following method.
- the pigment whose mass is measured is put in a mortar and ground with a pestle to remove the coating layer (DC), and then it is immersed in an amide solvent such as N, N-dimethylformamide to dissolve only the particles of the pigment and filtrate
- an amide solvent such as N, N-dimethylformamide
- metal oxides or metal hydroxides contained in (DC-2) metal oxide coating layer or (DC-3) metal hydroxide coating layer chemical resistance such as alkali resistance, heat resistance and light resistance
- physical properties such as Vickers hardness which can endure mechanical energy input suitably optimized in the dispersing step, and abrasion resistance.
- a metal oxide and a metal hydroxide an alumina, a zirconia, a zinc oxide, a titanium oxide, or iron oxide etc. are mentioned, for example.
- Alumina or zirconia is preferable from the viewpoint of insulation, ultraviolet transmittance and near infrared transmittance, and alumina is more preferable from the viewpoint of dispersibility in an alkali-soluble resin and a solvent.
- the metal oxide and the metal hydroxide may be surface-modified with a group containing an organic group.
- an alumina coating layer is formed as a (DC-2) metal oxide coating layer on the surface of the (DC-1) silica coating layer.
- Alumina is also effective in improving the dispersibility in an aqueous pigment suspension even in the pigment sizing step carried out after the pigment surface treatment step, so that the secondary aggregation particle diameter can be adjusted to a desired range. Furthermore, productivity and quality stability can be improved.
- the coating amount of the alumina coating layer as the (DC-2) metal oxide coating layer contained in the (DC) coating layer is 10 parts by mass based on 100 parts by mass of the silica contained in the (DC-1) silica coating layer. More than part is preferable and 20 mass parts or more are more preferable.
- the content of silica is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the pigment particles. Preferably, 5 parts by mass or more is more preferable.
- the coverage of the particle surface of the pigment can be increased, and the development residue derived from the pigment can be suppressed.
- 20 mass parts or less are preferable, and, as for content of silica, 10 mass parts or less are more preferable. By setting the content to 20 parts by mass or less, the pattern linearity of the pixel division layer can be improved.
- the total content of the metal oxide and the metal hydroxide is When 100 parts by mass of pigment particles is used, 0.1 parts by mass or more is preferable, and 0.5 parts by mass or more is more preferable. By setting the total content to 0.1 parts by mass or more, the dispersibility and the pattern linearity can be improved. On the other hand, 15 mass parts or less are preferable, and, as for the sum total of content of a metal oxide and a metal hydroxide, 10 mass parts or less are more preferable.
- the concentration gradient generation of the pigment is generated in the photosensitive composition of the present invention designed to have a low viscosity, preferably a viscosity of 15 mPa ⁇ s or less. It is possible to suppress the storage stability of the coating liquid.
- the content of silica is calculated from the silicon atom content, including the case where it does not become a single component in the inside and the surface layer of the (DC) coating layer, or the case where a difference in dehydration amount occurs due to heat history It is a silicon dioxide conversion value, and it is a SiO 2 conversion value.
- Content of a metal oxide and a metal hydroxide means the metal oxide and metal hydroxide conversion value calculated from metal atom content. That is, in the case of alumina, zirconia and titanium oxide, they refer to an Al 2 O 3 converted value, a ZrO 2 converted value and a TiO 2 converted value, respectively.
- the sum total of the content of the metal oxide and the metal hydroxide means the content when either of the metal oxide and the metal hydroxide is contained, and the total amount of the content when both are contained.
- the surface may be modified with an organic group using a silane coupling agent, with the hydroxy on the surface of the oxide as the reaction point.
- an organic group an ethylenically unsaturated double bond group is preferable.
- the outermost layer may be further subjected to surface treatment with an organic surface treatment agent.
- the (DC) coating layer may further contain a resin coating layer formed by coating treatment with a resin.
- the particle surface is coated with an insulating resin having low conductivity, the surface condition of the particles can be modified, and the light shielding property and the insulating property of the cured film can be improved.
- the above-mentioned (D) colorant preferably contains a (D2) dye.
- the (D) coloring agent described above contains the (D2) dye
- a dye is a compound that causes the surface structure of an object to be colored by causing a substituent such as an ionic group or a hydroxy group in the dye to interact with the surface structure of the object (D2) or the like. Generally, they are soluble in solvents and the like. In addition, coloring with the (D2) dye has high coloring power and high coloring efficiency because each molecule adsorbs with the object.
- (D2) By containing a dye, it is possible to color the color with excellent coloring power, and it is possible to improve the colorability and toning property of the film of the resin composition.
- (D2) dyes include direct dyes, reactive dyes, sulfur dyes, vat dyes, acid dyes, metal-containing dyes, metal-containing acid dyes, basic dyes, mordant dyes, acid mordant dyes, disperse dyes, cationic dyes Or fluorescent whitening dyes.
- the disperse dye is a dye which is insoluble or poorly soluble in water and does not have an anionic ionizable group such as a sulfonic acid group or a carboxy group.
- D2 Dyes include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, and srene dyes And perinone dyes, perylene dyes, triarylmethane dyes, and xanthene dyes. From the viewpoint of solubility in solvents and heat resistance described later, anthraquinone dyes, azo dyes, azine dyes, methine dyes, triarylmethane dyes and xanthene dyes are preferable.
- the above-mentioned (D2) dye is not limited to (D2a-1) black dye described later, (D2a-2) two or more dye mixtures, and (D2b) black It is preferable to contain one or more types selected from dyes.
- 0.01 mass% or more is preferable, and, as for the content ratio of the (D2) dye which occupies in the total solid of the negative photosensitive resin composition of this invention except a solvent, 0.05 mass% or more is more preferable, and 0 1% by mass or more is more preferable.
- the content ratio is 0.01% by mass or more, the colorability or the toning property can be improved.
- 50 mass% or less is preferable, as for the content ratio of (D2) dye, 45 mass% or less is more preferable, and 40 mass% or less is more preferable.
- the heat resistance of a cured film can be improved as a content ratio is 50 mass% or less.
- the above-mentioned (D2) dye is selected from (D2a-1) black dye, (D2a-2) two or more dye mixtures, and (D2b) dyes other than black It is preferable to contain one or more selected.
- the black dye is a dye that colors black by absorbing light of the wavelength of visible light.
- D2a-1 When the black dye is contained, the film of the resin composition turns black and the coloring property is excellent, so the light shielding property of the film of the resin composition can be improved.
- (D2a-2) A mixture of two or more dyes is artificially colored black by combining two or more dyes selected from white, red, orange, yellow, green, blue, and purple dyes. , Say dye mixtures. (D2a-2) By containing a dye mixture of two or more colors, the film of the resin composition turns black and the coloring property is excellent, so the light shielding property of the film of the resin composition can be improved. Furthermore, in order to mix two or more dyes, it is possible to adjust the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or blocking light of a desired specific wavelength, to improve the color matching property. As the black dye, red dye, orange dye, yellow dye, green dye, blue dye and purple dye, known dyes can be used.
- Dyes other than black are dyes that are colored in white, red, orange, yellow, green, blue, or purple except black by absorbing light of the wavelength of visible light.
- D2b By containing a dye other than black, the film of the resin composition can be colored, and coloring or toning can be imparted.
- D2b By combining two or more dyes other than black, the film of the resin composition can be toned to a desired color coordinate, and the toning property can be improved.
- Examples of dyes other than black include the dyes described above which are colored in white, red, orange, yellow, green, blue, or purple except black.
- the cured film obtained by curing the negative photosensitive resin composition according to the present invention preferably has an optical density of 0.3 or more in the visible light region per 1 ⁇ m of film thickness, and more preferably 0.5 or more. Preferably, it is 0.7 or more, more preferably 1.0 or more.
- the visible light region has a wavelength of about 400 to 700 nm. Since the light shielding property can be improved by the cured film when the optical density per 1 ⁇ m of film thickness is 0.3 or more, in a display device such as an organic EL display or a liquid crystal display, visualization of electrode wiring is prevented or external light is reflected. The reduction is possible, and the contrast in image display can be improved.
- the pixel division layer, the electrode insulating layer, the wiring insulating layer, the interlayer insulating layer, the TFT planarization layer, the electrode planarization layer, the wiring planarization layer, the TFT protective layer, the electrode protective layer, the wiring protective layer, the gate insulating layer It is suitable for applications such as color filters, black matrices, or black column spacers.
- a pixel division layer having a light shielding property of an organic EL display an electrode insulation layer, a wiring insulation layer, an interlayer insulation layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protection layer, a wiring
- a protective layer or a gate insulating layer and suitable for applications where high contrast is required by suppressing external light reflection, such as a pixel division layer having a light shielding property, an interlayer insulating layer, a TFT planarizing layer, or a TFT protective layer. is there.
- the optical density per 1 ⁇ m of film thickness is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less. While the sensitivity at the time of exposure can be improved as the optical density per film thickness per 1 micrometer is 5.0 or less, a cured film with a low taper pattern shape can be obtained.
- the optical density per 1 ⁇ m of the film thickness of the cured film can be adjusted by the composition and content ratio of the (D) colorant described above.
- the negative photosensitive resin composition of the present invention preferably further contains (E) a dispersant.
- the (E) dispersant is a surface affinity group that interacts with the surface of the disperse dye or the like as the (D1) pigment and / or (D2) dye described above, and a dispersion as the (D1) pigment and / or (D2) dye It refers to a compound having a dispersion stabilization structure that improves the dispersion stability of the dye.
- Examples of the dispersion stabilizing structure of the dispersant (E) include a polymer chain and / or a substituent having an electrostatic charge.
- the dispersion stability can be improved by containing the dispersant (E).
- the resolution after development can be improved.
- the surface area of the (D1) pigment particles increases, so aggregation of the (D1) pigment particles tends to occur. Become.
- the surface of the crushed (D1) pigment interacts with the surface affinity group of the (E) dispersant and the dispersion stabilization of the (E) dispersant Steric hindrance due to structure and / or electrostatic repulsion can inhibit aggregation of particles of the (D1) pigment and improve dispersion stability.
- the (E) dispersant having a surface affinity group for example, (E) dispersant having only a basic group, (E) dispersant having a basic group and an acidic group, and having only an acidic group (E) A dispersing agent or (E) dispersing agent which does not have any of a basic group and an acidic group is mentioned. From the viewpoint of improving the dispersion stability of the particles of the pigment (D1), the (E) dispersant having only a basic group and the (E) dispersant having a basic group and an acidic group are preferable. Moreover, it is also preferable that the basic group which is a surface affinity group and / or the acidic group have a structure formed with an acid and / or a base.
- the basic group or the structure formed by salt formation of the basic group possessed by the dispersant includes tertiary amino group, quaternary ammonium salt structure, or pyrrolidine skeleton, pyrrole skeleton, imidazole skeleton, pyrazole skeleton, triazole skeleton, Tetrazole skeleton, imidazoline skeleton, oxazole skeleton, isoxazole skeleton, oxazoline skeleton, isoxazoline skeleton, thiazole skeleton, isothiazole skeleton, thiazole skeleton, thiazole skeleton, thiazole skeleton, thiazole skeleton, thiazoline skeleton, thiazoline skeleton, isothiazoline skeleton, thiazine skeleton, piperidine skeleton, piperazine skeleton, morpholine skeleton, pyridine skeleton, pyridazine skeleton
- the structure in which a basic group or a basic group forms a salt includes a tertiary amino group, a quaternary ammonium salt structure, or a pyrrole skeleton, an imidazole skeleton, and a pyrazole skeleton Containing pyridine skeleton, pyridazine skeleton, pyrimidine skeleton, pyrazine skeleton, triazine skeleton, isocyanuric acid skeleton, imidazolidinone skeleton, propylene urea skeleton, butylene urea skeleton, hydantoin skeleton, barbituric acid skeleton, alloxan skeleton or glycoluril skeleton, etc.
- a nitrogen ring skeleton is preferred.
- (E) dispersant having only a basic group, for example, "DISPERBYK” (registered trademark) -108, -160, -167, -182, -2000, or -2164, “BYK” (Registered trademark)-9075, -LP-N 6919, or the same-LP-N 21116 (all of which are manufactured by Big Chemie Japan), "EFKA” (registered trademark) 4015, 4050, 4080, 4300, 4400 or 4800 (all are BASF Corporation), "Ajispar” (registered trademark) PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.), or "SOLSPERSE” (registered trademark) 13240, 20000, or 71000 (or more, All include Lubrizol's).
- (E) dispersant having a basic group and an acidic group for example, “ANTI-TERRA” (registered trademark) -U100 or -204, “DISPERBYK” (registered trademark) -106, -140, and- 145, -180, -191, -2001, or -2020, “BYK” (registered trademark)-9076 (manufactured by Bick Chemie Japan), "Azipasper” (registered trademark) PB 821 or PB 881 (above, All of them are made by Ajinomoto Fine Techno Co., Ltd., or “SOLSPERSE” (registered trademark) 9000, 13650, 24000, 33000, 37500, 39000, 56000, or 76500 (all are products of Lubrizol). It can be mentioned.
- (E) dispersant having only an acidic group for example, “DISPERBYK” (registered trademark) -102, -118, -170, or -2096, “BYK” (registered trademark) -P104, or the same -220S (all manufactured by Big Chemie Japan) or "SOLSPERSE” (registered trademark) 3000, 16000, 21000, 36000 or 55000 (all manufactured by Lubrizol).
- dispersant (E) having neither a basic group nor an acidic group examples include, for example, “DISPERBYK” (registered trademark) -103, -192, -2152, or -2200 (all of which are BIC Chem. And “SOLSPERSE” (registered trademark) 27000, 54000, or X300 (all of which are made by Lubrizol).
- the amine value of the dispersant (E) is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, and still more preferably 10 mg KOH / g or more.
- the dispersion stability of (D1) pigment can be improved as an amine value is 5 mgKOH / g or more.
- 150 mgKOH / g or less is preferable, 120 mgKOH / g or less is more preferable, and 100 mgKOH / g or less is more preferable.
- the storage stability of a resin composition can be improved as an amine titer is 150 mgKOH / g or less.
- the amine value referred to herein means the weight of potassium hydroxide equivalent to the acid to be reacted with 1 g of the (E) dispersant, and the unit is mg KOH / g.
- the amine equivalent weight (unit: g / mol), which is the resin weight per 1 mol of basic group such as amino group, can be calculated from the value of amine value, and (E) Basic group such as amino group in dispersant You can determine the number of
- the acid value of the dispersant (E) is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, and still more preferably 10 mg KOH / g or more.
- the dispersion stability of the (D1) pigment can be improved.
- 200 mgKOH / g or less is preferable, 170 mgKOH / g or less is more preferable, and 150 mgKOH / g or less is more preferable.
- the storage stability of a resin composition can be improved as an acid value is 200 mgKOH / g or less.
- the acid value as used herein refers to the weight of potassium hydroxide which reacts with 1 g of the (E) dispersant, and the unit is mg KOH / g. (E) It can obtain
- an acrylic resin dispersant As a (E) dispersant having a polymer chain, an acrylic resin dispersant, a polyoxyalkylene ether dispersant, a polyester dispersant, a polyurethane dispersant, a polyol dispersant, a polyethyleneimine dispersant, or a polyallylamine A system dispersant is mentioned. From the viewpoint of pattern processability with an alkaline developer, acrylic resin dispersants, polyoxyalkylene ether dispersants, polyester dispersants, polyurethane dispersants, or polyol dispersants are preferable.
- the negative photosensitive resin composition of the present invention contains a disperse dye as (D1) pigment and / or (D2) dye
- the content ratio of the (E) dispersant in the negative photosensitive resin composition of the present invention When the total of (D1) pigment and / or disperse dye and (E) dispersant is 100% by mass, 1% by mass or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is more preferable.
- the content ratio is 1% by mass or more, the dispersion stability of the (D1) pigment and / or the disperse dye can be improved, and the resolution after development can be improved.
- the heat resistance of a cured film can be improved as a content ratio is 60 mass% or less.
- the negative photosensitive resin composition of the present invention preferably further contains a chain transfer agent.
- a chain transfer agent refers to a compound capable of receiving a radical from a polymer growth terminal of a polymer chain obtained by radical polymerization at the time of exposure and capable of undergoing radical transfer to another polymer chain.
- the chain transfer agent preferably contains (F) a multifunctional thiol compound.
- F By including a polyfunctional thiol compound, the sensitivity at the time of exposure can be improved. It is presumed that this is because radicals generated by exposure to light move to other polymer chains to radically crosslink to the deep part of the film.
- the resin composition contains (Da) a blackening agent as the (D) coloring agent described above, the light from the exposure is absorbed by the (Da) blackening agent, so the light does not reach the deep part of the film There is a case.
- (F) a multifunctional thiol compound when (F) a multifunctional thiol compound is contained, radical transfer is performed to the deep part of the film by radical transfer, so that the sensitivity at the time of exposure can be improved.
- a cured film having a low taper pattern shape can be obtained. It is presumed that this is because the radical transfer can control the molecular weight of the polymer chain obtained by radical polymerization at the time of exposure. That is, by containing the (F) polyfunctional thiol compound, the formation of a remarkable high molecular weight polymer chain by excessive radical polymerization at the time of exposure is inhibited, and an increase in the softening point of the obtained film is suppressed. Therefore, it is thought that the reflow property of the pattern at the time of thermosetting is improved, and a low taper pattern shape can be obtained.
- the negative photosensitive resin composition of the present invention contains the above-mentioned (C1-1) specific oxime ester-based photopolymerization initiator and (F) polyfunctional thiol compound, thereby generating residues during development. While being able to control, change of pattern opening size width before and behind thermosetting can be controlled. This is presumed to be due to the fact that (G) the multifunctional thiol compound suppresses oxygen inhibition on the film surface, thereby promoting UV curing during exposure. That is, it is considered that (C1-1) UV curing by a specific oxime ester photopolymerization initiator is significantly promoted.
- (D1) pigment when (D1) pigment is contained as the coloring agent, (D1) pigment is fixed to the cured portion by crosslinking at the time of UV curing by oxygen inhibition suppression on the film surface.
- Generation of residues after development derived from when the (D1a-1a) benzofuranone-based black pigment is contained as the (Da) blackening agent, a development residue derived from the pigment may occur due to the insufficient alkali resistance of the pigment described above.
- the UV curing is promoted by the inhibition of oxygen inhibition on the film surface, and the generation of the development residue derived from the pigment described above can be suppressed.
- the negative photosensitive resin composition of the present invention is described above from the viewpoint of suppression of change in the dimension opening width of the pattern before and after thermosetting and formation of a low taper shape pattern after development (B4) It is preferable to contain an alicyclic group-containing radically polymerizable compound and a (F) polyfunctional thiol compound.
- (F) As the polyfunctional thiol compound, a compound selected from the group consisting of a compound represented by the general formula (83), a compound represented by the general formula (85), and a compound represented by the general formula (85) It is preferable to contain more than types.
- X 42 and X 43 each represent a divalent organic group.
- Each of X 44 and X 45 independently represents a direct bond or an alkylene chain having 1 to 10 carbon atoms.
- Y 42 to Y 53 each independently represent a direct bond, an alkylene chain having 1 to 10 carbon atoms, or a group represented by the general formula (86).
- Each of Z 40 to Z 51 independently represents a direct bond or an alkylene chain having 1 to 10 carbon atoms.
- R 231 to R 242 each independently represent an alkylene chain having 1 to 10 carbon atoms.
- Each of R 243 to R 245 independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- a, b, c, d, e, f, h, i, j, k, w and x each independently represent 0 or 1;
- g and l each independently represent an integer of 0 to 10;
- m, n, o, p, q, r, s, t, u, v, y and z each independently represent an integer of 0 to 10.
- ⁇ and ⁇ each independently represent an integer of 1 to 10.
- X 42 and X 43 each independently represent an aliphatic structure having 1 to 10 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or 6 to 30 carbon atoms.
- a divalent organic group having one or more kinds selected from aromatic structures is preferable.
- a, b, c, d, e, f, h, i, j, k, w and x are each independently preferably 1;
- g and l each independently are preferably an integer of 0 to 5.
- m, n, o, p, q, r, s, t, u, v, y and z are each independently preferably 0.
- Each of ⁇ and ⁇ is preferably independently an integer of 1 to 5, more preferably 1 or 2, and still more preferably 1.
- the alkyl group, the alkylene chain, the aliphatic structure, the alicyclic structure and the aromatic structure described above may have a hetero atom and may be either unsubstituted or substituted.
- R 246 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- Z 52 represents a group represented by General Formula (87) or a group represented by General Formula (88).
- a represents an integer of 1 to 10
- b represents an integer of 1 to 4
- c represents 0 or 1
- d represents an integer of 1 to 4
- e represents 0 or 1 .
- R 247 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- R 246 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- Z 52 represents a group represented by General Formula (87) or a group represented by General Formula (88).
- R 247 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
- c is preferably 1 and e is preferably 1.
- R 247 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably hydrogen or a methyl group.
- the polyfunctional thiol compound for example, ⁇ -mercaptopropionic acid, methyl ⁇ -mercaptopropionate, 2-ethylhexyl ⁇ -mercaptopropionate, stearyl ⁇ -mercaptopropionate, methoxybutyl ⁇ -mercaptopropionate, ⁇ -Mercaptobutanoic acid, methyl ⁇ -mercaptobutanoate, methyl thioglycolate, n-octyl thioglycolate, methoxybutyl thioglycolate, 1,4-bis (3-mercaptobutanoyloxy) butane, 1,4-bis (3-Mercaptopropionyloxy) butane, 1,4-bis (thioglycoloyloxy) butane, ethylene glycol bis (thioglycollate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptopropyl) (Pe
- Ethylene glycol bis (thioglycollate), ethylene glycol bis (3-mercapto propionate), ethylene glycol bis (2) from the viewpoints of sensitivity improvement at the time of exposure, pattern formation of a low taper shape, and suppression of residues after development.
- ethylene glycol bis (2-mercaptoethyl) ether, ethylene glycol bis (3-mercaptopropyl) ether, ethylene glycol bis (2-mercaptopropyl) ether, ethylene glycol bis (3- Mercaptobutyl) ether, 1,2-bis (2-mercaptoethylthio) ethane or 1,2-bis (3-mercaptopropylthio) ethane is more preferred.
- the content of the (F) polyfunctional thiol compound in the negative photosensitive resin composition of the present invention is 0 when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. .01 parts by mass or more is preferable, 0.1 parts by mass or more is more preferable, 0.3 parts by mass or more is more preferable, 0.5 parts by mass or more is still more preferable, and 1 parts by mass or more is particularly preferable. While the sensitivity at the time of exposure can be improved as content is 0.01 mass part or more, a cured film of pattern shape with a low taper can be obtained. In addition, the generation of residues during development can be suppressed.
- the content of the (F) polyfunctional thiol compound is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, and 5 parts by mass or less Is particularly preferred.
- the content is 15 parts by mass or less, a pattern with a low taper shape can be formed, generation of residues after development can be suppressed, and the heat resistance of the cured film can be improved.
- the negative photosensitive resin composition of the present invention preferably further contains a sensitizer.
- a sensitizer absorbs energy by exposure, generates an excited triplet electron by internal conversion and intersystem crossing, and generates a compound capable of energy transfer to the above-mentioned (C1) photopolymerization initiator and the like.
- the sensitivity at the time of exposure can be improved.
- the sensitizer absorbs light of long wavelength (C1) where the photopolymerization initiator and the like do not have absorption, and the energy is transferred from the sensitizer to the (C1) photopolymerization initiator etc. It is presumed that this is because the photoreaction efficiency can be improved.
- a thioxanthone type sensitizer is preferable.
- thioxanthone sensitizers include thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 2,4-dichlorothioxanthone.
- the content of the sensitizer in the negative photosensitive resin composition of the present invention is 0.01 parts by mass when the total of (A) the alkali soluble resin and the (B) radically polymerizable compound is 100 parts by mass.
- the above is preferable, 0.1 mass part or more is more preferable, 0.5 mass part or more is more preferable, 1 mass part or more is especially preferable.
- the sensitivity at the time of exposure can be improved as content is 0.01 mass part or more.
- the content of the sensitizer is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. When the content is 15 parts by mass or less, the resolution after development can be improved, and a cured film having a low taper pattern shape can be obtained.
- the negative photosensitive resin composition of the present invention preferably further contains a polymerization inhibitor.
- the polymerization inhibitor may be a radical generated at the time of exposure, or a radical of the polymer growth terminal of the polymer chain obtained by the radical polymerization at the time of exposure being captured and held as a stable radical to terminate the radical polymerization. Refers to possible compounds.
- a polymerization inhibitor By containing a polymerization inhibitor in an appropriate amount, it is possible to suppress the generation of residues after development and to improve the resolution after development. It is presumed that this is because the polymerization inhibitor captures excess radicals generated at the time of exposure or radicals at the growth terminals of high molecular weight polymer chains, thereby suppressing the progress of the radical polymerization.
- a phenol type polymerization inhibitor is preferable.
- phenolic polymerization inhibitors include 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, and the like.
- the content of the polymerization inhibitor in the negative photosensitive resin composition of the present invention is 0.01 parts by mass when the total of (A) alkali soluble resin and (B) radically polymerizable compound is 100 parts by mass.
- the above is preferable, 0.03 mass part or more is more preferable, 0.05 mass part or more is more preferable, 0.1 mass part or more is especially preferable.
- the content is 0.01 parts by mass or more, the resolution after development and the heat resistance of the cured film can be improved.
- 10 parts by mass or less is preferable, 8 parts by mass or less is more preferable, 5 parts by mass or less is more preferable, and 3 parts by mass or less is particularly preferable.
- the sensitivity at the time of exposure can be improved as content is 10 mass parts or less.
- the negative photosensitive resin composition of the present invention preferably further contains a crosslinking agent.
- the crosslinking agent refers to a compound having a crosslinkable group capable of binding to a resin.
- the pattern formation of the low taper shape is attained after thermosetting by containing a crosslinking agent.
- a crosslinking agent forms a cross-linked structure between the polymers, thereby inhibiting the close alignment of polymer chains and maintaining the reflowability of the pattern during heat curing, so a pattern with a low taper shape It is thought that formation becomes possible.
- the crosslinking agent a compound having two or more thermal crosslinking properties such as alkoxymethyl group, methylol group, epoxy group, or oxetanyl group in a molecule is preferable.
- Examples of compounds having two or more alkoxymethyl groups or methylol groups in the molecule include DML-PC, DML-OC, DML-PTBP, DML-PCHP, DML-MBPC, DML-MTrisPC, DMOM-PC, and DMOM- PTBP, TriML-P, TriML-35 XL, TML-HQ, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPHAP, or HMOM-TPHAP (any one, any Honshu Chemical Industry Co., Ltd.) or “NIKALAC” (registered trademark) MX-290, MX-280, MX-270, MX-279, MW-100 LM, MW-30 HM, MW-390, Or same MX-750LM ( On, manufactured by Sanwa Chemical Co., Ltd.) and the like.
- ETERNACOLL registered trademark
- OXBP OXBP
- OXTP OXTP
- OXMA oxetanized phenol novolak
- the content of the crosslinking agent in the negative photosensitive resin composition of the present invention is 0.5 parts by mass or more when the total of (A) alkali-soluble resin and (B) radically polymerizable compound is 100 parts by mass. Is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. While being able to improve the hardness and chemical resistance of a cured film as content is 0.5 mass part or more, the pattern of low taper shape can be formed after thermosetting.
- the pattern of low taper shape can be formed after thermosetting.
- the negative photosensitive resin composition of the present invention preferably further contains a silane coupling agent.
- the silane coupling agent refers to a compound having a hydrolyzable silyl group or silanol group.
- interaction between the cured film of the resin composition and the interface between the base and the substrate can be increased, and adhesion to the substrate of the base and chemical resistance of the cured film can be improved.
- a silane coupling agent a trifunctional organosilane, a tetrafunctional organosilane, or a silicate compound is preferable.
- trifunctional organosilanes examples include methyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 1-naphthyltriol.
- each of R 226 to R 229 independently represents hydrogen, an alkyl group, an acyl group or an aryl group, and x represents an integer of 1 to 15.
- R 226 to R 229 are preferably each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Hydrogen, an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms is more preferable.
- the above-mentioned alkyl group, acyl group and aryl group may be either unsubstituted or substituted.
- organosilane represented by the general formula (73) examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraacetoxysilane.
- methyl silicate 51 made by Sakai Chemical Industry Co., Ltd.
- M silicate 51, silicate 40, or silicate 45 all above, made by Tama Chemical Co., Ltd.
- methyl silicate 51 methyl silicate 53A, ethyl silicate 40,
- silicate compounds such as ethyl silicate 48 (all, all are manufactured by Corcoat Co., Ltd.) etc. are mentioned.
- the content of the silane coupling agent in the negative photosensitive resin composition of the present invention is 0.01 mass when the total of (A) alkali soluble resin and (B) radically polymerizable compound is 100 parts by mass.
- the amount is preferably at least 0.1 part by mass, more preferably at least 0.5 parts by mass, and particularly preferably at least 1 part by mass.
- the content of the silane coupling agent is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.
- the resolution after development can be improved as content is 15 mass parts or less.
- the negative photosensitive resin composition of the present invention may further contain a surfactant.
- the surfactant refers to a compound having a hydrophilic structure and a hydrophobic structure. By incorporating an appropriate amount of surfactant, the surface tension of the resin composition can be arbitrarily adjusted, the leveling property at the time of application can be improved, and the film thickness uniformity of the coating film can be improved.
- the surfactant is preferably a fluorocarbon resin surfactant, a silicone surfactant, a polyoxyalkylene ether surfactant, or an acrylic resin surfactant.
- the content ratio of the surfactant in the negative photosensitive resin composition of the present invention is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, of the entire negative photosensitive resin composition. .01 mass% or more is more preferable.
- the leveling property at the time of application can be improved as a content rate is 0.001 mass% or more.
- the content ratio of the surfactant is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.03% by mass or less.
- coating can be improved as a content ratio is 1 mass% or less.
- the negative photosensitive resin composition of the present invention further contains a solvent.
- the solvent means a compound capable of dissolving various resins and various additives to be contained in the resin composition.
- various resins and various additives to be contained in the resin composition can be uniformly dissolved, and the transmittance of the cured film can be improved.
- the viscosity of the resin composition can be arbitrarily adjusted, and a film can be formed on a substrate with a desired film thickness.
- the surface tension of the resin composition or the drying speed at the time of application can be arbitrarily adjusted, and the leveling property at the time of application and the film thickness uniformity of the coating film can be improved.
- the solvent is preferably a compound having an alcoholic hydroxyl group, a compound having a carbonyl group, or a compound having three or more ether bonds from the viewpoint of solubility of various resins and various additives.
- compounds having a boiling point of 110 to 250 ° C. under atmospheric pressure are more preferred.
- Examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include diacetone alcohol, ethyl lactate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, or tetrahydrofurfuryl alcohol is mentioned.
- Examples of the compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include, for example, 3-methoxy-n-butyl acetate, 3-methyl-3-n-butyl acetate, propylene glycol monomethyl ether acetate And dipropylene glycol monomethyl ether acetate or ⁇ -butyrolactone.
- Examples of the compound having three or more ether bonds and having a boiling point of 110 to 250 ° C. under atmospheric pressure include diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, or dipropylene glycol dimethyl ether.
- the content ratio of the solvent in the negative photosensitive resin composition of the present invention can be appropriately adjusted according to the coating method and the like.
- it is generally 50 to 95% by mass of the whole negative photosensitive resin composition.
- a solvent having a carbonyl group or an ester bond is preferable as the solvent.
- a solvent having a carbonyl group or an ester bond the dispersion stability of the disperse dye as the (D1) pigment and / or the (D2) dye can be improved.
- a solvent having an acetate bond is more preferable.
- the dispersion stability of the disperse dye as the (D1) pigment and / or the (D2) dye can be improved.
- the content ratio of the solvent having a carbonyl group or an ester bond in the solvent is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 70 to 100%. % Is more preferred.
- the content ratio is 30 to 100% by mass, the dispersion stability of the (D1) pigment can be improved.
- the negative photosensitive resin composition of the present invention may further contain other resins or their precursors.
- Other resins or their precursors include, for example, polyamide, polyamideimide, epoxy resin, novolac resin, urea resin, or polyurethane, or their precursors.
- Dispersers include, for example, ball mills, bead mills, sand grinders, three roll mills, or high speed impact mills.
- a bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion.
- a bead mill a co-ball mill, a basket mill, a pin mill, or a Dyno mill is mentioned, for example.
- the beads of the bead mill include, for example, titania beads, zirconia beads, or zircon beads.
- the bead diameter of the bead mill is preferably 0.01 to 6 mm, more preferably 0.015 to 5 mm, and still more preferably 0.03 to 3 mm.
- (D1) When the primary particle diameter of the pigment and the particle diameter of the secondary particles formed by aggregation of the primary particles are several hundred nm or less, fine beads of 0.015 to 0.1 mm are preferable. In this case, it is preferable to use a bead mill provided with a separator by a centrifugal separation method that can separate minute beads and a pigment dispersion. On the other hand, when the (D1) pigment contains coarse particles of several hundred nm or more, beads of 0.1 to 6 mm are preferable from the viewpoint of dispersion efficiency.
- the negative photosensitive resin composition of the present invention can obtain a cured film including a cured pattern having a low taper pattern shape.
- the taper angle of the inclined side in the cross section of the cured pattern contained in the cured film obtained from the negative photosensitive resin composition of the present invention is preferably 1 ° or more, more preferably 5 ° or more, and still more preferably 10 ° or more, 12 degrees or more are still more preferable, and 15 degrees or more are especially preferable.
- the taper angle is 1 ° or more, the resolution of the display device can be improved because the light emitting elements can be integrated and arranged with high density.
- the taper angle of the inclined side in the cross section of the cured pattern contained in the cured film is preferably 60 ° or less, more preferably 55 ° or less, still more preferably 50 ° or less, still more preferably 45 ° or less, and 40 ° or less Particularly preferred.
- the taper angle is 60 ° or less, disconnection at the time of forming an electrode such as a transparent electrode or a reflective electrode can be prevented.
- the concentration of the electric field at the edge portion of the electrode can be suppressed, deterioration of the light emitting element can be suppressed.
- the negative photosensitive resin composition of the present invention has a step shape having a sufficient film thickness difference between the thick film portion and the thin film portion while maintaining high sensitivity, and a cured pattern having a low taper pattern shape. It can be formed.
- the negative photosensitive resin composition of the present invention is particularly suitable in the application for collectively forming the step shape of the pixel division layer in the organic EL display.
- an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, black It is suitable for the use for forming a level
- FIG. 1 An example of the cross section of the cured pattern having a step shape obtained from the negative photosensitive resin composition of the present invention is shown in FIG.
- the thick film portion 34 in the step shape corresponds to a cured portion at the time of exposure, and has the largest film thickness of the cured pattern.
- the thin film portions 35a, 35b, and 35c in the step shape correspond to halftone exposure portions at the time of exposure, and have a film thickness smaller than the thickness of the thick film portion 34.
- the taper angles ⁇ a , ⁇ b , ⁇ c , ⁇ d and ⁇ e of the inclined sides 36 a, 36 b, 36 c, 36 d and 36 e in the cross section of the cured pattern having the step shape are all low tapers .
- taper angle ⁇ a, ⁇ b, ⁇ c , ⁇ d, ⁇ e and, as shown in FIG. 3, the horizontal edge 37 or the thin film part 35a, of the underlying substrate to cure the pattern is formed, 35b,
- the forward taper means that the taper angle is in the range of more than 0 ° and less than 90 °
- the reverse taper means that the taper angle is in the range of more than 90 ° and less than 180 °.
- a rectangle means that a taper angle is 90 degrees
- a low taper means that a taper angle is larger than 0 degree and in the range of 60 degrees.
- the thick-film portion 34 is a region having the largest thickness in the thickness between the flat surface of the lower surface and the flat surface of the upper surface of the cured pattern having a stepped shape obtained from the negative photosensitive resin composition of the present invention
- a region having a thickness smaller than the thickness of the thick film portion 34 is referred to as a thin film portion 35.
- the film thickness of the thick film portion 34 is (T FT ) ⁇ m
- the film thickness of the thin film portions 35 a, 35 b, 35 c disposed on the thick film portion 34 via at least one step shape is (T HT ) ⁇ m
- the film thickness difference ( ⁇ T FT -HT ) ⁇ m between (T FT ) and (T HT ) is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, further preferably 1.5 ⁇ m or more, 2.0 ⁇ m
- the above is even more preferable, 2.5 ⁇ m or more is particularly preferable, and 3.0 ⁇ m or more is most preferable.
- the film thickness difference is within the above range, the contact area with the deposition mask when forming the light emitting layer can be made small, so that it is possible to suppress the decrease in yield of the panel due to particle generation and to suppress the deterioration of the light emitting element. Can.
- the film thickness difference ( ⁇ T FT -HT) ⁇ m is preferably 10.0 ⁇ m or less, more preferably 9.5 ⁇ m or less, still more preferably 9.0 ⁇ m or less, still more preferably 8.5 ⁇ m or less, and 8.0 ⁇ m or less Is particularly preferred.
- the film thickness (T FT ) ⁇ m of the thick film portion 34 and the film thickness (T HT ) ⁇ m of the thin film portions 35a, 35b, 35c satisfy the relationships represented by general formulas ( ⁇ ) to ( ⁇ ).
- the film thickness (T FT ) ⁇ m of the thick film portion 34 and the film thickness (T HT ) ⁇ m of the thin film portions 35 a, 35 b, 35 c further satisfy the relationships represented by general formulas ( ⁇ ) to ( ⁇ ) .
- the film thickness of the thick portion 34 (T FT) ⁇ m and the thin film portion 35a, 35b, the 35c of the thickness (T HT) [mu] m is within the range described above, it is possible to suppress the deterioration of the light emitting element, the process Time can be shortened.
- the taper angle of the inclined side in the cross section of the cured pattern having a step shape obtained from the negative photosensitive resin composition is preferably 1 ° or more, more preferably 5 ° or more, and 10 ° The above is more preferable, 12 ° or more is further more preferable, and 15 ° or more is particularly preferable.
- the taper angle is in the above-mentioned range, the light emitting elements can be integrated and arranged at high density, whereby the resolution of the organic EL display can be improved.
- the taper angle of the inclined side in the cross section of the cured pattern is preferably 60 ° or less, more preferably 55 ° or less, still more preferably 50 ° or less, still more preferably 45 ° or less, and particularly preferably 40 ° or less.
- the taper angle is in the above-described range, disconnection at the time of forming an electrode such as a transparent electrode or a reflective electrode can be prevented.
- the concentration of the electric field at the edge portion of the electrode can be suppressed, the deterioration of the light emitting element can be suppressed.
- Step 1 A thin film transistor (hereinafter referred to as "TFT") 2 is formed on a glass substrate 1, a photosensitive material for a TFT planarization film is formed, patterned by photolithography, and thermally cured. Thus, a cured film 3 for flattening the TFT is formed.
- TFT thin film transistor
- Step 2 Silver-palladium-copper alloy (hereinafter, “APC”) is formed by sputtering, patterned by etching using a photoresist to form an APC layer, and further, an upper layer of the APC layer Indium tin oxide (hereinafter, "ITO") is formed into a film by sputtering and patterned by etching using a photoresist to form a reflective electrode 4 as a first electrode.
- step 3 the negative photosensitive resin composition of the present invention is applied and prebaked to form a prebaked film 5a.
- Step 4 the active actinic radiation 7 is irradiated through the mask 6 having a desired pattern.
- Step 5 after development and pattern processing, bleaching exposure and middle baking as necessary, and heat curing are performed to obtain a cured pattern 5b having a desired pattern as a light-shielding pixel division layer.
- Step 6 an EL light emitting material is formed into a film by vapor deposition through a mask to form an EL light emitting layer 8, a magnesium-silver alloy (hereinafter, "MgAg") is formed by vapor deposition, and a photoresist is formed.
- Pattern processing is carried out by etching using this to form a transparent electrode 9 as a second electrode.
- Step 7 A photosensitive material for a planarization film is formed, patterned by photolithography, and then thermally cured to form a hardening film 10 for planarization, and then bonding a cover glass 11
- an organic EL display having the negative photosensitive resin composition of the present invention as a light-shielding pixel division layer is obtained.
- a cured film of the composition is used as a black column spacer (hereinafter "BCS") of a liquid crystal display and a black matrix (hereinafter "BM”) of a color filter.
- BCS black column spacer
- BM black matrix
- a backlight unit (hereinafter, "BLU") 13 is formed on a (step 1) glass substrate 12 to obtain a glass substrate 14 having a BLU.
- Step 2 A TFT 16 is formed on another glass substrate 15, a photosensitive material for a TFT planarization film is formed, patterned by photolithography, and then thermally cured to planarize the TFT. A cured film 17 is formed.
- Step 3 ITO is deposited by sputtering, patterned by etching using a photoresist, a transparent electrode 18 is formed, and a planarizing film 19 and an alignment film 20 are formed thereon. Thereafter, (step 4) the negative photosensitive resin composition of the present invention is applied and prebaked to form a prebaked film 21a.
- Step 5 the active actinic radiation 23 is irradiated through the mask 22 having the desired pattern.
- Step 6 after development and pattern processing, bleaching exposure and middle baking are carried out if necessary, and heat curing is carried out to form a cured pattern 21b having a desired pattern as a light blocking BCS, A glass substrate 24 having BCS is obtained.
- Step 7 the glass substrate 14 described above and the glass substrate 24 are bonded to obtain a glass substrate 25 having BLU and BCS.
- Step 8 The color filters 27 of three colors of red, green and blue are formed on another glass substrate 26.
- step 9 a cured pattern 28 having a desired pattern as a light-shielding BM is formed from the negative photosensitive resin composition of the present invention in the same manner as the method described above.
- Step 10 A photosensitive material for planarization is formed into a film, patterned by photolithography, and then thermally cured to form a cured film 29 for planarization, and an alignment film 30 is formed thereon Thus, the color filter substrate 31 is obtained.
- Step 11 the glass substrate 25 having BLU and BCS described above is bonded to the color filter substrate 31 to obtain a glass substrate 32 having BLU, BCS, and BM (Step 12).
- Step 13 liquid crystal is injected to form a liquid crystal layer 33, whereby a liquid crystal display having the negative photosensitive resin composition of the present invention as BCS and BM is obtained.
- the manufacturing method of the organic electroluminescent display and liquid crystal display using the negative photosensitive resin composition of this invention it is patterned and contains a polyimide and / or polybenzoxazole, and is high heat resistance. And since it is possible to obtain a cured film having a light shielding property, it leads to an improvement in yield, performance and reliability in the manufacture of organic EL displays and liquid crystal displays.
- the resin composition is photosensitive, it can be directly patterned by photolithography. Therefore, since the number of processes can be reduced as compared with the process using the photoresist, the productivity of the organic EL display and the liquid crystal display can be improved, the process time can be shortened, and the tact time can be shortened.
- the cured film obtained from the negative photosensitive resin composition of this invention can comprise an organic electroluminescent display or a liquid crystal display suitably.
- the negative photosensitive resin composition of the present invention can obtain a low taper pattern shape, and can obtain a cured film excellent in high heat resistance. Therefore, it is suitable for applications requiring high heat resistance and low taper pattern shapes, such as insulating layers such as pixel division layers of an organic EL display, a TFT planarization layer, or a TFT protective layer.
- insulating layers such as pixel division layers of an organic EL display, a TFT planarization layer, or a TFT protective layer.
- problems due to heat resistance and pattern shape are expected, such as defective or deteriorated elements of the element due to degassing due to thermal decomposition, disconnection of electrode wiring due to high taper pattern shape, etc.
- the cured film of the photosensitive resin composition it becomes possible to manufacture a highly reliable device which does not cause the above-mentioned problems.
- the cured film is excellent in the light shielding property, the visualization of the electrode wiring can be prevented or the reflection of external light can be reduced, and the contrast in image display can be improved. Therefore, by using the cured film obtained from the negative photosensitive resin composition of the present invention as a pixel division layer, a TFT flattening layer, or a TFT protective layer of an organic EL display, it is possible to polarize light on the light extraction side of the light emitting element. The contrast can be improved without forming a plate and a quarter wave plate.
- the organic electroluminescent display of this invention has a display part of a curved surface.
- the radius of curvature of the curved surface is preferably 0.1 mm or more, and more preferably 0.3 mm or more, from the viewpoint of suppressing display defects caused by disconnection or the like in the display portion including the curved surface.
- the radius of curvature of the curved surface is preferably 10 mm or less, more preferably 7 mm or less, and still more preferably 5 mm or less, from the viewpoint of downsizing and high resolution of the organic EL display.
- a method of manufacturing a display device using the negative photosensitive resin composition of the present invention has the following steps (1) to (4). (1) forming a film of the negative photosensitive resin composition of the present invention on a substrate; (2) irradiating the coating film of the negative photosensitive resin composition with actinic radiation through a photomask; (3) developing using an alkaline solution to form a pattern of the negative photosensitive resin composition; (4) A step of heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.
- the method for producing a display device using the negative photosensitive resin composition of the present invention comprises (1) forming a coating film of the negative photosensitive resin composition on a substrate.
- a method of forming a film of the negative photosensitive resin composition of the present invention for example, a method of applying the above-described resin composition on a substrate, or a method of applying the above-described resin composition in a pattern on a substrate Methods are included.
- an oxide, metal (molybdenum, silver, copper, aluminum, chromium, or titanium) having one or more selected from indium, tin, zinc, aluminum, and gallium as an electrode or wiring on glass And the like, or a substrate on which CNT (Carbon Nano Tube) is formed is used.
- an oxide having one or more selected from indium, tin, zinc, aluminum, and gallium for example, indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), indium gallium zinc oxide, and the like (IGZO) or zinc oxide (ZnO).
- substrate microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, or slit coating is mentioned, for example.
- the coating thickness varies depending on the coating method, solid content concentration and viscosity of the resin composition, etc. Usually, coating is performed so that the thickness after coating and prebaking becomes 0.1 to 30 ⁇ m.
- prebaking can use an oven, a hot plate, infrared rays, a flash annealing apparatus, a laser annealing apparatus, or the like.
- the pre-bake temperature is preferably 50 to 150.degree.
- the pre-bake time is preferably 30 seconds to several hours. After prebaking at 80 ° C. for 2 minutes, prebaking may be performed in two or more stages, such as prebaking at 120 ° C. for 2 minutes.
- ⁇ Method of applying the negative photosensitive resin composition of the present invention in a pattern on a substrate for example, letterpress printing, intaglio printing, stencil printing, lithographic printing, screen printing, inkjet printing, offset printing, or laser printing Can be mentioned.
- the coating thickness varies depending on the coating method, solid concentration and viscosity of the negative photosensitive resin composition of the present invention, etc. Usually, coating is performed so that the thickness after coating and prebaking becomes 0.1 to 30 ⁇ m. .
- prebaking can use an oven, a hot plate, infrared rays, a flash annealing apparatus, a laser annealing apparatus, or the like.
- the pre-bake temperature is preferably 50 to 150.degree.
- the pre-bake time is preferably 30 seconds to several hours. After prebaking at 80 ° C. for 2 minutes, prebaking may be performed in two or more stages, such as prebaking at 120 ° C. for 2 minutes.
- ⁇ Method of patterning a coating film formed on a substrate> As a method of pattern-processing the coating film of the negative photosensitive resin composition of this invention formed into a film on a board
- a method of producing a display device using the negative photosensitive resin composition of the present invention comprises the steps of: (2) irradiating the coating film of the above-mentioned negative photosensitive resin composition with actinic radiation through a photomask; Have. After the negative photosensitive resin composition of the present invention is applied and prebaked on a substrate to form a film, an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA) is used. Expose.
- MPA mirror projection mask aligner
- PDA parallel light mask aligner
- Examples of the active actinic radiation applied at the time of exposure include ultraviolet light, visible light, electron beam, X-ray, KrF (wavelength 248 nm) laser, and ArF (wavelength 193 nm) laser. It is preferable to use j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) of a mercury lamp.
- the exposure dose is usually about 100 to 40,000 J / m 2 (10 to 4,000 mJ / cm 2 ) (the value of the i-line illuminance meter), and exposure is performed via a photomask having a desired pattern as necessary. can do.
- post-exposure baking may be performed. By performing post-exposure baking, effects such as improvement of resolution after development or increase of tolerance of development conditions can be expected.
- Post-exposure baking can be performed using an oven, a hot plate, infrared light, a flash annealing apparatus, a laser annealing apparatus, or the like.
- the post-exposure baking temperature is preferably 50 to 180 ° C., and more preferably 60 to 150 ° C.
- the post-exposure bake time is preferably 10 seconds to several hours. If the post-exposure bake time is 10 seconds to several hours, the reaction may proceed favorably and the development time may be shortened.
- a halftone photomask is a photomask having a pattern including a light transmitting portion and a light shielding portion, and the transmittance between the light transmitting portion and the light shielding portion is lower than the value of the light transmitting portion, and the transmittance is This refers to a photomask having a semi-transparent portion higher than the value of the light shielding portion.
- the cured portion irradiated with the active actinic radiation through the light transmitting portion corresponds to the thick film portion
- the halftone exposure portion irradiated with the active actinic radiation through the semi-light transmitting portion is the thin film portion It corresponds to
- the halftone photomask has a portion where the light transmitting portion and the semi-light transmitting portion are adjacent to each other.
- the thick film portion corresponding to the light transmitting portion on the photomask after development corresponds to the semi light transmitting portion on the photomask And the thin film portion may be formed.
- the halftone photomask has a portion where the light shielding portion and the semi-light transmitting portion are adjacent to each other.
- a pattern having an opening corresponding to the light shielding part on the photomask after development and the thin film part corresponding to the semi-light transmitting part on the photomask can be formed. Since the halftone photomask has the above-described portions, it is possible to form a pattern having a step shape including the thick film portion, the thin film portion, and the opening after development.
- the transmittance (% T FT )% of the semilight transmitting portion is 10% or more of (% T FT ) Is preferable, 15% or more is more preferable, 20% or more is more preferable, and 25% or more is particularly preferable.
- the transmittance (% T HT )% of the semi-transparent portion is in the above range, the exposure amount at the time of forming the cured pattern having the step shape can be reduced, and the tact time can be shortened.
- the transmittance of the semi-light-transmitting portion (% T HT)% is, (% T FT) 60% or less are preferred, more preferably 55% or less, more preferably 50% or less, particularly preferably 45% or less. If the transmissivity (% T HT )% of the semi-transparent part is within the above range, the film thickness difference between the thick film part and the thin film part and the film thickness difference between the thin film parts adjacent on both sides of any step difference Thus, deterioration of the light emitting element can be suppressed. In addition, since there is a sufficient film thickness difference in one cured pattern having a step shape, process time can be shortened.
- the transmissivity (% T HT )% of the semitransparent portion is 30% of (% T FT ) the film thickness of the thin portion of the case (T HT30) [mu] m, and the transmittance of the semi-light-transmitting portion (% T HT)% is, the thickness of the thin portion of the case is 20% of (% T FT)
- the film thickness difference ( ⁇ T HT30 -HT 20 ) ⁇ m between (T HT30 ) and (T HT20 ) is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and 0.7 ⁇ m or more Is more preferable, and 0.8 ⁇ m or more is particularly preferable.
- the film thickness difference is within the above range, the film thickness difference between the thick film part and the thin film part and the film thickness difference between the thin film parts adjacent on both sides of any step can be sufficiently large, thereby deteriorating the light emitting element. It can be suppressed. In addition, since there is a sufficient film thickness difference in one cured pattern having a step shape, process time can be shortened.
- the film thickness difference ( ⁇ T HT30 -HT20 ) ⁇ m is preferably 1.5 ⁇ m or less, more preferably 1.4 ⁇ m or less, still more preferably 1.3 ⁇ m or less, and particularly preferably 1.2 ⁇ m or less.
- the film thickness difference is within the above range, the occurrence of film thickness variation due to slight exposure amount fluctuation due to an apparatus etc. can be reduced, whereby film thickness uniformity and yield in organic EL display manufacturing can be improved. .
- a method of producing a display device using the negative photosensitive resin composition of the present invention comprises the steps of (3) developing with an alkaline solution to form a pattern of the above-mentioned negative photosensitive resin composition . After exposure, development is performed using an automatic developing device or the like. Since the negative photosensitive resin composition of the present invention has negative photosensitivity, the unexposed area is removed by a developer after development, and a relief pattern can be obtained.
- an alkaline developing solution is generally used.
- an alkali developing solution for example, an organic alkaline solution or an aqueous solution of a compound exhibiting alkalinity is preferable, and from the environmental viewpoint, an aqueous solution of a compound exhibiting alkalinity, that is, an alkaline aqueous solution is more preferable.
- organic alkaline solutions or compounds exhibiting alkalinity examples include 2-aminoethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, diethanolamine, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, acetic acid (2-Dimethylamino) ethyl, (meth) acrylic acid (2-dimethylamino) ethyl, cyclohexylamine, ethylenediamine, hexamethylenediamine, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide And magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, or potassium carbonate, but from the viewpoint of reducing metal impurities of the cured film and suppressing display defects of the display device.
- Et al. Tetramethylammonium hydroxide or tetraethylammonium hydroxide is preferred.
- An organic solvent may be used as the developer.
- Examples of the development method include paddle development, spray development, or dip development.
- paddle development for example, a method of applying the above-mentioned developing solution as it is to the film after exposure as it is and leaving it for an arbitrary time, or spraying the developing solution mentioned above onto the film after exposure for an arbitrary time After radiation and application, there may be mentioned a method of leaving for an arbitrary time.
- spray development include a method in which the above-described developer is emitted in the form of a mist to the film after exposure and the film is continuously applied for an arbitrary time.
- dip development there is a method of immersing a film after exposure in a developer as described above for an arbitrary time or a method of immersing a film after exposure in a developer as described above and continuing irradiation of ultrasonic waves for an arbitrary time. It can be mentioned.
- paddle development is preferable from the viewpoint of process cost reduction due to suppression of apparatus contamination during development and reduction in the amount of use of the developing solution. By suppressing the apparatus contamination at the time of development, the substrate contamination at the time of development can be suppressed, and the display defect of the display apparatus can be suppressed.
- spray development is preferable as a development method from a viewpoint of suppression of residue generation after development.
- dip development is preferable from the viewpoint of reduction of the amount of use of the developing solution by reuse of the developing solution and reduction of process cost.
- the development time is preferably 30 minutes or less, more preferably 15 minutes or less, still more preferably 10 minutes or less, and particularly preferably 5 minutes or less.
- the obtained relief pattern is preferably washed with a rinse solution.
- a rinse solution water is preferable when an alkaline aqueous solution is used as the developer.
- An organic solvent may be used as the rinse solution.
- the method for producing a display device using the negative photosensitive resin composition of the present invention is the step (3) of development using an alkaline solution to form a pattern of the negative photosensitive resin composition, Furthermore, it is preferable to have the process of photocuring the pattern of the said negative photosensitive resin composition.
- the crosslink density of the pattern is improved, and the low molecular component that is a cause of degassing is reduced, so that the reliability of the light emitting device provided with the pattern of the negative photosensitive resin composition is improved. it can.
- the pattern of the negative photosensitive resin composition is a pattern having a step shape
- the pattern reflow at the time of heat curing of the pattern can be suppressed, and the film thickness difference between the thick film portion and the thin film portion is sufficient even after heat curing. It is possible to form a pattern having a stepped shape.
- the flatness can be improved, and the decrease in yield of the panel can be suppressed.
- the contact area with the deposition mask when forming the organic EL layer can be reduced, thereby suppressing a decrease in yield of panels due to particle generation.
- the deterioration of the light emitting element can be suppressed.
- the method of irradiating active actinic radiation include a method of bleaching exposure using an exposure machine such as a stepper, a scanner, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
- an exposure machine such as a stepper, a scanner, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
- a lamp used for irradiation of active actinic radiation in the step of photocuring the pattern for example, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a Xe excimer lamp, a KrF excimer lamp, or an ArF excimer lamp Etc.
- the active actinic radiation in the step of photocuring the pattern for example, ultraviolet light, visible light, electron beam, X-ray, XeF (wavelength 351 nm) laser, XeCl (wavelength 308 nm) laser, KrF (wavelength 248 nm) laser, or ArF (Wavelength 193 nm) A laser etc. are mentioned.
- j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) of mercury lamp, or
- the g line (wavelength 436 nm) or a mixed line of i line, h line and g line is preferable.
- the exposure dose of active actinic radiation in the step of photocuring the pattern is preferably 100 J / m 2 (10 mJ / cm 2 ) or more as the i-line illuminance value.
- the exposure dose of active actinic radiation is preferably 50,000 J / m 2 (5,000 mJ / cm 2 ) or less in i-line illuminance value.
- the photo mask in the process of irradiating the active actinic radiation to the coating film of (2) negative photosensitive resin composition through a photo mask is a halftone photo mask
- the photo activity of the process in which the pattern is photocured In the step of irradiating the active actinic radiation through the (2) photomask with the exposure dose of actinic radiation being (E BLEACH ) mJ / cm 2 , the exposure dose at the transmission part of the photomask is (E EXPO ) mJ / cm
- the exposure dose ratio (E BLEACH ) / (E EXPO ) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 0.7 or more.
- the exposure dose ratio is preferably 0.5 or more, more preferably 0.7 or more, and still more preferably 1 or more.
- the exposure dose ratio is preferably less than 4, more preferably less than 3.5, and still more preferably less than 3.
- middle baking may be performed.
- the middle bake can use an oven, a hot plate, an infrared ray, a flash annealing apparatus, a laser annealing apparatus, or the like.
- the middle bake temperature is preferably 50 to 250 ° C., and more preferably 70 to 220 ° C.
- the middle bake time is preferably 10 seconds to several hours. After middle baking for 5 minutes at 100 ° C., middle baking may be performed in two or more stages, such as middle baking for 5 minutes at 150 ° C.
- the manufacturing method of a display apparatus using the negative photosensitive resin composition of this invention heats the pattern of the (4) negative photosensitive resin composition mentioned above, and the negative photosensitive resin composition mentioned above Obtaining a curing pattern.
- An oven, a hot plate, infrared rays, a flash annealing apparatus, a laser annealing apparatus etc. can be used for the heating of the pattern of the negative photosensitive resin composition of this invention formed into a film on the board
- thermoset 150 ° C or more is preferred, 200 ° C or more is more preferred, and 250 ° C or more is still more preferred. While being able to improve the heat resistance of a cured film as heat curing temperature is 150 degreeC or more, the pattern shape after heat curing can be made into a lower taper.
- the temperature for thermosetting is preferably 500 ° C. or less, more preferably 450 ° C. or less, and still more preferably 400 ° C. or less.
- the heat curing time is preferably 1 minute or more, more preferably 5 minutes or more, further preferably 10 minutes or more, and particularly preferably 30 minutes or more.
- the heat curing time is preferably 300 minutes or less, more preferably 250 minutes or less, still more preferably 200 minutes or less, and particularly preferably 150 minutes or less.
- heat curing may be performed in two or more stages such as heat curing at 250 ° C. for 30 minutes.
- a pixel division layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer It is possible to obtain a cured film suitably used for applications such as an electrode protection layer, a wiring protection layer, a gate insulating layer, a color filter, a black matrix, or a black column spacer. Moreover, it becomes possible to obtain the element and display apparatus provided with those cured films.
- the cured film is divided into a pixel division layer, an electrode insulation layer, a wiring insulation layer, an interlayer insulation layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protection layer And at least one selected from the group consisting of a wiring protective layer, a gate insulating layer, a color filter, a black matrix, and a black column spacer.
- the negative photosensitive resin composition of the present invention is excellent in the light shielding property, a pixel divided layer having a light shielding property, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring It is preferable as a planarizing layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, or a gate insulating layer, and more preferable as a pixel division layer having a light shielding property, an interlayer insulating layer, a TFT planarizing layer, or a TFT protective layer.
- a cured film having high heat resistance and light shielding property is patterned and contains polyimide and / or polybenzoxazole. Since it is possible to obtain, it leads to the yield improvement, performance improvement, and reliability improvement in manufacture of an organic electroluminescent display and a liquid crystal display.
- the negative photosensitive resin composition of the present invention can be directly patterned by photolithography, the number of steps can be reduced as compared to the process using a photoresist, and therefore, the productivity can be improved. It is possible to improve, shorten the process time and shorten the tact time.
- BYK-167 "DISPERBYK” (registered trademark)-167 (manufactured by Bick Chemie Japan Ltd .; polyurethane-based dispersant having a tertiary amino group having an amine value of 13 mg KOH / g (solid content concentration: 52% by mass))
- DFA N, N-dimethylformamide dimethyl acetal
- DPCA-60 "KAYARAD” (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd .; ⁇ -caprolactone modified dipenta having 6 oxypentylene carbonyl structures in the molecule) Erythritol hexaacrylate)
- DPHA "KAYARAD” (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd .; dipentaerythritol hexaacrylate)
- EGME ethylene glycol bis (2-mercaptoethyl)
- Synthesis example (A) In a three-necked flask, 18.31 g (0.05 mol) of BAHF, 17.42 g (0.3 mol) of propylene oxide, and 100 mL of acetone were weighed and dissolved. To this was added dropwise a solution of 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride in 10 mL of acetone. After completion of the dropwise addition, the reaction was carried out at -15.degree. C. for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50 ° C.
- Synthesis Example 1 Synthesis of Polyimide (PI-1) In a three-necked flask, 31.13 g (0.085 mol; 77.3 mol% with respect to structural units derived from all amines and their derivatives) of BAHF in a three-necked flask under dry nitrogen gas flow, SiDA To 1.24 g (0.0050 mol; 4.5 mol% relative to the structural units derived from all amines and their derivatives), 2.18 g (0.020 mol; all amines and their derivatives) as a capping agent 150.00 g of NMP was weighed and dissolved with respect to the structural unit derived (18.2 mol%).
- Synthesis Examples 2 to 5 Synthesis of Polyimide (PI-2) to Polyimide (PI-5) The polymerization was carried out in the same manner as in Synthesis Example 1 using the monomer species and ratio thereof shown in Table 1-1 to obtain polyimide (PI- 2) to obtain a polyimide (PI-5).
- Synthesis Example 6 Synthesis of Polyimide Precursor (PIP-1) In a three-necked flask under a stream of dry nitrogen, 44.42 g (0.10 mol; 100 mol% with respect to structural units derived from all carboxylic acids and their derivatives) of 6FDA 150 g of NMP was weighed and dissolved.
- the resulting solid was washed three times with water and then dried in a vacuum drier at 80 ° C. for 24 hours to obtain a polyimide precursor (PIP-1).
- the Mw of the obtained polyimide precursor was 20,000, and the acid equivalent was 450.
- Synthesis Example 7 Synthesis of Polyimide Precursor (PIP-2) The polymerization was carried out in the same manner as in Synthesis Example 6 with the types of monomers shown in Table 1-1 and the ratio thereof to obtain a polyimide precursor (PIP-2). .
- Synthesis Example 8 Synthesis of Polybenzoxazole (PBO-1) In a 500 mL round bottom flask equipped with a Dean-Stark water separator and a condenser filled with toluene, 34.79 g (0.095 mol; total amine and its derivative) of BAHF were added. 95.0 mol% relative to the structural unit derived), 1.24 g (0.0050 mol; 5.0 mol% relative to the structural units derived from all amines and their derivatives) of SiDA, 75.00 g NMP , Dissolved.
- the obtained solid was washed 3 times with water and then dried in a vacuum drier at 80 ° C. for 24 hours to obtain polybenzoxazole (PBO-1).
- the Mw of the obtained polybenzoxazole was 25,000, and the acid equivalent was 330.
- Synthesis Example 9 Synthesis of Polybenzoxazole Precursor (PBOP-1) 34.79 g (0.095 mol; total amine and its amine) of BAHF in a 500 mL round bottom flask equipped with a Dean-Stark water separator and a condenser filled with toluene. 95.0 mol% of the structural unit derived from the derivative), 1.24 g (0.0050 mol; 5.0 mol% relative to the structural units derived from all amines and their derivatives) of SiDA, 70.00 g of NMP And allowed to dissolve.
- PBOP-1 Polybenzoxazole Precursor
- the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was obtained by filtration.
- the obtained solid was washed three times with water and then dried in a vacuum drier at 80 ° C. for 24 hours to obtain a polybenzoxazole precursor (PBOP-1).
- the Mw of the obtained polybenzoxazole precursor was 20,000, and the acid equivalent was 330.
- Synthesis Example 10 Synthesis of Polysiloxane Solution (PS-1) In a three-necked flask, 20.43 g (30 mol%) MeTMS, 49.57 g (50 mol%) PhTMS, 12.32 g (10 mol%) cyEpoTMS, 7 TMOS .61 g (10 mol%) and 83.39 g of PGMEA were charged. The flask was flushed with air at 0.05 L / min, and the mixed solution was heated to 40 ° C. in an oil bath while stirring. A phosphoric acid aqueous solution in which 0.270 g of phosphoric acid was dissolved in 28.83 g of water was added dropwise over 10 minutes while further stirring the mixed solution.
- PS-1 Polysiloxane Solution
- the silane compound was hydrolyzed by stirring at 40 ° C. for 30 minutes. After completion of the hydrolysis, the bath temperature was adjusted to 70 ° C. and stirred for 1 hour, and then the bath temperature was raised to 115 ° C. About 1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (the internal temperature is 100 to 110 ° C.). The resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath to obtain a polysiloxane solution (PS-1). The Mw of the obtained polysiloxane was 4,500.
- PS-1 polysiloxane solution
- Synthesis Example 11 Synthesis of Polysiloxane Solution (PS-2) In a three-necked flask, 27.24 g (40 mol%) MeTMS, 49.57 g (50 mol%) PhTMS, 12.32 g (10 mol%) cyEpoTMS, PGMEA 83. I charged 91 g. The flask was flushed with air at 0.05 L / min, and the mixed solution was heated to 40 ° C. in an oil bath while stirring. While further stirring the mixed solution, a phosphoric acid aqueous solution in which 0.267 g of phosphoric acid was dissolved in 27.93 g of water was added over 10 minutes.
- PS-2 Polysiloxane Solution
- the silane compound was hydrolyzed by stirring at 40 ° C. for 30 minutes. After completion of the hydrolysis, the bath temperature was adjusted to 70 ° C. and stirred for 1 hour, and then the bath temperature was raised to 115 ° C. About 1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (the internal temperature is 100 to 110 ° C.). The resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath to obtain a polysiloxane solution (PS-2). The Mw of the obtained polysiloxane was 4,000.
- PS-2 polysiloxane solution
- Synthesis Example 12 Synthesis of Polycyclic Side Chain-Containing Resin Solution (CR-1)
- 35.04 g (0.10 mol) of BHPF and 40.31 g of MBA were weighed and dissolved.
- a solution of 27.92 g (0.090 mol) of ODPA and 2.96 g (0.020 mol) of PHA as an end capping agent in 3 g of MBA was added and stirred at 20 ° C. for 1 hour. Then, it stirred at 150 degreeC under nitrogen atmosphere for 5 hours.
- Bk-CBF1 Surface-Coated Benzofuranone-Based Black Pigment
- Sodium silicate aqueous solution Na 2 O ⁇ nSiO 2 ⁇ mH so that the coating amount of silica is 10.0 parts by mass in terms of SiO 2 with respect to 100 parts by mass of the black pigment with respect to the aqueous pigment suspension 2 O: 30% by mass as sodium oxide, 10% by mass as silicon dioxide
- pH is maintained in the range of 2 or more and less than 7
- the addition was carried out in parallel, and the surface of the black pigment particles was coated with the deposited silica.
- an aqueous solution of sodium aluminate Na 2 O ⁇ is used so that the coating amount of alumina is 2.0 parts by mass in terms of Al 2 O 3 relative to 100 parts by mass of the black pigment with respect to the aqueous pigment suspension nAl 2 O 3 ⁇ mH 2 O; 40% by mass as sodium oxide, 50% by mass as alumina) diluted 100 times with deionized water and sulfuric acid at 0.001 mol / L, pH 2 or more and less than 7
- the addition was carried out in parallel while adjusting each addition rate so as to be maintained in the range, and alumina was deposited and coated on the surface of the silica coating layer.
- the coverage of silica and alumina of the obtained surface-coated benzofuranone-based black pigment (Bk-CBF1) was 100 parts by mass of the black pigment, respectively. It was 10.0 parts by mass in terms of SiO 2 , 2.0 parts by mass in terms of Al 2 O 3 , and the average coverage of the coating layer with respect to the pigment was 97.5%.
- Preparation Examples 3 to 18 Preparation of pigment dispersion (Bk-3) to pigment dispersion (Bk-18) Types of colorants described in Table 2-1, (A1) first resin and (E) dispersant, and The pigment was dispersed at these ratios in the same manner as in Preparation Example 2 to obtain pigment dispersion (Bk-3) to pigment dispersion (Bk-18).
- compositions of Preparation Examples 1 to 18 are summarized in Table 2-1.
- the maximum transmission wavelength of each of the colorants (a mixture of P.R. 179, P.Y. 192 and P.B. 60) contained in the dispersion (Bk-9) is shown below.
- Bk-S0084 350 nm P. R. 179, P.I. Y. 192 and P.I. B. Mixture of 60: 390 nm
- the structural units possessed by the acid-modified epoxy resin (AE-1) obtained in Synthesis Example 14 are shown below.
- the acid-modified epoxy resin (AE-1) has a structural unit represented by the general formula (38a).
- Nuclear magnetic resonance device JNM-GX270; manufactured by Nippon Denshi Co., Ltd.
- Measurement method Gated decoupling measurement Nuclear frequency: 53.6693 MHz ( 29 Si nucleus) Spectrum width: 20000 Hz Pulse width: 12 ⁇ s (45 ° pulse) Pulse repetition time: 30.0 seconds
- Solvent acetone-d6 Reference material: tetramethylsilane Measurement temperature: 23 ° C Sample rotation speed: 0.0 Hz.
- ITO substrate Glass substrate on which ITO is deposited to a thickness of 100 nm by sputtering is a desktop type light surface treatment apparatus (PL16-110; Sen Special Light Source, Ltd. ) And used for 100 seconds for UV-O 3 cleaning.
- a Si wafer manufactured by Electronics End Materials Corporation was used after being subjected to dehydration baking by heating at 130 ° C. for 2 minutes using a hot plate (HP-1SA; manufactured by As One).
- Sensitivity A gray scale mask (MDRM MODEL 4000-5-FS) for sensitivity measurement using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) according to the method described in Example 1 below.
- mask aligner PEM-6M manufactured by Union Optical Co., Ltd.
- i-line wavelength 365 nm
- h-line wavelength 405 nm
- g-line wavelength 436 nm
- the resolution pattern of the developed film is observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), and the exposure dose for forming a 20 ⁇ m line and space pattern in a width of 1: 1 (The value of i ray illuminance meter) was taken as the sensitivity.
- sensitivity is 90 mJ / cm 2 or less
- a +, A, B, and C are accepted
- sensitivity is 60 mJ / cm 2 or less
- a +, A, and B are sensitivity.
- a + and A which have a sensitivity of 45 mJ / cm 2 or less, were regarded as excellent in sensitivity.
- a + no residue at the opening A: the area of the residue at the opening is 1 to 5%
- B 6 to 10% of the area of the residue at the opening
- C 11 to 30% of the area of the residue at the opening
- D Remaining area of 31 to 50% at the opening
- E The existing area of the residue at the opening is 51 to 100%.
- a cross section of a line and space pattern with a space dimension width of 20 ⁇ m is observed.
- the taper angle of the cross section was measured.
- the taper angle of the cross section is determined to be 60 ° or less, A +, A, and B are accepted, and the taper angle of the cross section is 45 ° or less.
- a + with a taper angle of 30 ° or less was regarded as excellent in pattern shape.
- the taper angle of the cross section is 1 to 30 °
- the taper angle of the cross section is 31 to 45 °
- B The taper angle of the cross section is 46 to 60 °
- C The taper angle of the cross section is 61 to 70 °
- D The taper angle of the cross section is 71 to 80 °
- E The taper angle of the cross section is 81 to 179 °.
- the cross section of a line and space pattern with a space dimension width of 20 ⁇ m is observed by using a field emission scanning electron microscope (S-4800; manufactured by Hitachi High-Technologies Corporation) The taper angle of was measured.
- the taper angle of the cross section is determined to be 60 ° or less, A +, A, and B are accepted, and the taper angle of the cross section is 45 ° or less.
- a + with a taper angle of 30 ° or less was regarded as excellent in pattern shape.
- the taper angle of the cross section is 1 to 30 °
- the taper angle of the cross section is 31 to 45 °
- B The taper angle of the cross section is 46 to 60 °
- C The taper angle of the cross section is 61 to 70 °
- D The taper angle of the cross section is 71 to 80 °
- E The taper angle of the cross section is 81 to 179 °.
- AD-2000 small photolithographic developing apparatus manufactured by Takizawa Sangyo Co., Ltd.
- the resolution pattern of the developed film is observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the opening dimension width of the 20 ⁇ m line and space pattern is measured, and after development
- the film after development described above is thermally cured using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) by the method described in Example 1 below to obtain a negative photosensitive resin composition.
- a cured film was produced.
- the resolution pattern of the produced cured film is observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), and the opening dimension of the 20 ⁇ m line and space pattern at the same place as the place observed after development The width was measured and used as the pattern opening width after heat curing (CD CURE ).
- the change in the pattern opening dimension width before and after heat curing ((CD DEV ) ⁇ (CD CURE )) was calculated.
- a +, A, and B pass the pattern opening dimension width change before and after heat curing is 0.60 ⁇ m or less, change in pattern opening dimension width before and after heat curing is 0.40 ⁇ m or less Therefore, A + and A indicate that the change in pattern dimension width is good, and A + indicates that the change in pattern aperture width before and after heat curing is 0.20 ⁇ m or less.
- the change in pattern dimension width is excellent.
- a cured film of the negative photosensitive resin composition was produced using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.).
- thermogravimetric apparatus TGA-50; Shimadzu Corporation
- thermogravimetric analysis was performed while maintaining the temperature at 150 ° C. for 30 minutes and further raising the temperature to 500 ° C. at a temperature rising rate of 10 ° C./min.
- the weight 100% by mass after heating at 150 ° C. for 30 minutes, the weight residual rate at 350 ° C.
- a +, A, and B are accepted as the high temperature weight residual ratio difference becomes 25.0 mass% or less, A +, A as the high temperature weight residual ratio difference becomes 15.0% or less A + was regarded as excellent in heat resistance because it had good heat resistance and the difference in high temperature weight retention rate was 5.0% or less.
- a + High temperature weight residual rate difference is 0 to 5.0%
- C High temperature residual weight difference 25.1 to 35.0%
- D High temperature residual weight difference 35.1 to 45.0%
- E High temperature weight residual rate difference 45.1 to 100%.
- a cured film of the negative photosensitive resin composition was produced using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.).
- the incident light intensity (I 0 ) and the transmitted light intensity (I) of the produced cured film were measured using a transmission densitometer (X-Rite 361 T (V); manufactured by X-Rite).
- a gray scale mask (MDRM MODEL 4000-5-FS; Opto-Line) for sensitivity measurement using a double-sided alignment single-sided exposure apparatus (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) by the method described in Example 1 below.
- a cured film of the negative photosensitive resin composition was produced using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.).
- the surface resistivity ( ⁇ / ⁇ ) of the produced cured film was measured using a high resistance resistivity meter (“Hiresta” UP; manufactured by Mitsubishi Chemical Corporation).
- FIG. 4 shows a schematic view of the used substrate.
- an ITO transparent conductive film 10 nm was formed on the entire surface of a 38 ⁇ 46 mm non-alkali glass substrate 47 by a sputtering method, and etched as a first electrode 48 to form a transparent electrode.
- an auxiliary electrode 49 was also formed at the same time to take out the second electrode (FIG. 4 (step 1)).
- the obtained substrate was subjected to ultrasonic cleaning for 10 minutes with "SEMICOCLEAN” (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) and washed with ultrapure water.
- SEMICOCLEAN registered trademark
- a negative photosensitive resin composition is applied and prebaked on this substrate by the method described in Example 1, and after patterning exposure, development and rinsing through a photomask having a predetermined pattern, It was heated and cured thermally.
- the openings 70 ⁇ m wide and 260 ⁇ m long are arranged at a pitch of 155 ⁇ m in the width direction and at a pitch of 465 ⁇ m in the length direction, and each opening is shaped to expose the first electrode. It limited to the board
- the substrate effective area was 16 mm square, and the thickness of the insulating layer 50 was about 1.0 ⁇ m.
- an organic EL display was manufactured using the substrate on which the first electrode 48, the auxiliary electrode 49, and the insulating layer 50 were formed.
- an organic EL layer 51 including a light emitting layer was formed by vacuum evaporation (FIG. 4 (Step 3)).
- the degree of vacuum at the time of deposition was 1 ⁇ 10 ⁇ 3 Pa or less, and the substrate was rotated relative to the deposition source during the deposition.
- the compound (HT-1) was deposited to 10 nm as a hole injection layer, and the compound (HT-2) was deposited to 50 nm as a hole transport layer.
- a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were vapor deposited to a thickness of 40 nm so that the doping concentration was 10%.
- a compound (ET-1) and a compound (LiQ) were laminated at a thickness ratio of 40 nm at a volume ratio of 1: 1.
- the structures of the compounds used in the organic EL layer are shown below.
- sealing was performed by bonding a cap-like glass plate using an epoxy resin adhesive under a low humidity nitrogen atmosphere, and four 5 mm square bottom emission type organic EL displays were fabricated on one substrate.
- the film thickness is a crystal oscillation type film thickness monitor display value.
- the organic EL display manufactured by the above-described method was made to emit light by direct current drive at 10 mA / cm 2 , and it was observed whether there was a light emission failure such as a non-emission area or uneven brightness.
- the manufactured organic EL display was held at 80 ° C. for 500 hours as a durability test. After the durability test, the organic EL display was made to emit light by direct current drive at 10 mA / cm 2 , and it was observed whether or not the light emission characteristics such as the light emission region and the luminance unevenness were changed.
- the light emission area area after the endurance test is 80% or more when the light emission area area before the endurance test is determined to be 100% as determined below, A +, A, and B are accepted, and the light emission area area is A + and A, which are 90% or more, have good light emission characteristics, and A +, which has a light emission area of 95% or more, is excellent in light emission characteristics.
- a + 95 to 100% of light emitting area after endurance test A: 90 to 94% of light emitting area after endurance test B: 80 to 89% of light emitting area after endurance test C: 70 to 79% of light emitting area after endurance test D: 50 to 69% of light emitting area after endurance test E: The light emitting area after the endurance test is 0 to 49%.
- Example 1 Under a yellow light, 0.152 g of OXL-21 was weighed, 7.274 g of MBA and 5.100 g of PGMEA were added and dissolved by stirring. Next, 6.566 g of a 30 wt% MBA solution of polyimide (PI-1) obtained in Synthesis Example 1, 0.606 g of a 50 wt% MBA solution of DPHA, 50 wt% MBA of DPCA-60 1.515 g of the solution was added and stirred to obtain a preparation as a homogeneous solution. Next, 7.323 g of the pigment dispersion (Bk-1) obtained in Preparation Example 1 was weighed, and 17.77 g of the prepared liquid obtained by the method described above was added and stirred to obtain a uniform solution. did. Thereafter, the resulting solution was filtered through a 0.45 ⁇ m filter to prepare Composition 1.
- the prepared composition 1 is applied on an ITO substrate by spin coating at any rotation speed using a spin coater (MS-A100; manufactured by Mikasa), and then a buzzer hot plate (HPD-3000BZN; manufactured by As One Corporation) is formed. Using this, prebaking was performed at 110 ° C. for 120 seconds to prepare a prebaked film having a film thickness of about 1.8 ⁇ m.
- MS-A100 manufactured by Mikasa
- HPD-3000BZN manufactured by As One Corporation
- the prepared pre-bake film is spray-developed with a 2.38 mass% TMAH aqueous solution using a small photolithographic developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), and the time required for the pre-bake film (unexposed area) to completely dissolve (Breaking Point; hereinafter, "BP") was measured.
- AD-2000 small photolithographic developing apparatus
- BP Bonding Point
- a gray scale mask (MDRM MODEL 4000-5) for sensitivity measurement was prepared using the double-sided alignment single-sided exposure apparatus (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.). Patterning exposure with an i-line (wavelength: 365 nm), an h-line (wavelength: 405 nm), and a g-line (wavelength: 436 nm) of an ultra-high pressure mercury lamp via FS (manufactured by Opto-Line International). After exposure, development was performed with a 2.38 mass% TMAH aqueous solution using a small photolithographic developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), and rinsed with water for 30 seconds. The developing time is B.I. P. 1.5 times the
- thermal curing was performed at 250 ° C. using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to prepare a cured film having a thickness of about 1.2 ⁇ m.
- the heat curing conditions were heat curing at 250 ° C. for 60 minutes under a nitrogen atmosphere.
- Examples 2 to 83 and Comparative Examples 1 to 8 Compositions 2 to 91 were prepared in the same manner as in Example 1 with the compositions described in Tables 3-1 to 14-1. A composition was formed into a film on a substrate like Example 1, using each composition obtained, and evaluation of the photosensitive characteristic and the characteristic of a cured film was performed. The evaluation results are summarized in Tables 3-2 to 14-2. In order to facilitate comparison, Table 4-1 to Table 5-1, Table 7-1 to Table 13-1, Table 4-2 to Table 5-2, and Table 7-2 to Table 13-2 The composition and evaluation result of Example 7 are described in each.
- Example 84 Metal of manufacturing organic EL display without polarizing layer
- the outline of the organic electroluminescent display to produce is shown in FIG. First, a laminated film of chromium and gold was formed on a 38 ⁇ 46 mm non-alkali glass substrate 53 by electron beam evaporation, and the source electrode 54 and the drain electrode 55 were formed by etching.
- APC ITO was deposited to a thickness of 10 nm on the upper layer by sputtering, and a reflective electrode 56 was formed as a first electrode by etching.
- an amorphous IGZO film was formed by sputtering, and an oxide semiconductor layer 57 was formed between the source and drain electrodes by etching.
- a positive type photosensitive polysiloxane material SP-P 2301; manufactured by Toray Industries, Inc.
- SP-P 2301 a positive type photosensitive polysiloxane material
- the via holes 58 and the pixel region 59 are opened by photolithography and then thermally cured to form a gate.
- An insulating layer 60 was formed.
- a gold film is formed by an electron beam evaporation method, and a gate electrode 61 is formed by etching to form an oxide TFT array.
- the composition 7 is applied and prebaked on the oxide TFT array by the method described in Example 1 to form a film, patterning exposure through a photomask having a predetermined pattern, development and rinsing to form a pixel area Were opened and then thermally cured to form a TFT protective layer / pixel division layer 62 having a light shielding property.
- the openings of 70 ⁇ m in width and 260 ⁇ m in length are arranged at a pitch of 155 ⁇ m in the width direction and at a pitch of 465 ⁇ m in the length direction, and each opening has a shape for exposing the reflective electrode It was formed limited to the effective area. This opening finally becomes a light emitting pixel of the organic EL display.
- the substrate effective area is 16 mm square, and the thickness of the pixel division layer is about 1.0 ⁇ m.
- the compound (HT-1) as the hole injection layer, the compound (HT-2) as the hole transport layer, the compound (GH-1) as the host material, and the dopant material The organic EL light emitting layer 63 was formed using the compound (GD-1), and the compound (ET-1) and the compound (LiQ) as electron transport materials.
- a transparent electrode 64 was formed as a second electrode by etching.
- a sealing film 65 was formed using an organic EL sealing material (Structbond (registered trademark) XMF-T; manufactured by Mitsui Chemicals, Inc.) in a low humidity nitrogen atmosphere.
- the non-alkali glass substrate 66 was bonded on the sealing film, and four 5 mm square top emission type organic EL displays having no polarization layer were produced on one substrate.
- the film thickness is a crystal oscillation type film thickness monitor display value.
- the organic EL display manufactured by the above-mentioned method is made to emit light by direct current drive at 10 mA / cm 2 , and the luminance (Y ') when the outside light is irradiated to the pixel division layer portion, the luminance when the outside light is not irradiated ( Y 0 ) was measured.
- a +, A, and B are acceptable with a contrast of 0.80 or more, A + and A are favorable for an external light reflection reduction effect with a contrast of 0.90 or more, and the contrast is 0 A +, which is more than .95, is regarded as excellent in the external light reflection reduction effect. It was confirmed that the organic EL display manufactured by the above-described method has a contrast of 0.90 and can reduce external light reflection.
- Contrast is 0.70 to 0.79
- D Contrast of 0.50 to 0.69
- Contrast is 0.01 to 0.49.
- Example 85 Evaluation of halftone characteristics
- a pre-baked film of composition 7 is formed to a thickness of 5 ⁇ m on an ITO substrate by the method described in Example 1 described above, and a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) is used.
- the i-line wavelength of the ultra-high pressure mercury lamp
- the exposure of the light transmitting part becomes the exposure of the sensitivity when the film thickness after prebaking is 5 ⁇ m.
- a photomask having a light transmitting portion, a light shielding portion, and a semi-light transmitting portion between the light transmitting portion and the light shielding portion was used.
- the transmissivity (% T HT )% of the semi-translucent part is 10%, 15%, 20%, 25%, 30%, 35%, 40% of the transmissivity (% T FT ) of the translucent part, respectively. , 45% and 50%.
- the light transmitting portion and the semi-light transmitting portion are adjacent to each other, and the light transmitting portion and the light shielding portion are adjacent to each other.
- the pattern shapes of the light transmitting portion, the semi-light transmitting portion, and the light shielding portion all have a line shape.
- the light transmitting portion and the light shielding portion both have a square shape.
- the pattern dimension of the light transmitting portion is 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m or 100 ⁇ m, respectively.
- the pattern dimension of the light shielding portion is 10 ⁇ m.
- the pattern dimensions of the semi-transparent portion have portions of 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m and 100 ⁇ m, respectively.
- the halftone photomask As an example of the halftone photomask, an arrangement of the light transmitting part, the light shielding part, and the semi-light transmitting part, and an example of the dimensions are shown in FIG.
- a +, A, B and C pass when the maximum step thickness is 1.0 ⁇ m or more, A +, A and B half tones when the maximum step thickness is 1.5 ⁇ m or more A + and A were considered to have excellent halftone characteristics, with the characteristics being excellent and the maximum step thickness being 2.0 ⁇ m or more.
- the cured film of the composition 7 prepared by the above method has a film thickness (T FT ) of the light-transmitting portion after heat curing of 4.0 ⁇ m, and a minimum film thickness of the semi-light-transmitting portion after heat curing (T HT / min ) was 2.3 ⁇ m, so that the maximum step thickness was 1.7 ⁇ m, and it was confirmed that the halftone characteristics were good.
- compositions 18-35, 60-68, 1, 5, 43, 45, 47, 48, 51, 53, 54-56, and 78-81 are used as Examples 86-129.
- Compositions 87, 88, 84, 90, and 89 were used as Comparative Examples 9 to 13 to evaluate halftone characteristics.
- the evaluation results of Examples 85 to 129 and Comparative Examples 9 to 13 are shown in Tables 15-1 and 15-2.
- the negative photosensitive resin composition, the cured film, the organic EL display and the method for producing the same according to the present invention are suitable for an organic EL display having improved display characteristics and reliability.
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Abstract
Description
(I)ナフタレンカルボニル構造、トリメチルベンゾイル構造、チオフェンカルボニル構造、及びフランカルボニル構造からなる群より選ばれる一種類以上の構造
(II)ニトロ基、カルバゾール構造、及び一般式(11)で表される基
(III)ニトロ基、並びに、フルオレン構造、ジベンゾフラン構造、ジベンゾチオフェン構造、ナフタレン構造、ジフェニルメタン構造、ジフェニルアミン構造、ジフェニルエーテル構造、及びジフェニルスルフィド構造からなる群より選ばれる一種類以上の構造
(I)ナフタレンカルボニル構造、トリメチルベンゾイル構造、チオフェンカルボニル構造、及びフランカルボニル構造からなる群より選ばれる一種類以上の構造
(II)ニトロ基、カルバゾール構造、及び一般式(11)で表される基
(III)ニトロ基、並びに、フルオレン構造、ジベンゾフラン構造、ジベンゾチオフェン構造、ナフタレン構造、ジフェニルメタン構造、ジフェニルアミン構造、ジフェニルエーテル構造、及びジフェニルスルフィド構造からなる群より選ばれる一種類以上の構造
本発明のネガ型感光性樹脂組成物は、(A)アルカリ可溶性樹脂として、少なくとも(A1)第1の樹脂を含有する。(A1)第1の樹脂として、(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上を含有する。本発明において、(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体は、単一の樹脂又はそれらの共重合体のいずれであっても構わない。
(A1-2)ポリイミド前駆体としては、例えば、テトラカルボン酸、対応するテトラカルボン酸二無水物、又はテトラカルボン酸ジエステル二塩化物などと、ジアミン、対応するジイソシアネート化合物、又はトリメチルシリル化ジアミンなどと、を反応させることによって得られるものが挙げられ、テトラカルボン酸残基及び/又はその誘導体残基と、ジアミン残基及び/又はその誘導体残基を有する。(A1-2)ポリイミド前駆体としては、例えば、ポリアミド酸、ポリアミド酸エステル、ポリアミド酸アミド、又はポリイソイミドが挙げられる。
(A1-4)ポリベンゾオキサゾール前駆体としては、例えば、ジカルボン酸、対応するジカルボン酸二塩化物、又はジカルボン酸活性ジエステルなどと、ジアミンとしてビスアミノフェノール化合物などと、を反応させることによって得られるものが挙げられ、ジカルボン酸残基及び/又はその誘導体残基と、ビスアミノフェノール化合物残基及び/又はその誘導体残基を有する。(A1-4)ポリベンゾオキサゾール前駆体としては、例えば、ポリヒドロキシアミドが挙げられる。
テトラカルボン酸としては、例えば、芳香族テトラカルボン酸、脂環式テトラカルボン酸、又は脂肪族テトラカルボン酸が挙げられる。これらのテトラカルボン酸は、カルボキシ基の酸素原子以外にヘテロ原子を有してもよい。
ジアミン及びその誘導体としては、例えば、芳香族ジアミン、ビスアミノフェノール化合物、脂環式ジアミン、脂環式ジヒドロキシジアミン、脂肪族ジアミン、又は脂肪族ジヒドロキシジアミンが挙げられる。これらのジアミン及びその誘導体は、アミノ基及びその誘導体が有する窒素原子、酸素原子以外に、ヘテロ原子を有してもよい。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上は、フッ素原子を有する構造単位を、全構造単位の10~100mol%で含有する。(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上が、フッ素原子を有する構造単位を含有することで、透明性が向上し、露光時の感度を向上させることができるとともに、現像後に低テーパー形状のパターンを形成することができる。加えて、ハーフトーン特性を向上できる。これは、膜の透明性向上による、膜の深部でのラジカル硬化が可能となったためと推測される。また、後述する(C1-1)特定のオキシムエステル系光重合開始剤が、ハロゲンで置換された基を有する場合、樹脂と開始剤との相溶性を高めることができ、膜の深部においても露光時のUV硬化が効率的に進行するためと考えられる。加えて、フッ素原子によって膜表面に撥水性を付与することができ、アルカリ現像時における膜表面への現像液の浸み込みを抑制し、現像液によるサイドエッチングを抑制できるためと考えられる。ここでいう露光とは、活性化学線(放射線)の照射のことであり、例えば、可視光線、紫外線、電子線、又はX線などの照射が挙げられる。一般的に使用されている光源であるという観点から、例えば、可視光線や紫外線の照射が可能な超高圧水銀灯光源が好ましく、j線(波長313nm)、i線(波長365nm)、h線(波長405nm)、又はg線(波長436nm)の照射がより好ましい。以降、露光とは、活性化学線(放射線)の照射をいう。
(A1-1)ポリイミド及び/又は(A1-2)ポリイミド前駆体は、芳香族カルボン酸に由来する構造単位及び/又はその誘導体に由来する構造単位を含有することが好ましい。(A1-1)ポリイミド及び/又は(A1-2)ポリイミド前駆体が、芳香族カルボン酸に由来する構造単位及び/又はその誘導体に由来する構造単位を含有することで、芳香族基の耐熱性により、硬化膜の耐熱性を向上させることができる。芳香族カルボン酸及びその誘導体としては、芳香族テトラカルボン酸及び/又はその誘導体が好ましい。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上は、芳香族アミンに由来する構造単位及び/又はその誘導体に由来する構造単位を含有することが好ましい。(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上が、芳香族アミンに由来する構造単位及び/又はその誘導体に由来する構造単位を含有することで、芳香族基の耐熱性により、硬化膜の耐熱性を向上させることができる。芳香族アミン及びその誘導体としては、芳香族ジアミン、ビスアミノフェノール化合物、芳香族トリアミン、若しくはトリスアミノフェノール化合物、及び/又はそれらの誘導体が好ましく、芳香族ジアミン若しくはビスアミノフェノール化合物、及び/又はそれらの誘導体がより好ましい。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上は、シリル基又はシロキサン結合を有するジアミンに由来する構造単位、及び/又はその誘導体に由来する構造単位を含有することが好ましい。(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上が、シリル基又はシロキサン結合を有するジアミンに由来する構造単位、及び/又はその誘導体に由来する構造単位を含有することで、ネガ型感光性樹脂組成物の硬化膜と下地の基板界面における相互作用が増大し、下地の基板との密着性及び硬化膜の耐薬品性を向上させることができる。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上は、オキシアルキレン構造を有するアミンに由来する構造単位及び/又はその誘導体に由来する構造単位を含有することが好ましい。(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上が、オキシアルキレン構造を有するアミンに由来する構造単位及び/又はその誘導体に由来する構造単位を含有することで、低テーパーのパターン形状の硬化膜を得ることができるとともに、硬化膜の機械特性及びアルカリ現像液でのパターン加工性を向上させることができる。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上は、樹脂の末端が、モノアミン、ジカルボン酸無水物、モノカルボン酸、モノカルボン酸塩化物、又はモノカルボン酸活性エステルなどの末端封止剤で封止されていても構わない。樹脂の末端が、末端封止剤で封止されることで、(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上を含有する樹脂組成物の塗液の保管安定性を向上させることができる。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上は、エチレン性不飽和二重結合基を有することが好ましい。エチレン性不飽和二重結合基を導入する反応により、これらの樹脂の側鎖に、エチレン性不飽和二重結合基を導入したものも好ましい。エチレン性不飽和二重結合基を有することで、現像後に低テーパー形状のパターンを形成することができる。
(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体から選ばれる一種類以上の重量平均分子量(以下、「Mw」)としては、ゲルパーミエーションクロマトグラフィー(以下、「GPC」)で測定されるポリスチレン換算で、1,000以上が好ましく、3,000以上がより好ましく、5,000以上がさらに好ましい。Mwが1,000以上であると、現像後の解像度を向上させることができる。一方、Mwとしては、500,000以下が好ましく、300,000以下がより好ましく、100,000以下がさらに好ましい。Mwが500,000以下であると、塗布時のレベリング性及びアルカリ現像液でのパターン加工性を向上させることができる。
本発明のネガ型感光性樹脂組成物は、(A)アルカリ可溶性樹脂として、(A2)第2の樹脂を含有することが好ましい。(A2)第2の樹脂として、露光時の感度向上及び現像後のパターン形状制御による低テーパー化の観点から、(A2-1)ポリシロキサン、(A2-2)多環側鎖含有樹脂、(A2-3)酸変性エポキシ樹脂、及び(A2-4)アクリル樹脂から選ばれる一種類以上を含有することが好ましい。本発明において、(A2-1)ポリシロキサン、(A2-2)多環側鎖含有樹脂、(A2-3)酸変性エポキシ樹脂、及び(A2-4)アクリル樹脂は、単一の樹脂又はそれらの共重合体のいずれであっても構わない。
本発明に用いられる(A2-1)ポリシロキサンとしては、例えば、三官能オルガノシラン、四官能オルガノシラン、二官能オルガノシラン、及び一官能オルガノシランから選ばれる一種類以上を加水分解し、脱水縮合させて得られるポリシロキサンが挙げられる。
本発明に用いられる(A2-1)ポリシロキサンとしては、硬化膜の耐熱性向上及び現像後の解像度向上の観点から、三官能オルガノシラン単位及び/又は四官能オルガノシラン単位を含有することが好ましい。三官能オルガノシランとしては、一般式(7)で表されるオルガノシラン単位が好ましい。四官能オルガノシラン単位としては、一般式(8)で表されるオルガノシラン単位が好ましい。また、パターン形状の低テーパー化及び硬化膜の機械特性向上の観点から、二官能オルガノシラン単位を含有しても構わない。二官能オルガノシランとしては、一般式(9)で表されるオルガノシラン単位が好ましい。また、樹脂組成物の塗液の保管安定性向上の観点から、一官能オルガノシラン単位を含有しても構わない。一官能オルガノシラン単位としては、一般式(10)で表されるオルガノシラン単位が好ましい。
本発明に用いられる(A2-1)ポリシロキサンとしては、芳香族基を有するオルガノシラン単位を含有することが好ましい。そのような(A2-1)ポリシロキサンは、一般式(7)、一般式(9)、又は一般式(10)で表されるオルガノシラン単位を有するオルガノシランとして、芳香族基を有するオルガノシランを用いて得られるものであることが好ましい。(A2-1)ポリシロキサンが芳香族基を有するオルガノシラン単位を含有することで、芳香族基の耐熱性により、硬化膜の耐熱性を向上させることができる。
本発明に用いられる(A2-1)ポリシロキサンのMwとしては、GPCで測定されるポリスチレン換算で、500以上が好ましく、700以上がより好ましく、1,000以上がさらに好ましい。Mwが500以上であると、現像後の解像度を向上させることができる。一方、Mwとしては、100,000以下が好ましく、50,000以下がより好ましく、20,000以下がさらに好ましい。Mwが100,000以下であると、塗布時のレベリング性及びアルカリ現像液でのパターン加工性を向上させることができる。
本発明に用いられる(A2-2)多環側鎖含有樹脂としては、例えば、以下の(I)~(IV)の多環側鎖含有樹脂が挙げられる。
(I)多官能フェノール化合物と多官能カルボン酸無水物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる多環側鎖含有樹脂。
(II)多官能フェノール化合物とエポキシ化合物とを反応させて得られる化合物に、多官能カルボン酸無水物を反応させて得られる多環側鎖含有樹脂。
(III)多官能エポキシ化合物と多官能カルボン酸化合物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる多環側鎖含有樹脂。
(IV)多官能エポキシ化合物とカルボン酸化合物とを反応させて得られる化合物に、多官能カルボン酸無水物を反応させて得られる多環側鎖含有樹脂。
本発明に用いられる(A2-2)多環側鎖含有樹脂としては、芳香族基カルボン酸及びその誘導体に由来する構造単位を含有することが好ましい。(A2-2)多環側鎖含有樹脂が芳香族基カルボン酸及びその誘導体に由来する構造単位を含有することで、芳香族基の耐熱性により、硬化膜の耐熱性を向上させることができる。芳香族カルボン酸及びその誘導体としては、芳香族基を有するテトラカルボン酸、芳香族基を有するテトラカルボン酸二無水物、芳香族基を有するトリカルボン酸、及び芳香族基を有するジカルボン酸から選ばれる一種類以上が好ましい。
本発明に用いられる(A2-2)多環側鎖含有樹脂としては、カルボン酸及びその誘導体に由来する構造単位を含有し、(A2-2)多環側鎖含有樹脂が、酸性基を有することが好ましい。(A2-2)多環側鎖含有樹脂が酸性基を有することで、アルカリ現像液でのパターン加工性及び現像後の解像度を向上させることができる。
本発明に用いられる(A2-2)多環側鎖含有樹脂としては、例えば、“ADEKA ARKLS”(登録商標) WR-101若しくは同 WR-301(以上、いずれもADEKA社製)、OGSOL(登録商標) CR-1030、同 CR-TR1、同 CR-TR2、同 CR-TR3、同 CR-TR4、同 CR-TR5、同 CR-TR6、同 CR-TR7、同 CR-TR8、同 CR-TR9、若しくは同 CR-TR10(以上、いずれも大阪ガスケミカル社製)、又はTR-B201若しくはTR-B202(以上、いずれもTRONLY社製)が挙げられる。
本発明に用いられる(A2-2)多環側鎖含有樹脂のMwとしては、GPCで測定されるポリスチレン換算で、500以上が好ましく、1,000以上がより好ましく、1,500以上がさらに好ましい。Mwが500以上であると、現像後の解像度を向上させることができる。一方、Mwとしては、100,000以下が好ましく、50,000以下がより好ましく、20,000以下がさらに好ましい。Mwが100,000以下であると、塗布時のレベリング性及びアルカリ現像液でのパターン加工性を向上させることができる。
本発明に用いられる(A2-3)酸変性エポキシ樹脂としては、例えば、以下の(I)~(VI)の酸変性エポキシ樹脂が挙げられる。
(I)多官能フェノール化合物と多官能カルボン酸無水物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる酸変性エポキシ樹脂。
(II)多官能フェノール化合物とエポキシ化合物とを反応させて得られる化合物に、多官能カルボン酸無水物を反応させて得られる酸変性エポキシ樹脂。
(III)多官能アルコール化合物と多官能カルボン酸無水物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる酸変性エポキシ樹脂。
(IV)多官能アルコール化合物とエポキシ化合物とを反応させて得られる化合物に、多官能カルボン酸無水物を反応させて得られる酸変性エポキシ樹脂。
(V)多官能エポキシ化合物と多官能カルボン酸化合物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる酸変性エポキシ樹脂。
(VI)多官能エポキシ化合物とカルボン酸化合物とを反応させて得られる化合物に、多官能カルボン酸無水物を反応させて得られる酸変性エポキシ樹脂。
本発明に用いられる(A2-3)酸変性エポキシ樹脂としては、芳香族カルボン酸及びその誘導体に由来する構造単位を含有することが好ましい。(A2-3)酸変性エポキシ樹脂が、芳香族カルボン酸及びその誘導体に由来する構造単位を含有することで、芳香族基の耐熱性により、硬化膜の耐熱性を向上させることができる。芳香族カルボン酸及びその誘導体としては、芳香族基を有するテトラカルボン酸、芳香族基を有するトリカルボン酸、芳香族基を有するトリカルボン酸無水物、芳香族基を有するジカルボン酸、及び芳香族基を有するジカルボン酸無水物から選ばれる一種類以上が好ましい。
本発明に用いられる(A2-3)酸変性エポキシ樹脂としては、カルボン酸及びその誘導体に由来する構造単位を含有し、(A2-3)酸変性エポキシ樹脂が、酸性基を有することが好ましい。(A2-3)酸変性エポキシ樹脂が酸性基を有することで、アルカリ現像液でのパターン加工性及び現像後の解像度を向上させることができる。
本発明に用いられる(A2-3)酸変性エポキシ樹脂としては、例えば、“KAYARAD”(登録商標) PCR-1222H、同 CCR-1171H、同 TCR-1348H、同 ZAR-1494H、同 ZFR-1401H、同 ZCR-1798H、同 ZXR-1807H、同 ZCR-6002H、若しくは同 ZCR-8001H(以上、いずれも日本化薬社製)、又は“NK OLIGO”(登録商標) EA-6340、同 EA-7140、若しくは同 EA-7340(以上、いずれも新中村化学工業社製)が挙げられる。
本発明に用いられる(A2-3)酸変性エポキシ樹脂のMwとしては、GPCで測定されるポリスチレン換算で、500以上が好ましく、1,000以上がより好ましく、1,500以上がさらに好ましい。Mwが上述した範囲内であると、現像後の解像度を向上させることができる。一方、Mwとしては、100,000以下が好ましく、50,000以下がより好ましく、20,000以下がさらに好ましい。Mwが上述した範囲内であると、塗布時のレベリング性及びアルカリ現像液でのパターン加工性を向上させることができる。
本発明に用いられる(A2-4)アクリル樹脂としては、例えば、酸性基を有する共重合成分、(メタ)アクリル酸エステルに由来する共重合成分、及びその他の共重合成分から選ばれる一種類以上の共重合成分を、ラジカル共重合させて得られるアクリル樹脂が挙げられる。
本発明に用いられる(A2-4)アクリル樹脂としては、酸性基を有する共重合成分に由来する構造単位を含有し、(A2-4)アクリル樹脂が、酸性基を有することが好ましい。(A2-4)アクリル樹脂が酸性基を有することで、アルカリ現像液でのパターン加工性及び現像後の解像度を向上させることができる。
本発明に用いられる(A2-4)アクリル樹脂としては、芳香族基を有する共重合成分に由来する構造単位を含有することが好ましい。(A2-4)アクリル樹脂が芳香族基を有する共重合成分に由来する構造単位を含有することで、芳香族基の耐熱性により、硬化膜の耐熱性を向上させることができる。
本発明に用いられる(A2-4)アクリル樹脂としては、脂環式基を有する共重合成分に由来する構造単位を含有することが好ましい。(A2-4)アクリル樹脂が脂環式基を有する共重合成分に由来する構造単位を含有することで、脂環式基の耐熱性及び透明性により、硬化膜の耐熱性及び透明性を向上させることができる。
本発明に用いられる(A2-4)アクリル樹脂のMwとしては、GPCで測定されるポリスチレン換算で、1,000以上が好ましく、3,000以上がより好ましく、5,000以上がさらに好ましい。Mwが1,000以上であると、現像後の解像度を向上させることができる。一方、Mwとしては、100,000以下が好ましく、70,000以下がより好ましく、50,000以下がさらに好ましい。Mwが100,000以下であると、塗布時のレベリング性及びアルカリ現像液でのパターン加工性を向上させることができる。
本発明のネガ型感光性樹脂組成物としては、さらに、(B)ラジカル重合性化合物を含有することが好ましい。(B)ラジカル重合性化合物とは、分子中に複数のエチレン性不飽和二重結合基を有する化合物をいう。露光時、後述する(C1)光重合開始剤から発生するラジカルによって、(B)ラジカル重合性化合物のラジカル重合が進行し、樹脂組成物の膜の露光部がアルカリ現像液に対して不溶化することで、ネガ型のパターンを形成することができる。
本発明のネガ型感光性樹脂組成物は、さらに、(B)ラジカル重合性化合物として、(B1)フルオレン骨格含有ラジカル重合性化合物及び(B2)インダン骨格含有ラジカル重合性化合物からなる群より選ばれる一種類以上を含有することが好ましい。
本発明のネガ型感光性樹脂組成物は、さらに、(B)ラジカル重合性化合物として、(B3)柔軟鎖含有脂肪族ラジカル重合性化合物を含有することが好ましい。(B3)柔軟鎖含有脂肪族ラジカル重合性化合物とは、分子中に複数のエチレン性不飽和二重結合基と、脂肪族鎖又はオキシアルキレン鎖などの柔軟骨格とを有する化合物をいう。
本発明のネガ型感光性樹脂組成物は、さらに、(B)ラジカル重合性化合物として、(B4)脂環式基含有ラジカル重合性化合物を含有することが好ましい。(B4)脂環式基含有ラジカル重合性化合物とは、分子中に複数のエチレン性不飽和二重結合基と、脂環式基とを有する化合物をいう。
縮合多環脂環式骨格としては、例えば、ビシクロ[4.3.0]ノナン骨格、ビシクロ[5.4.0]ウンデカン骨格、ビシクロ[2.2.2]オクタン骨格、トリシクロ[5.2.1.02,6]デカン骨格、ペンタシクロペンタデカン骨格、アダマンタン骨格又はヒドロキシアダマンタン骨格が挙げられる。
本発明のネガ型感光性樹脂組成物は、さらに、(C)感光剤として、(C1)光重合開始剤を含有する。(C1)光重合開始剤とは、露光によって結合開裂及び/又は反応してラジカルを発生する化合物をいう。(C1)光重合開始剤を含有させることで、上述した(B)ラジカル重合性化合物のラジカル重合が進行し、樹脂組成物の膜の露光部がアルカリ現像液に対して不溶化することで、ネガ型のパターンを形成することができる。また、露光時のUV硬化が促進されて、感度を向上させることができる。
本発明のネガ型感光性樹脂組成物は、(C1)光重合開始剤として、(I)、(II)、及び(III)からなる群より選ばれる一種類以上の構造を有する(C1-1)オキシムエステル系光重合開始剤(以下、「(C1-1)特定のオキシムエステル系光重合開始剤」)を含有する。
(II)ニトロ基、カルバゾール構造、及び一般式(11)で表される基
(III)ニトロ基、並びに、フルオレン構造、ジベンゾフラン構造、ジベンゾチオフェン構造、ナフタレン構造、ジフェニルメタン構造、ジフェニルアミン構造、ジフェニルエーテル構造、及びジフェニルスルフィド構造からなる群より選ばれる一種類以上の構造
本発明のネガ型感光性樹脂組成物は、さらに、(C1)光重合開始剤として、(C1-2)α-アミノケトン系光重合開始剤、(C1-3)アシルホスフィンオキシド系光重合開始剤及び(C1-4)ビイミダゾール系光重合開始剤からなる群より選ばれる一種類以上を含有することが好ましい。
本発明のネガ型感光性樹脂組成物は、さらに、(C)感光剤として、(C2)光酸発生剤を含有しても構わない。(C2)光酸発生剤とは、露光によって結合開裂を起こして酸を発生する化合物をいう。(C2)光酸発生剤を含有させることで、露光時のUV硬化が促進されて、感度を向上させることができる。また、樹脂組成物の熱硬化後の架橋密度が向上し、硬化膜の耐薬品性を向上させることができる。(C2)光酸発生剤としては、イオン性化合物と、非イオン性化合物と、がある。
本発明のネガ型感光性樹脂組成物は、さらに、(D)着色剤として、(Da)黒色剤を含有する。(D)着色剤とは、特定波長の光を吸収する化合物であり、特に、可視光線の波長(380~780nm)の光を吸収することで、着色する化合物をいう。(D)着色剤を含有させることで、ネガ型感光性樹脂組成物から得られる膜を着色させることができ、樹脂組成物の膜を透過する光、又は、樹脂組成物の膜から反射する光を、所望の色に着色させる、着色性を付与することができる。また、樹脂組成物の膜を透過する光、又は、樹脂組成物の膜から反射する光から、(D)着色剤が吸収する波長の光を遮光する、遮光性を付与することができる。
本発明のネガ型感光性樹脂組成物としては、上述した(D)着色剤が、(D1)顔料を含有することが好ましい。上述した(D)着色剤が、(D1)顔料を含有する態様としては、上述した(Da)黒色剤を必ず含有し、任意に(Db)黒色以外の着色剤を含有することができる。(D1)顔料とは、対象物の表面に(D1)顔料が物理吸着、又は、対象物の表面と(D1)顔料と、が相互作用などをすることで、対象物を着色させる化合物をいい、一般的に溶剤等に不溶である。また、(D1)顔料による着色は隠蔽性が高く、紫外線等による色褪せがしにくい。(D1)顔料を含有させることで、隠蔽性に優れた色に着色することでき、樹脂組成物の膜の遮光性及び耐候性を向上させることができる。
本発明のネガ型感光性樹脂組成物としては、上述した(D1)顔料が、(D1a)黒色顔料、又は(D1a)黒色顔料と(D1b)黒色以外の顔料とを含有することが好ましい。
本発明のネガ型感光性樹脂組成物としては、上述した(D1a)黒色顔料が、(D1a-1)黒色有機顔料、(D1a-2)黒色無機顔料、及び(D1a-3)二色以上の着色顔料混合物から選ばれる一種類以上であることが好ましい。
本発明のネガ型感光性樹脂組成物としては、上述した(D1b)黒色以外の顔料が、(D1b-1)黒色以外の有機顔料及び/又は(D1b-2)黒色以外の無機顔料であることが好ましい。
本発明のネガ型感光性樹脂組成物としては、露光時の感度向上、現像後のパターン形状制御による低テーパー化、熱硬化前後におけるパターン開口寸法幅変化抑制、及び、ハーフトーン特性向上の観点から、上述した(D1a-1)黒色有機顔料が、(D1a-1a)ベンゾフラノン系黒色顔料、(D1a-1b)ペリレン系黒色顔料、及び(D1a-1c)アゾ系黒色顔料からなる群より選ばれる一種類以上であることが好ましく、(D1a-1a)ベンゾフラノン系黒色顔料がより好ましい。
本発明のネガ型感光性樹脂組成物としては、上述した(D1a-3)二色以上の顔料混合物が、(D1a-3a)青色顔料、赤色顔料、及び黄色顔料を含む着色顔料混合物、(D1a-3b)紫色顔料、及び黄色顔料を含む着色顔料混合物、(D1a-3c)青色顔料、赤色顔料、及び橙色顔料を含む着色顔料混合物、又は(D1a-3d)青色顔料、紫色顔料、及び橙色顔料を含む着色顔料混合物であることが好ましい。
本発明のネガ型感光性樹脂組成物としては、前記(D1a-1)黒色有機顔料が、さらに、(DC)被覆層を含有することが好ましい。(DC)被覆層とは、例えば、シランカップリング剤による表面処理、ケイ酸塩による表面処理、金属アルコキシドによる表面処理又は樹脂による被覆処理などの処理することで形成される、顔料表面を被覆する層をいう。
被覆率M(%)={L1/(L1+L2)}×100
L1:粒子の外周のうち、被覆層により覆われた部位の合計長さ(nm)
L2:粒子の外周のうち、被覆層により覆われていない部位(界面と埋め込み樹脂が直接接する部位)の合計長さ(nm)
L1+L2:粒子の外周長さ(nm)。
(DC)被覆層としては、(DC-1)シリカ被覆層、(DC-2)金属酸化物被覆層及び(DC-3)金属水酸化物被覆層からなる群より選ばれる一種類を含有することが好ましい。シリカ、金属酸化物及び金属水酸化物は、顔料に耐アルカリ性を付与する機能を有するため、顔料由来の現像残渣発生を抑制することができる。
本発明のネガ型感光性樹脂組成物としては、上述した(D)着色剤が、(D2)染料を含有することが好ましい。上述した(D)着色剤が、(D2)染料を含有する態様としては、上述した(Da)黒色剤及び/又は(Db)黒色以外の着色剤として、(D2)染料を含有することが好ましい。
本発明のネガ型感光性樹脂組成物としては、上述した(D2)染料が、(D2a-1)黒色染料、(D2a-2)二色以上の染料混合物、及び(D2b)黒色以外の染料から選ばれる一種類以上を含有することが好ましい。
本発明のネガ型感光性樹脂組成物としては、さらに、(E)分散剤を含有することが好ましい。(E)分散剤とは、上述した(D1)顔料及び/又は(D2)染料として分散染料などの表面と相互作用する表面親和性基と、(D1)顔料及び/又は(D2)染料として分散染料の分散安定性を向上させる分散安定化構造とを有する化合物をいう。(E)分散剤の分散安定化構造としては、ポリマー鎖及び/又は静電荷を有する置換基などが挙げられる。
本発明のネガ型感光性樹脂組成物としては、さらに、連鎖移動剤を含有することが好ましい。連鎖移動剤とは、露光時のラジカル重合により得られるポリマー鎖の、ポリマー生長末端からラジカルを受け取り、他のポリマー鎖へのラジカル移動を介することが可能な化合物をいう。
本発明のネガ型感光性樹脂組成物としては、さらに、増感剤を含有することが好ましい。増感剤とは、露光によるエネルギーを吸収し、内部転換及び項間交差によって励起三重項の電子を生じ、上述した(C1)光重合開始剤などへのエネルギー移動を介することが可能な化合物をいう。
本発明のネガ型感光性樹脂組成物としては、さらに、重合禁止剤を含有することが好ましい。重合禁止剤とは、露光時に発生したラジカル、又は、露光時のラジカル重合により得られるポリマー鎖の、ポリマー生長末端のラジカルを捕捉し、安定ラジカルとして保持することで、ラジカル重合を停止することが可能な化合物をいう。
本発明のネガ型感光性樹脂組成物としては、さらに、架橋剤を含有することが好ましい。架橋剤とは、樹脂と結合可能な架橋性基を有する化合物をいう。架橋剤を含有させることで、硬化膜の硬度及び耐薬品性を向上させることができる。これは、架橋剤により、樹脂組成物の硬化膜に新たな架橋構造を導入することができるため、架橋密度が向上するためと推測される。
本発明のネガ型感光性樹脂組成物としては、さらに、シランカップリング剤を含有することが好ましい。シランカップリング剤とは、加水分解性のシリル基又はシラノール基を有する化合物をいう。シランカップリング剤を含有させることで、樹脂組成物の硬化膜と下地の基板界面における相互作用が増大し、下地の基板との密着性及び硬化膜の耐薬品性を向上させることができる。シランカップリング剤としては、三官能オルガノシラン、四官能オルガノシラン、又はシリケート化合物が好ましい。
本発明のネガ型感光性樹脂組成物としては、さらに、界面活性剤を含有しても構わない。界面活性剤とは、親水性の構造及び疎水性の構造を有する化合物をいう。界面活性剤を適量含有させることで、樹脂組成物の表面張力を任意に調整することができ、塗布時のレベリング性が向上し、塗膜の膜厚均一性を向上させることができる。界面活性剤としては、フッ素樹脂系界面活性剤、シリコーン系界面活性剤、ポリオキシアルキレンエーテル系界面活性剤、又はアクリル樹脂系界面活性剤が好ましい。
本発明のネガ型感光性樹脂組成物としては、さらに、溶剤を含有することが好ましい。溶剤とは、樹脂組成物中に含有させる各種樹脂及び各種添加剤を溶解させることができる化合物をいう。溶剤を含有させることで、樹脂組成物中に含有させる各種樹脂及び各種添加剤を均一に溶解させ、硬化膜の透過率を向上させることができる。また、樹脂組成物の粘度を任意に調整することができ、基板上に所望の膜厚で成膜することができる。加えて、樹脂組成物の表面張力又は塗布時の乾燥速度などを任意に調整することができ、塗布時のレベリング性及び塗膜の膜厚均一性を向上させることができる。
本発明のネガ型感光性樹脂組成物としては、さらに、他の樹脂又はそれらの前駆体を含有しても構わない。他の樹脂又はそれらの前駆体としては、例えば、ポリアミド、ポリアミドイミド、エポキシ樹脂、ノボラック樹脂、ウレア樹脂、若しくはポリウレタン、又はそれらの前駆体が挙げられる。
本発明のネガ型感光性樹脂組成物の、代表的な製造方法について説明する。(D)着色剤として(Da)黒色剤を含む(D1)顔料を含有する場合、(A1)第1の樹脂及び(A2)第2の樹脂の溶液に(E)分散剤を加え、分散機を用いて、この混合溶液に(D1)顔料を分散させ、顔料分散液を調製する。次に、この顔料分散液に、(B)ラジカル重合性化合物、(C1)光重合開始剤、その他の添加剤、及び任意の溶剤を加え、20分~3時間攪拌して均一な溶液とする。攪拌後、得られた溶液をろ過することで、本発明のネガ型感光性樹脂組成物が得られる。
本発明のネガ型感光性樹脂組成物は、低テーパーのパターン形状の硬化パターンを含む硬化膜を得ることが可能である。本発明のネガ型感光性樹脂組成物から得られる、硬化膜が含む硬化パターンの断面における傾斜辺のテーパー角は、1°以上が好ましく、5°以上がより好ましく、10°以上がさらに好ましく、12°以上がさらにより好ましく、15°以上が特に好ましい。テーパー角が1°以上であると、発光素子を高密度に集積及び配置できることで、表示装置の解像度を向上させることができる。一方、硬化膜が含む硬化パターンの断面における傾斜辺のテーパー角は、60°以下が好ましく、55°以下がより好ましく、50°以下がさらに好ましく、45°以下がさらにより好ましく、40°以下が特に好ましい。テーパー角が60°以下であると、透明電極又は反射電極などの電極を形成する際の断線を防止することができる。また、電極のエッジ部における電界集中を抑制できることで、発光素子の劣化を抑制することができる。
本発明のネガ型感光性樹脂組成物は、高感度を維持しつつ、厚膜部と薄膜部とで十分な膜厚差がある段差形状を有し、低テーパーのパターン形状を有する硬化パターンを形成することができる。加えて、現像後のパターン形状制御による低テーパー化が可能で、熱硬化前後におけるパターン開口寸法幅の変化を抑制可能なため、現像後に形成した段差形状及びパターン開口寸法を熱硬化後に維持できる。そのため、本発明のネガ型感光性樹脂組成物は、有機ELディスプレイにおける画素分割層の、段差形状を一括形成するための用途において、特に好適である。同様に、電極絶縁層、配線絶縁層、層間絶縁層、TFT平坦化層、電極平坦化層、配線平坦化層、TFT保護層、電極保護層、配線保護層、ゲート絶縁層、カラーフィルタ、ブラックマトリックス又はブラックカラムスペーサーの、段差形状を一括形成するための用途に好適である。
2.0≦(TFT)≦10.0 (α)
0.20≦(THT)≦7.5 (β)
0.10×(TFT)≦(THT)≦0.75×(TFT) (γ)
2.0≦(TFT)≦10.0 (δ)
0.30≦(THT)≦7.0 (ε)
0.15×(TFT)≦(THT)≦0.70×(TFT) (ζ)
本発明のネガ型感光性樹脂組成物を用いたプロセスとして、該組成物の硬化膜を有機ELディスプレイの遮光性の画素分割層として用いたプロセスを例に、図1に模式的断面図を示して説明する。まず、(工程1)ガラス基板1上に、薄膜トランジスタ(以下、「TFT」)2を形成し、TFT平坦化膜用の感光性材料を成膜し、フォトリソグラフィーによってパターン加工した後、熱硬化させてTFT平坦化用の硬化膜3を形成する。次に、(工程2)銀‐パラジウム‐銅合金(以下、「APC」)をスパッタにより成膜し、フォトレジストを用いてエッチングによりパターン加工してAPC層を形成し、さらに、APC層の上層に酸化インジウムスズ(以下、「ITO」)をスパッタにより成膜し、フォトレジストを用いたエッチングによりパターン加工し、第1電極として反射電極4を形成する。その後、(工程3)本発明のネガ型感光性樹脂組成物を塗布及びプリベークして、プリベーク膜5aを形成する。次いで、(工程4)所望のパターンを有するマスク6を介して、活性化学線7を照射する。次に、(工程5)現像してパターン加工をした後、必要に応じてブリーチング露光及びミドルベークし、熱硬化させることで、遮光性の画素分割層として、所望のパターンを有する硬化パターン5bを形成する。その後、(工程6)EL発光材料を、マスクを介した蒸着によって成膜してEL発光層8を形成し、マグネシウム‐銀合金(以下、「MgAg」)を蒸着により成膜し、フォトレジストを用いてエッチングによりパターン加工し、第2電極として透明電極9を形成する。次に(工程7)平坦化膜用の感光性材料を成膜し、フォトリソグラフィーによってパターン加工した後、熱硬化させて平坦化用の硬化膜10を形成し、その後、カバーガラス11を接合させることで、本発明のネガ型感光性樹脂組成物を遮光性の画素分割層として有する有機ELディスプレイを得る。
本発明のネガ型感光性樹脂組成物を用いた別のプロセスとして、該組成物の硬化膜を液晶ディスプレイのブラックカラムスペーサー(以下、「BCS」)及びカラーフィルタのブラックマトリックス(以下、「BM」)として用いたプロセスを例に、図2に模式的断面図を示して説明する。
本発明のネガ型感光性樹脂組成物から得られる硬化膜は、有機ELディスプレイ又は液晶ディスプレイを好適に構成することができる。
(1)基板上に、本発明のネガ型感光性樹脂組成物の塗膜を成膜する工程、
(2)前記ネガ型感光性樹脂組成物の塗膜にフォトマスクを介して活性化学線を照射する工程、
(3)アルカリ溶液を用いて現像し、前記ネガ型感光性樹脂組成物のパターンを形成する工程、及び、
(4)前記パターンを加熱して、前記ネガ型感光性樹脂組成物の硬化パターンを得る工程。
本発明のネガ型感光性樹脂組成物を用いた、表示装置の製造方法は、(1)基板上に、ネガ型感光性樹脂組成物の塗膜を成膜する工程、を有する。本発明のネガ型感光性樹脂組成物を成膜する方法としては、例えば、基板上に、上述した樹脂組成物を塗布する方法、又は、基板上に、上述した樹脂組成物をパターン状に塗布する方法が挙げられる。
基板上に、本発明のネガ型感光性樹脂組成物を塗布する方法としては、例えば、マイクログラビアコーティング、スピンコーティング、ディップコーティング、カーテンフローコーティング、ロールコーティング、スプレーコーティング、又はスリットコーティングが挙げられる。塗布膜厚は、塗布方法、樹脂組成物の固形分濃度や粘度などによって異なるが、通常は塗布及びプリベーク後の膜厚が0.1~30μmになるように塗布する。
基板上に、本発明のネガ型感光性樹脂組成物をパターン状に塗布する方法としては、例えば、凸版印刷、凹版印刷、孔版印刷、平版印刷、スクリーン印刷、インクジェット印刷、オフセット印刷、又はレーザー印刷が挙げられる。塗布膜厚は、塗布方法、本発明のネガ型感光性樹脂組成物の固形分濃度や粘度などによって異なるが、通常は塗布及びプリベーク後の膜厚が0.1~30μmになるように塗布する。
基板上に成膜した、本発明のネガ型感光性樹脂組成物の塗膜をパターン加工する方法としては、例えば、フォトリソグラフィーにより直接パターン加工する方法又はエッチングによりパターン加工する方法が挙げられる。工程数の削減による生産性の向上及びプロセスタイム短縮の観点から、フォトリソグラフィーにより直接パターン加工する方法が好ましい。
本発明のネガ型感光性樹脂組成物を用いた、表示装置の製造方法は、(2)上述したネガ型感光性樹脂組成物の塗膜にフォトマスクを介して活性化学線を照射する工程、を有する。基板上に、本発明のネガ型感光性樹脂組成物を塗布及びプリベークして成膜した後、ステッパー、ミラープロジェクションマスクアライナー(MPA)、又はパラレルライトマスクアライナー(PLA)などの露光機を用いて露光する。露光時に照射する活性化学線としては、例えば、紫外線、可視光線、電子線、X線、KrF(波長248nm)レーザー、又はArF(波長193nm)レーザーなどが挙げられる。水銀灯のj線(波長313nm)、i線(波長365nm)、h線(波長405nm)、又はg線(波長436nm)を用いることが好ましい。また露光量は通常100~40,000J/m2(10~4,000mJ/cm2)程度(i線照度計の値)であり、必要に応じて所望のパターンを有するフォトマスクを介して露光することができる。
本発明のネガ型感光性樹脂組成物を用いた、表示装置の製造方法は、(3)アルカリ溶液を用いて現像し、上述したネガ型感光性樹脂組成物のパターンを形成する工程、を有する。露光後、自動現像装置などを用いて現像する。本発明のネガ型感光性樹脂組成物は、ネガ型の感光性を有するため、現像後、未露光部が現像液で除去され、レリーフ・パターンを得ることができる。
本発明のネガ型感光性樹脂組成物を用いた、表示装置の製造方法は、前記(3)アルカリ溶液を用いて現像し、前記ネガ型感光性樹脂組成物のパターンを形成する工程の後、さらに、前記ネガ型感光性樹脂組成物のパターンを光硬化させる工程、を有することが好ましい。
本発明のネガ型感光性樹脂組成物を用いた、表示装置の製造方法は、(4)上述したネガ型感光性樹脂組成物のパターンを加熱して、上述したネガ型感光性樹脂組成物の硬化パターンを得る工程、を有する。基板上に成膜した、本発明のネガ型感光性樹脂組成物のパターンの加熱は、オーブン、ホットプレート、赤外線、フラッシュアニール装置、又はレーザーアニール装置などを使用することができる。本発明のネガ型感光性樹脂組成物のパターンを加熱して熱硬化させることで、硬化膜の耐熱性を向上させることができるとともに、低テーパーのパターン形状を得ることができる。
6FDA:2,2-(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物;4,4’-ヘキサフルオロプロパン-2,2-ジイル-ビス(1,2-フタル酸無水物)
A-BPEF:“NK ESTER”(登録商標) A-BPEF(新中村化学工業社製;9,9-ビス[4-(2-アクリロキシエトキシ)フェニル]フルオレン)
A-DCP:“NK ESTER”(登録商標) A-DCP(新中村化学工業社製;ジメチロール-トリシクロデカンジアクリレート)
A-DPH-6E:“NK ESTER”(登録商標) A-DPH-6E(新中村化学工業社製;オキシエチレン構造を分子中に6個有する、エトキシ化ジペンタエリスリトールヘキサアクリレート)
APC:Argentum‐Palladium‐Cupper(銀‐パラジウム‐銅合金)
BAHF:2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン
BFE:1,2-ビス(4-ホルミルフェニル)エタン
BGPF:9,9-ビス(4-グリシドキシフェニル)フルオレン
BHPF:9,9-ビス(4-ヒドロキシフェニル)フルオレン
Bis-A-AF:2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパン
Bk-A1103:“CHROMOFINE”(登録商標) BLACK A1103(大日精化工業社製;一次粒子径50~100nmのアゾ系黒色顔料)
Bk-S0084:“PALIOGEN”(登録商標) BLACK S0084(BASF社製;一次粒子径50~100nmのペリレン系黒色顔料)
Bk-S0100CF:“IRGAPHOR”(登録商標) BLACK S0100CF(BASF社製;一次粒子径40~80nmのベンゾフラノン系黒色顔料)
cyEpoTMS:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン
D.BYK-167:“DISPERBYK”(登録商標)-167(ビックケミー・ジャパン社製;アミン価が13mgKOH/g(固形分濃度:52質量%)の三級アミノ基を有するポリウレタン系分散剤)
DFA:N,N-ジメチルホルムアミドジメチルアセタール
DPCA-60:“KAYARAD”(登録商標) DPCA-60(日本化薬社製;オキシペンチレンカルボニル構造を分子中に6個有する、ε-カプロラクトン変性ジペンタエリスリトールヘキサアクリレート)
DPHA:“KAYARAD”(登録商標) 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)
EGME:エチレングリコールビス(2-メルカプトエチル)エーテル
GMA:メタクリル酸グリシジル
HABI-102:2,2’,5-トリス(2-クロロフェニル)-4-(3,4-ジメトキシフェニル)-4’,5’-ジフェニル-1,2’-ビイミダゾール(Tronly社製;ビイミダゾール系光重合開始剤)
HA:N,N’-ビス[5,5’-ヘキサフルオロプロパン-2,2-ジイル-ビス(2-ヒドロキシフェニル)]ビス(3-アミノ安息香酸アミド)
IC-379EG:“IRGACURE”(登録商標) 379EG(BASF社製;2-ジメチルアミノ-2-(4-メチルベンジル)-1-(4-モルホリノフェニル)-ブタン-1-オン;α-アミノケトン系光重合開始剤)
IC-819:“IRGACURE”(登録商標) 819(BASF社製;ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキシド;アシルホスフィンオキシド系光重合開始剤)
IDN-1:1,1-ビス[4-(2-アクリロキシエトキシ)フェニル]インダン
IGZO:酸化インジウムガリウム亜鉛
ITO:酸化インジウムスズ
MAA:メタクリル酸
MAP:3-アミノフェノール;メタアミノフェノール
MBA:3-メトキシ-n-ブチルアセテート
MeTMS:メチルトリメトキシシラン
MgAg:Magnesium‐Argentum(マグネシウム‐銀合金)
NA:5-ノルボルネン-2,3-ジカルボン酸無水物;ナジック酸無水物
NC-7300L:ナフタレン骨格、ベンゼン骨格、及び2つのエポキシ基を含む構造単位を有するエポキシ樹脂(日本化薬社製)
NMP:N-メチル-2-ピロリドン
ODPA:ビス(3,4-ジカルボキシフェニル)エーテル二無水物;オキシジフタル酸二無水物
OXE-02:“IRGACURE”(登録商標) OXE-02(BASF社製;1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]エタノン-1-(O-アセチル)オキシム;オキシムエステル系光重合開始剤)
P.B.15:6:C.I.ピグメントブルー15:6
P.B.60:C.I.ピグメントブルー60
P.O.43:C.I.ピグメントオレンジ43
P.R.179:C.I.ピグメントレッド179
P.R.254:C.I.ピグメントレッド254
P.V.23:C.I.ピグメントバイオレット23
P.V.37:C.I.ピグメントバイオレット37
P.Y.139:C.I.ピグメントイエロー139
P.Y.192:C.I.ピグメントイエロー192
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
PHA:フタル酸無水物
PhTMS:フェニルトリメトキシシラン
S-20000:“SOLSPERSE”(登録商標) 20000(Lubrizol社製;アミン価が32mgKOH/g(固形分濃度:100質量%)の三級アミノ基を有するポリオキシアルキレンエーテル系分散剤)
SiDA:1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン
STR:スチレン
TCDM:メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イル;ジメチロール-トリシクロデカンジメタアクリレート
THPHA:1,2,3,6-テトラヒドロフタル酸無水物
TMAH:水酸化テトラメチルアンモニウム
TMOS:テトラメトキシシラン
TMMP:トリメチロールプロパントリス(3-メルカプトプロピオネート)
TPK-1227:スルホン酸基を導入する表面処理がされたカーボンブラック(CABOT社製)
WR-301:“ADEKA ARKLS”(登録商標) WR-301(ADEKA社製;エポキシ基を有する芳香族化合物及び不飽和カルボン酸を開環付加反応させて得られる樹脂に、カルボン酸無水物を反応させて得られる多環側鎖含有樹脂、酸当量:560、二重結合当量:450)
三口フラスコに、BAHFを18.31g(0.05mol)、プロピレンオキシドを17.42g(0.3mol)、アセトンを100mL秤量して溶解させた。ここに、アセトン10mLに塩化3-ニトロベンゾイルを20.41g(0.11mol)溶かした溶液を滴下した。滴下終了後、-15℃で4時間反応させ、その後室温に戻した。析出した白色固体をろ取し、50℃で真空乾燥させた。得られた固体30gを、300mLのステンレスオートクレーブに入れ、2-メトキシエタノール250mLに分散させ、5%パラジウム-炭素を2g加えた。ここに水素を風船で導入して、室温で2時間反応させた。2時間後、風船がこれ以上しぼまないことを確認した。反応終了後、ろ過して触媒であるパラジウム化合物を除去し、減圧留去させて濃縮し、下記構造のヒドロキシ基含有ジアミン化合物(HA)を得た。
乾燥窒素気流下、三口フラスコに、BAHFを31.13g(0.085mol;全アミン及びその誘導体に由来する構造単位に対して77.3mol%)、SiDAを1.24g(0.0050mol;全アミン及びその誘導体に由来する構造単位に対して4.5mol%)、末端封止剤として、MAPを2.18g(0.020mol;全アミン及びその誘導体に由来する構造単位に対して18.2mol%)、NMPを150.00g秤量して溶解させた。ここに、NMP50.00gにODPAを31.02g(0.10mol;全カルボン酸及びその誘導体に由来する構造単位に対して100mol%)溶かした溶液を添加し、20℃で1時間攪拌し、次いで50℃で4時間攪拌した。その後、キシレン15gを添加し、水をキシレンとともに共沸しながら、150℃で5時間攪拌した。反応終了後、反応溶液を水3Lに投入し、析出した固体沈殿をろ過して得た。得られた固体を水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、ポリイミド(PI-1)を得た。得られたポリイミドのMwは27,000、酸当量は350であった。
表1-1に記載のモノマー種及びその比率にて、合成例1と同様に重合をして、ポリイミド(PI-2)~ポリイミド(PI-5)を得た。
乾燥窒素気流下、三口フラスコに、6FDAを44.42g(0.10mol;全カルボン酸及びその誘導体に由来する構造単位に対して100mol%)、NMPを150g秤量して溶解させた。ここに、NMP50gにBAHFを14.65g(0.040mol;全アミン及びその誘導体に由来する構造単位に対して32.0mol%)、HAを18.14g(0.030mol;全アミン及びその誘導体に由来する構造単位に対して24.0mol%)、SiDAを1.24g(0.0050mol;全アミン及びその誘導体に由来する構造単位に対して4.0mol%)溶かした溶液を添加し、20℃で1時間攪拌し、次いで50℃で2時間攪拌した。次に、末端封止剤として、NMP15gにMAPを5.46g(0.050mol;全アミン及びその誘導体に由来する構造単位に対して40.0mol%)溶かした溶液を添加し、50℃で2時間攪拌した。その後、NMP15gにDFAを23.83g(0.20mol)溶かした溶液を10分かけて滴下した。滴下終了後、50℃で3時間攪拌した。反応終了後、反応溶液を室温に冷却した後、反応溶液を水3Lに投入し、析出した固体沈殿をろ過して得た。得られた固体を水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、ポリイミド前駆体(PIP-1)を得た。得られたポリイミド前駆体のMwは20,000、酸当量は450であった。
表1-1に記載のモノマー種及びその比率にて、合成例6と同様に重合をして、ポリイミド前駆体(PIP-2)を得た。
トルエンを満たしたディーンスターク水分離器及び冷却管を付けた500mL丸底フラスコに、BAHFを34.79g(0.095mol;全アミン及びその誘導体に由来する構造単位に対して95.0mol%)、SiDAを1.24g(0.0050mol;全アミン及びその誘導体に由来する構造単位に対して5.0mol%)、NMPを75.00g秤量して、溶解させた。ここに、NMP25.00gに、BFEを19.06g(0.080mol;全カルボン酸及びその誘導体に由来する構造単位に対し66.7mol%)、末端封止剤として、NAを6.57g(0.040mol;全カルボン酸及びその誘導体に由来する構造単位に対し33.3mol%)溶かした溶液を添加し、20℃で1時間攪拌し、次いで50℃で1時間攪拌した。その後、窒素雰囲気下、200℃以上で10時間加熱攪拌し、脱水反応を行った。反応終了後、反応溶液を水3Lに投入し、析出した固体沈殿をろ過して得た。得られた固体を水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、ポリベンゾオキサゾール(PBO-1)を得た。得られたポリベンゾオキサゾールのMwは25,000、酸当量は330であった。
トルエンを満たしたディーンスターク水分離器及び冷却管を付けた500mL丸底フラスコに、BAHFを34.79g(0.095mol;全アミン及びその誘導体に由来する構造単位に対して95.0mol%)、SiDAを1.24g(0.0050mol;全アミン及びその誘導体に由来する構造単位に対して5.0mol%)、NMPを70.00g秤量して、溶解させた。ここに、NMP20.00gに、BFEを19.06g(0.080mol;全カルボン酸及びその誘導体に由来する構造単位に対し66.7mol%)溶かした溶液を添加し、20℃で1時間攪拌し、次いで50℃で2時間攪拌した。次に、末端封止剤として、NMP10gにNAを6.57g(0.040mol;全カルボン酸及びその誘導体に由来する構造単位に対し33.3mol%)溶かした溶液を添加し、50℃で2時間攪拌した。その後、窒素雰囲気下、100℃で2時間攪拌した。反応終了後、反応溶液を水3Lに投入し、析出した固体沈殿をろ過して得た。得られた固体を水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、ポリベンゾオキサゾール前駆体(PBOP-1)を得た。得られたポリベンゾオキサゾール前駆体のMwは20,000、酸当量は330であった。
三口フラスコに、MeTMSを20.43g(30mol%)、PhTMSを49.57g(50mol%)、cyEpoTMSを12.32g(10mol%)、TMOSを7.61g(10mol%)、PGMEAを83.39g仕込んだ。フラスコ内に空気を0.05L/分で流し、混合溶液を攪拌しながらオイルバスで40℃に加熱した。混合溶液をさらに攪拌しながら、水28.83gにリン酸0.270gを溶かしたリン酸水溶液を10分かけて滴下した。滴下終了後、40℃で30分間攪拌して、シラン化合物を加水分解させた。加水分解終了後、バス温を70℃にして1時間攪拌した後、続いてバス温を115℃まで昇温した。昇温開始後、約1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌した(内温は100~110℃)。2時間加熱攪拌して得られた樹脂溶液を氷浴にて冷却し、ポリシロキサン溶液(PS-1)を得た。得られたポリシロキサンのMwは4,500であった。
三口フラスコにMeTMSを27.24g(40mol%)、PhTMSを49.57g(50mol%)、cyEpoTMSを12.32g(10mol%)、PGMEAを83.91g仕込んだ。フラスコ内に空気を0.05L/分で流し、混合溶液を攪拌しながらオイルバスで40℃に加熱した。混合溶液をさらに攪拌しながら、水27.93gにリン酸0.267gを溶かしたリン酸水溶液を10分かけて添加した。添加終了後、40℃で30分間攪拌して、シラン化合物を加水分解させた。加水分解終了後、バス温を70℃にして1時間攪拌した後、続いてバス温を115℃まで昇温した。昇温開始後、約1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌した(内温は100~110℃)。2時間加熱攪拌して得られた樹脂溶液を氷浴にて冷却し、ポリシロキサン溶液(PS-2)を得た。得られたポリシロキサンのMwは4,000であった。
三口フラスコに、BHPFを35.04g(0.10mol)、MBAを40.31g秤量して溶解させた。ここに、MBA30.00gにODPAを27.92g(0.090mol)、末端封止剤として、PHAを2.96g(0.020mol)溶かした溶液を添加し、20℃で1時間攪拌した。その後、窒素雰囲気下、150℃で5時間攪拌した。反応終了後、得られた溶液に、MBA10.00gにGMAを14.22g(0.10mol)、ジベンジルアミンを0.135g(0.0010mol)、4-メトキシフェノールを0.037g(0.0003mol)溶かした溶液を添加し、90℃で4時間攪拌して、多環側鎖含有樹脂溶液(CR-1)を得た。得られた多環側鎖含有樹脂のMwは4,000、カルボン酸当量は810g/molであり、二重結合当量は810g/molであった。
三口フラスコに、BGPFを46.25g(0.10mol)、MBAを54.53g秤量して溶解させた。ここに、MBA10.00gにMAAを17.22g(0.20mol)、ジベンジルアミンを0.135g(0.0010mol)、4-メトキシフェノールを0.037g(0.0003mol)溶かした溶液を添加し、90℃で4時間攪拌した。その後、MBA30.00gにODPAを27.92g(0.090mol)、末端封止剤として、PHAを2.96g(0.020mol)溶かした溶液を添加し、20℃で1時間攪拌した。その後、窒素雰囲気下、150℃で5時間攪拌して、多環側鎖含有樹脂溶液(CR-2)を得た。得られた多環側鎖含有樹脂のMwは4,700、カルボン酸当量は470g/molであり、二重結合当量は470g/molであった。
三口フラスコに、NC-7300L(エポキシ当量:210g/mol)を42.00g、MBAを47.91g秤量して溶解させた。ここに、MBA10.00gにMAAを17.22g(0.20mol)、ジベンジルアミンを0.270g(0.0020mol)、4-メトキシフェノールを0.074g(0.0006mol)溶かした溶液を添加し、90℃で4時間攪拌した。その後、MBA30.00gにTHPHAを24.34g(0.160mol)溶かした溶液を添加し、20℃で1時間攪拌した。その後、窒素雰囲気下、150℃で5時間攪拌して、酸変性エポキシ樹脂溶液(AE-1)を得た。得られた酸変性エポキシ樹脂のMwは5,000、酸当量は510g/molであり、二重結合当量は410g/molであった。
三口フラスコに、2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを29.29g仕込んだ。次に、MAAを21.52g(50mol%)、TCDMを22.03g(20mol%)、STRを15.62g(30mol%)仕込み、室温でしばらく攪拌して、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間攪拌した。次に、得られた溶液に、PGMEAを59.47gにGMAを14.22g(20mol%)、ジベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)溶かした溶液を添加し、90℃で4時間攪拌して、アクリル樹脂溶液(AC-1)を得た。得られたアクリル樹脂のMwは15,000、カルボン酸当量は490g/molであり、二重結合当量は740g/molであった。
黒色顔料として、ベンゾフラノン系黒色顔料であるBk-S0100CF(表面未処理品;顔料表面のpH4.5)150gを、2,850gの脱イオン水を入れたガラス容器に投入してディゾルバーで攪拌し、水性顔料懸濁液を得た。これをチューブポンプで吸い上げ、0.4mmφジルコニアビーズ(“トレセラム”(登録商標);東レ社製)が充填された横型ビーズミル内に送液して2パス分散処理を行った後、元のガラス容器内に全量を吐出させ、再びディゾルバーで攪拌した。pHメーターを、その先端電極部が、ガラス容器内で攪拌中の水性顔料懸濁液の液面から3~5cmの深さで漬かるようにセットし、得られた水性顔料懸濁液のpHを測定したところ、pH4.5(液温25℃)を示した。その後、攪拌しながら水性顔料懸濁液の液温を60℃に上げ、30分後に一旦攪拌を止めて、2分後ガラス容器の底に沈降堆積物が無いことを確認し、攪拌を再開した。
分散剤として、S-20000を34.5g、溶剤として、MBAを782.0g秤量して混合し、10分間攪拌して拡散した後、着色剤として、Bk-S0100CFを103.5g秤量して混合して30分間攪拌し、0.40mmφのジルコニアビーズが充填された横型ビーズミルを用いて、数平均粒子径が100nmとなるように湿式メディア分散処理を行い、固形分濃度15質量%、着色剤/分散剤=75/25(質量比)の顔料分散液(Bk-1)を得た。得られた顔料分散液中の顔料の数平均粒子径は100nmであった。
樹脂として、合成例1で得られた、ポリイミド(PI-1)の30質量%のMBA溶液を92.0g、分散剤として、S-20000を27.6g、溶剤として、MBAを717.6g秤量して混合し、10分間攪拌して拡散した後、着色剤として、Bk-S0100CFを82.8g秤量して混合して30分間攪拌し、0.40mmφのジルコニアビーズが充填された横型ビーズミルを用いて、数平均粒子径が100nmとなるように湿式メディア分散処理を行い、固形分濃度15質量%、着色剤/樹脂/分散剤=60/20/20(質量比)の顔料分散液(Bk-2)を得た。得られた顔料分散液中の顔料の数平均粒子径は100nmであった。
表2-1に記載の着色剤、(A1)第1の樹脂及び(E)分散剤の種類並びにこれらの比率にて、調製例2と同様に顔料分散をして、顔料分散液(Bk-3)~顔料分散液(Bk-18)を得た。
Bk-S0100CF:340nm
Bk-S0084:350nm
P.R.179、P.Y.192及びP.B.60の混合物:390nm
GPC分析装置(HLC-8220;東ソー社製)を用い、流動層としてテトラヒドロフラン又はNMPを用いて、「JIS K7252-3(2008)」に基づき、常温付近での方法により、ポリスチレン換算の重量平均分子量を測定して求めた。
電位差自動滴定装置(AT-510;京都電子工業社製)を用い、滴定試薬として0.1mol/Lの水酸化ナトリウム/エタノール溶液、滴定溶剤としてキシレン/N,N-ジメチルホルムアミド=1/1(質量比)を用いて、「JIS K2501(2003)」に基づき、電位差滴定法により、酸価(単位はmgKOH/g)を測定して求めた。測定した酸価の値から、酸当量(単位はg/mol)を算出した。
電位差自動滴定装置(AT-510;京都電子工業社製)を用い、ヨウ素供給源として一塩化ヨウ素溶液(三塩化ヨウ素=7.9g、ヨウ素=8.9g、酢酸=1,000mLの混合溶液)、未反応ヨウ素の捕捉水溶液として100g/Lのヨウ化カリウム水溶液、滴定試薬として0.1mol/Lのチオ硫酸ナトリウム水溶液を用いて、JIS K0070:1992「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価、及び不けん化物の試験方法」の「第6項よう素価」に記載の方法に基づき、ウィイス法により、樹脂のヨウ素価を測定した。測定したヨウ素価(単位はgI/100g)の値から、二重結合当量(単位はg/mol)を算出した。
29Si-NMRの測定を行い、オルガノシランに由来するSi全体の積分値に対する、特定のオルガノシラン単位に由来するSiの積分値の割合を算出して、それらの含有比率を計算した。試料(液体)は、直径10mm の“テフロン”(登録商標)製NMRサンプル管に注入して測定に用いた。29Si-NMR測定条件を以下に示す。
装置:核磁気共鳴装置(JNM-GX270;日本電子社製)
測定法:ゲーテッドデカップリング法
測定核周波数:53.6693MHz(29Si核)
スペクトル幅:20000Hz
パルス幅:12μs(45°パルス)
パルス繰り返し時間:30.0秒
溶媒:アセトン-d6
基準物質:テトラメチルシラン
測定温度:23℃
試料回転数:0.0Hz。
ゼータ電位・粒子径・分子量測定装置(ゼータサイザーナノZS;シスメックス社製)を用い、希釈溶媒としてPGMEAを用いて、顔料分散液を1.0×10-5~40体積%の濃度に希釈し、希釈溶媒の屈折率をPGMEAの屈折率に、測定対象の屈折率を1.6に設定して、波長633nmのレーザー光を照射して顔料分散液中の顔料の数平均粒子径を測定した。
ガラス上に、ITOをスパッタにより100nm成膜したガラス基板(ジオマテック社製;以下、「ITO基板」)は、卓上型光表面処理装置(PL16-110;セン特殊光源社製)を用いて、100秒間UV-O3洗浄処理をして使用した。Siウェハ(エレクトロニクス エンド マテリアルズ コーポレーション社製)は、ホットプレート(HP-1SA;アズワン社製)を用いて、130℃で2分間加熱して脱水ベーク処理をして使用した。
表面粗さ・輪郭形状測定機(SURFCOM1400D;東京精密社製)を用いて、測定倍率を10,000倍、測定長さを1.0mm、測定速度を0.30mm/sとして、プリベーク後、現像後及び熱硬化後の膜厚を測定した。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像し、ネガ型感光性樹脂組成物の現像後膜を作製した。
A+:感度が1~30mJ/cm2
A:感度が31~45mJ/cm2
B:感度が46~60mJ/cm2
C:感度が61~90mJ/cm2
D:感度が91~150mJ/cm2
E:感度が151~500mJ/cm2。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像した後、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム社製)を用いて、ネガ型感光性樹脂組成物の現像後膜を作製した。
A+:開口部における残渣無し
A:開口部における残渣の存在面積が1~5%
B:開口部における残渣の存在面積が6~10%
C:開口部における残渣の存在面積が11~30%
D:開口部における残渣の存在面積が31~50%
E:開口部における残渣の存在面積が51~100%。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像し、ネガ型感光性樹脂組成物の現像後膜を作製した。
A+:断面のテーパー角が1~30°
A:断面のテーパー角が31~45°
B:断面のテーパー角が46~60°
C:断面のテーパー角が61~70°
D:断面のテーパー角が71~80°
E:断面のテーパー角が81~179°。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像した後、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム社製)を用いて、ネガ型感光性樹脂組成物の硬化膜を作製した。
A+:断面のテーパー角が1~30°
A:断面のテーパー角が31~45°
B:断面のテーパー角が46~60°
C:断面のテーパー角が61~70°
D:断面のテーパー角が71~80°
E:断面のテーパー角が81~179°。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像し、ネガ型感光性樹脂組成物の現像後膜を作製した。
A+:熱硬化前後のパターン開口寸法幅の変化が0~0.20μm
A:熱硬化前後のパターン開口寸法幅の変化が0.21~0.40μm
B:熱硬化前後のパターン開口寸法幅の変化が0.41~0.60μm
C:熱硬化前後のパターン開口寸法幅の変化が0.61~1.00μm
D:熱硬化前後のパターン開口寸法幅の変化が1.01~2.00μm
E:熱硬化前後のパターン開口寸法幅の変化が2.01μm以上。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像した後、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム社製)を用いて、ネガ型感光性樹脂組成物の硬化膜を作製した。
A+:高温重量残存率差が0~5.0%
A:高温重量残存率差が5.1~15.0%
B:高温重量残存率差が15.1~25.0%
C:高温重量残存率差が25.1~35.0%
D:高温重量残存率差が35.1~45.0%
E:高温重量残存率差が45.1~100%。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像した後、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム社製)を用いて、ネガ型感光性樹脂組成物の硬化膜を作製した。
OD値=log10(I0/I)。
下記、実施例1記載の方法で、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、感度測定用のグレースケールマスク(MDRM MODEL 4000-5-FS;Opto-Line International社製)を介して、超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光した後、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像した後、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム社製)を用いて、ネガ型感光性樹脂組成物の硬化膜を作製した。高抵抗抵抗率計(“ハイレスタ”UP;三菱化学社製)を用いて、作製した硬化膜の表面抵抗率(Ω/□)を測定した。
(有機ELディスプレイの作製方法)
図4に、使用した基板の概略図を示す。まず、38×46mmの無アルカリガラス基板47に、スパッタ法により、ITO透明導電膜10nmを基板全面に形成し、第1電極48としてエッチングし、透明電極を形成した。また、第2電極を取り出すため補助電極49も同時に形成した(図4(工程1))。得られた基板を“セミコクリーン”(登録商標)56(フルウチ化学社製)で10分間超音波洗浄し、超純水で洗浄した。次に、この基板上に、ネガ型感光性樹脂組成物を実施例1に記載された方法で塗布及びプリベークし、所定のパターンを有するフォトマスクを介してパターンニング露光、現像及びリンスした後、加熱し熱硬化させた。以上の方法で、幅70μm及び長さ260μmの開口部が、幅方向にピッチ155μm及び長さ方向にピッチ465μmで配置され、それぞれの開口部が第1電極を露出せしめる形状の絶縁層50を、基板有効エリアに限定して形成した(図4(工程2))。なお、この開口部が、最終的に有機ELディスプレイの発光画素となる。また、基板有効エリアは、16mm四方であり、絶縁層50の厚さは、約1.0μmで形成した。
上述した方法で作製した有機ELディスプレイを、10mA/cm2で直流駆動にて発光させ、非発光領域や輝度ムラなどの発光不良がないかを観察した。作製した有機ELディスプレイを、耐久性試験として、80℃で500時間保持した。耐久性試験後、有機ELディスプレイを、10mA/cm2で直流駆動にて発光させ、発光領域や輝度ムラなどの発光特性に変化がないかを観察した。下記のように判定し、耐久試験前の発光領域面積を100%とした場合の、耐久試験後の発光領域面積が80%以上となる、A+、A、及びBを合格とし、発光領域面積が90%以上となる、A+及びAを発光特性良好とし、発光領域面積が95%以上となる、A+を発光特性優秀とした。
A+:耐久試験後の発光領域面積が95~100%
A:耐久試験後の発光領域面積が90~94%
B:耐久試験後の発光領域面積が80~89%
C:耐久試験後の発光領域面積が70~79%
D:耐久試験後の発光領域面積が50~69%
E:耐久試験後の発光領域面積が0~49%。
黄色灯下、OXL-21を0.152g秤量し、MBAを7.274g、PGMEAを5.100g添加し、攪拌して溶解させた。次に、合成例1で得られたポリイミド(PI-1)の30質量%のMBA溶液を6.566g、DPHAの50質量%のMBA溶液を0.606g、DPCA-60の50質量%のMBA溶液を1.515g添加して攪拌し、均一溶液として調合液を得た。次に、調製例1で得られた顔料分散液(Bk-1)を7.323g秤量し、ここに、上述した方法によって得られた調合液を17.677g添加して攪拌し、均一溶液とした。その後、得られた溶液を0.45μmφのフィルターでろ過し、組成物1を調製した。
実施例1と同様に、組成物2~91を表3-1~表14-1に記載の組成にて調製した。得られた各組成物を用いて、実施例1と同様に、基板上に組成物を成膜し、感光特性及び硬化膜の特性の評価を行った。これらの評価結果をまとめて、表3-2~表14-2に示す。なお、比較しやすくするために、表4-1~表5-1、表7-1~表13-1、表4-2~表5-2、及び表7-2~表13-2のそれぞれに、実施例7の組成及び評価結果を記載した。
(偏光層を有しない有機ELディスプレイの製造方法)
作製する有機ELディスプレイの概略を図5に示す。まず、38×46mmの無アルカリガラス基板53上に、電子ビーム蒸着法により、クロムと金の積層膜を成膜し、エッチングによりソース電極54とドレイン電極55を形成した。次に、APC(銀/パラジウム/銅=98.07/0.87/1.06(質量比))をスパッタにより100nm成膜し、エッチングによりパターン加工してAPC層を形成し、さらに、APC層の上層にITOをスパッタにより10nm成膜し、エッチングにより、第1電極として反射電極56を形成した。電極表面を酸素プラズマで洗浄した後、スパッタ法により、アモルファスIGZOを成膜し、エッチングによりソース・ドレイン電極間に酸化物半導体層57を形成した。次に、スピンコート法により、ポジ型感光性ポリシロキサン系材料(SP-P2301;東レ社製)を成膜し、フォトリソグラフィーにより、ビアホール58と画素領域59を開口した後、熱硬化させてゲート絶縁層60を形成した。その後、電子ビーム蒸着法により、金を成膜し、エッチングによりゲート電極61を形成することで、酸化物TFTアレイとした。
上述した方法で作製した有機ELディスプレイを、10mA/cm2で直流駆動にて発光させ、外光を画素分割層部に照射した場合の輝度(Y’)、外光を照射しない場合の輝度(Y0)を測定した。外光反射低減の指標として、コントラストを下記式により算出した。
コントラスト=Y0/Y’。
A+:コントラストが0.95~1.00
A:コントラストが0.90~0.94
B:コントラストが0.80~0.89
C:コントラストが0.70~0.79
D:コントラストが0.50~0.69
E:コントラストが0.01~0.49。
(ハーフトーン特性の評価)
上述した、実施例1記載の方法で、ITO基板上に組成物7のプリベーク膜を5μmの膜厚で成膜し、両面アライメント片面露光装置(マスクアライナー PEM-6M;ユニオン光学社製)を用いて、ハーフトーン特性評価用のハーフトーンフォトマスクを介して、透光部の露光量が、プリベーク後の膜厚が5μmの場合の感度の露光量となるように超高圧水銀灯のi線(波長365nm)、h線(波長405nm)、及びg線(波長436nm)でパターニング露光し、フォトリソ用小型現像装置(AD-2000;滝沢産業社製)を用いて現像した後、高温イナートガスオーブン(INH-9CD-S;光洋サーモシステム社製)を用いて、組成物7の硬化膜を作製した。
最大段差膜厚=(TFT)-(THT/min)。
A+:最大段差膜厚が2.5μm以上
A:最大段差膜厚が2.0μm以上かつ2.5μm未満
B:最大段差膜厚が1.5μm以上かつ2.0μm未満
C:最大段差膜厚が1.0μm以上かつ1.5μm未満
D:最大段差膜厚が0.5μm以上かつ1.0μm未満
E:最大段差膜厚が0.1μm以上かつ0.5μm未満
F:最大段差膜厚が0.1μm未満又は現像後に残膜せず測定不能。
2,16 TFT
3,17 TFT平坦化用の硬化膜
4 反射電極
5a,21a プリベーク膜
5b,21b,28 硬化パターン
6,22 マスク
7,23 活性化学線
8 EL発光層
9,18,64 透明電極
10,29 平坦化用の硬化膜
11 カバーガラス
13 BLU
14 BLUを有するガラス基板
19 平坦化膜
20,30 配向膜
24 BCSを有するガラス基板
25 BLU及びBCSを有するガラス基板
27 カラーフィルタ
31 カラーフィルタ基板
32 BLU、BCS及びBMを有するガラス基板
33 液晶層
34 厚膜部
35a,35b,35c 薄膜部
36a,36b,36c,36d,36e 硬化パターンの断面における傾斜辺
37 下地の基板の水平辺
47,53,66 無アルカリガラス基板
48 第1電極
49 補助電極
50 絶縁層
51 有機EL層
52 第2電極
54 ソース電極
55 ドレイン電極
56 反射電極
57 酸化物半導体層
58 ビアホール
59 画素領域
60 ゲート絶縁層
61 ゲート電極
62 TFT保護層/画素分割層
63 有機EL発光層
65 封止膜
Claims (24)
- (A)アルカリ可溶性樹脂、(C1)光重合開始剤、及び(Da)黒色剤を含有するネガ型感光性樹脂組成物であって、
前記(A)アルカリ可溶性樹脂が、(A1-1)ポリイミド、(A1-2)ポリイミド前駆体、(A1-3)ポリベンゾオキサゾール、及び(A1-4)ポリベンゾオキサゾール前駆体からなる群より選ばれる一種類以上を含む(A1)第1の樹脂を含有し、
前記(A1-1)ポリイミド、前記(A1-2)ポリイミド前駆体、前記(A1-3)ポリベンゾオキサゾール、及び前記(A1-4)ポリベンゾオキサゾール前駆体からなる群より選ばれる一種類以上が、フッ素原子を有する構造単位を、全構造単位の10~100mol%で有し、
前記(C1)光重合開始剤が、(C1-1)オキシムエステル系光重合開始剤を含有し、
前記(C1-1)オキシムエステル系光重合開始剤が、(I)、(II)、及び(III)からなる群より選ばれる一種類以上の構造を有する、ネガ型感光性樹脂組成物。
(I)ナフタレンカルボニル構造、トリメチルベンゾイル構造、チオフェンカルボニル構造、及びフランカルボニル構造からなる群より選ばれる一種類以上の構造
(II)ニトロ基、カルバゾール構造、及び一般式(11)で表される基
(III)ニトロ基、並びに、フルオレン構造、ジベンゾフラン構造、ジベンゾチオフェン構造、ナフタレン構造、ジフェニルメタン構造、ジフェニルアミン構造、ジフェニルエーテル構造、及びジフェニルスルフィド構造からなる群より選ばれる一種類以上の構造
- 前記(Da)黒色剤が、(D1a)黒色顔料を含有し、
前記(D1a)黒色顔料が、(D1a-1)黒色有機顔料として、(D1a-1a)ベンゾフラノン系黒色顔料、(D1a-1b)ペリレン系黒色顔料、及び(D1a-1c)アゾ系黒色顔料からなる群より選ばれる一種類以上を含有する、
請求項1に記載のネガ型感光性樹脂組成物。 - 前記(D1a-1)黒色有機顔料が、(D1a-1a)ベンゾフラノン系黒色顔料を含有する、
請求項2に記載のネガ型感光性樹脂組成物。 - 前記(Da)黒色剤が、(D1a)黒色顔料を含有し、
前記(D1a)黒色顔料が、(D1a-3)二色以上の着色顔料混合物として、(D1a-3a)青色顔料、赤色顔料、及び黄色顔料を含む着色顔料混合物、(D1a-3b)紫色顔料及び黄色顔料を含む着色顔料混合物、(D1a-3c)青色顔料、赤色顔料、及び橙色顔料を含む着色顔料混合物、又は(D1a-3d)青色顔料、紫色顔料、及び橙色顔料を含む着色顔料混合物であって、
前記青色顔料が、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:6、及びC.I.ピグメントブルー60からなる群より選ばれる一種類以上であって、
前記赤色顔料が、C.I.ピグメントレッド123、C.I.ピグメントレッド149、C.I.ピグメントレッド177、C.I.ピグメントレッド179、及びC.I.ピグメントレッド190からなる群より選ばれる一種類以上であって、
前記黄色顔料が、C.I.ピグメントイエロー120、C.I.ピグメントイエロー151、C.I.ピグメントイエロー175、C.I.ピグメントイエロー180、C.I.ピグメントイエロー181、C.I.ピグメントイエロー192、及びC.I.ピグメントイエロー194からなる群より選ばれる一種類以上であって、
前記紫色顔料が、C.I.ピグメントバイオレット19、C.I.ピグメントバイオレット29、及びC.I.ピグメントバイオレット37からなる群より選ばれる一種類以上であって、
前記橙色顔料が、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ64、及びC.I.ピグメントオレンジ72からなる群より選ばれる一種類以上である、
請求項1~3のいずれか1項に記載のネガ型感光性樹脂組成物。 - さらに、(D1b-1)黒色以外の有機顔料として、青色顔料、赤色顔料、黄色顔料、紫色顔料、橙色顔料、及び緑色顔料からなる群より選ばれる一種類以上を含有し、
前記青色顔料が、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:6、及びC.I.ピグメントブルー60からなる群より選ばれる一種類以上であって、
前記赤色顔料が、C.I.ピグメントレッド123、C.I.ピグメントレッド149、C.I.ピグメントレッド177、C.I.ピグメントレッド179、及びC.I.ピグメントレッド190からなる群より選ばれる一種類以上であって、
前記黄色顔料が、C.I.ピグメントイエロー120、C.I.ピグメントイエロー151、C.I.ピグメントイエロー175、C.I.ピグメントイエロー180、C.I.ピグメントイエロー181、C.I.ピグメントイエロー192、及びC.I.ピグメントイエロー194からなる群より選ばれる一種類以上であって、
前記紫色顔料が、C.I.ピグメントバイオレット19、C.I.ピグメントバイオレット29、及びC.I.ピグメントバイオレット37からなる群より選ばれる一種類以上であって、
前記橙色顔料が、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ64、及びC.I.ピグメントオレンジ72からなる群より選ばれる一種類以上である、
請求項1~3のいずれか1項に記載のネガ型感光性樹脂組成物。 - 前記(C1-1)オキシムエステル系光重合開始剤が、ハロゲンで置換された基を有する、
請求項1~5のいずれか1項に記載のネガ型感光性樹脂組成物。 - 前記(Da)黒色剤の極大透過波長が、330~410nmであって、
前記(C1-1)オキシムエステル系光重合開始剤の極大吸収波長が、330~410nmであって、
前記(C1-1)オキシムエステル系光重合開始剤の0.01g/L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液における、波長360nmの吸光度が0.20以上である、
請求項1~6のいずれか1項に記載のネガ型感光性樹脂組成物。 - 前記(C1-1)オキシムエステル系光重合開始剤の極大吸収波長が、340~400nmであって、
前記(C1-1)オキシムエステル系光重合開始剤の0.01g/L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液における、波長360nmの吸光度が0.25以上である、
請求項7に記載のネガ型感光性樹脂組成物。 - 前記(A)アルカリ可溶性樹脂が、さらに、(A2-1)ポリシロキサン、(A2-2)多環側鎖含有樹脂、(A2-3)酸変性エポキシ樹脂、及び(A2-4)アクリル樹脂からなる群より選ばれる一種類以上を含む(A2)第2の樹脂を含有する、
請求項1~8のいずれか1項に記載のネガ型感光性樹脂組成物。 - 前記(C1-1)オキシムエステル系光重合開始剤が、一般式(12)で表される化合物、一般式(13)で表される化合物、及び一般式(14)で表される化合物からなる群より選ばれる一種類以上を含有する、
請求項1~9のいずれか1項に記載のネガ型感光性樹脂組成物。
- 前記(C1-1)オキシムエステル系光重合開始剤が、前記一般式(13)で表される化合物を含有する、
請求項10に記載のネガ型感光性樹脂組成物。 - 前記(C1-1)オキシムエステル系光重合開始剤が、前記一般式(12)で表される化合物及び/又は前記一般式(13)で表される化合物を含有し、
前記一般式(12)、及び前記一般式(13)において、Y1及びY2が、炭素又は窒素であって、R46及びR47が、少なくとも炭素数1~10のアルケニル基を含み、R49及びR50が、少なくとも炭素数1~10のアルケニル基を含む、
請求項10に記載のネガ型感光性樹脂組成物。 - さらに、(F)多官能チオール化合物として、一般式(83)で表される化合物、一般式(84)で表される化合物、及び一般式(85)で表される化合物からなる群より選ばれる一種類以上を含有する、
請求項1~12のいずれか1項に記載のネガ型感光性樹脂組成物。
- さらに、(B)ラジカル重合性化合物として、(B4)脂環式基含有ラジカル重合性化合物を含有し、
前記(B4)脂環式基含有ラジカル重合性化合物が、縮合多環脂環式骨格を含有する、
請求項13に記載のネガ型感光性樹脂組成物。 - さらに、前記(C1)光重合開始剤が、(C1-2)α-アミノケトン系光重合開始剤、(C1-3)アシルホスフィンオキシド系光重合開始剤及び(C1-4)ビイミダゾール系光重合開始剤からなる群より選ばれる一種類以上を含有し、
前記(C1)光重合開始剤に占める、前記(C1-1)オキシムエステル系光重合開始剤の含有比率が、55~95質量%である、
請求項1~14のいずれか1項に記載のネガ型感光性樹脂組成物。 - さらに、(B)ラジカル重合性化合物として、(B1)フルオレン骨格含有ラジカル重合性化合物及び/又は(B2)インダン骨格含有ラジカル重合性化合物からなる群より選ばれる一種類以上を含有する、
請求項1~15のいずれか1項に記載のネガ型感光性樹脂組成物。 - さらに、(B)ラジカル重合性化合物として、(B3)柔軟鎖含有脂肪族ラジカル重合性化合物を含有し、
前記(B3)柔軟鎖含有脂肪族ラジカル重合性化合物が、少なくとも1つのラクトン変性鎖及び/又は少なくとも1つのラクタム変性鎖を有する、
請求項1~16のいずれか1項に記載のネガ型感光性樹脂組成物。 - 有機ELディスプレイにおける画素分割層の、段差形状を一括形成するために用いられる、
請求項1~17のいずれか1項に記載のネガ型感光性樹脂組成物。 - 請求項1~18のいずれか1項に記載のネガ型感光性樹脂組成物が硬化されてなる、
硬化膜。 - 請求項19に記載の硬化膜の膜厚1μm当たりの光学濃度が、0.3~5.0であって、
前記硬化膜を画素分割層、電極絶縁層、配線絶縁層、層間絶縁層、TFT平坦化層、電極平坦化層、配線平坦化層、TFT保護層、電極保護層、配線保護層及びゲート絶縁層からなる群より選ばれる一種類以上として備える、
有機ELディスプレイ。 - 前記硬化膜が、段差形状を有する硬化パターンを含む、
請求項20に記載の有機ELディスプレイ。 - 前記段差形状を有する硬化パターンにおける、厚膜部の膜厚を(TFT)μm、及び薄膜部の膜厚を(THT)μmとするとき、前記(TFT)と前記(THT)との膜厚差(ΔTFT-HT)μmが、1.5~10.0μmである、
請求項21に記載の有機ELディスプレイ。 - 有機ELディスプレイの製造方法であって、
基板上に、請求項1~18のいずれか1項に記載のネガ型感光性樹脂組成物の塗膜を成膜する工程、
前記ネガ型感光性樹脂組成物の塗膜にフォトマスクを介して活性化学線を照射する工程、
アルカリ溶液を用いて現像し、前記ネガ型感光性樹脂組成物のパターンを形成する工程、及び
前記パターンを加熱して、前記ネガ型感光性樹脂組成物の硬化パターンを得る工程、を含む、有機ELディスプレイの製造方法。 - 前記フォトマスクが、透光部及び遮光部を含むパターンを有するフォトマスクであって、前記透光部と前記遮光部の間に、透過率が透光部の値より低く、かつ透過率が遮光部の値より高い、半透光部を有するハーフトーンフォトマスクである、
請求項23に記載の有機ELディスプレイの製造方法。
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CN111522200A (zh) * | 2020-04-07 | 2020-08-11 | 中国科学院化学研究所 | 一种用于12英寸硅晶圆的负型pspi树脂及其制备方法与应用 |
WO2021006315A1 (ja) * | 2019-07-10 | 2021-01-14 | 東レ株式会社 | ネガ型感光性樹脂組成物、硬化膜、有機elディスプレイ及び硬化膜の製造方法 |
WO2021035907A1 (zh) * | 2019-08-26 | 2021-03-04 | 武汉华星光电半导体显示技术有限公司 | 含氟基聚酰亚胺及其制造方法、柔性衬底及显示装置 |
WO2021177654A1 (ko) * | 2020-03-03 | 2021-09-10 | 주식회사 테크늄 | 신규한 옥심에스테르 카바졸 유도체 화합물 |
WO2021177653A1 (ko) * | 2020-03-03 | 2021-09-10 | 주식회사 테크늄 | 신규한 옥심에스테르 카바졸 유도체 화합물 |
WO2023054116A1 (ja) | 2021-09-29 | 2023-04-06 | 東レ株式会社 | 感光性組成物、硬化物、表示装置、電子部品、及び硬化物の製造方法 |
WO2023195319A1 (ja) * | 2022-04-04 | 2023-10-12 | 東レ株式会社 | ポジ型感光性顔料組成物およびその硬化物を含む硬化膜ならびに有機el表示装置 |
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TWI829929B (zh) * | 2020-05-14 | 2024-01-21 | 奇美實業股份有限公司 | 黑色感光性樹脂組成物、黑色圖案、彩色濾光片以及液晶顯示裝置 |
TW202208470A (zh) * | 2020-07-22 | 2022-03-01 | 日商富士軟片股份有限公司 | 樹脂組成物、膜、濾光器、固體攝像元件、圖像顯示裝置、樹脂及化合物 |
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