CN109073799A - Composition, cured film, colour filter, photomask, solid-state imager and image display device - Google Patents

Composition, cured film, colour filter, photomask, solid-state imager and image display device Download PDF

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Publication number
CN109073799A
CN109073799A CN201780020774.2A CN201780020774A CN109073799A CN 109073799 A CN109073799 A CN 109073799A CN 201780020774 A CN201780020774 A CN 201780020774A CN 109073799 A CN109073799 A CN 109073799A
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group
composition
particle
compound
nitrogen titanium
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CN109073799B (en
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久保田诚
浜田大辅
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Fujifilm Corp
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
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    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
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Abstract

The present invention provides a kind of composition for the cured film that anti-corrosive properties that can make electrode are excellent and patternability is excellent.Also, provide a kind of cured film, colour filter, photomask, solid-state imager and image display device.Composition contains the nitrogen titanium particle comprising chlorine atom, and the content of the above-mentioned chlorine atom in above-mentioned nitrogen titanium particle is 0.001~0.3 mass %.

Description

Composition, cured film, colour filter, photomask, solid-state imager and image are shown Device
Technical field
The present invention relates to a kind of composition, cured film, colour filter, photomask, solid-state imager and image display devices.
Background technique
Solid-state imaging apparatus have photographic lens, be disposed in the photographic lens behind CCD (charge coupled cell) and The solid-state imagers such as CMOS (complementary metal oxide film semiconductor) are (hereinafter, be also referred to as " image sensing for solid-state imager Device ".) and the circuit substrate of the solid-state imager is installed.The solid-state imaging apparatus is equipped on digital camera, the shifting with camera Mobile phone and smart phone etc..
In solid-state imaging apparatus, the noise as caused by the reflection of visible light is generated sometimes.As a result, in order to realize that inhibition is made an uproar Defined photomask is arranged in the generation of sound in solid-state imaging apparatus.As the composition for being used to form photomask, using containing The black combination of the black equal black pigments of titanium.
On the other hand, it is configured in the colour filter of solid-state imager and liquid crystal image device etc., colours picture in order to prevent The colour mixture of light between element improves contrast etc., sometimes R (red), G (green), B (blue) each pixel between formed There is black matrix.In addition, the light leakage of the acceptance part of solid-state imager, is formed in its frame region in order to prevent in colour filter Imaging sensor periphery photomask (frame photomask).
It is used to form and also uses the black combination containing the black equal black pigments of titanium in the composition of above-mentioned black matrix.Example Such as, a kind of " resin black matrix black-colored resin composition, including at least light screening material, resin in patent document 1, is disclosed And solvent, titanium nitride particle is at least contained as light screening material, wherein using CuK alpha ray as above-mentioned nitridation when x-ray source 2 θ of the angle of diffraction at the peak from (200) face of titanium particle is 42.5 ° or more and 42.8 ° or less." (claim 1).
Conventional art document
Patent document
Patent document 1: No. 5136139 bulletins of Japanese Patent No.
Summary of the invention
The invention technical task to be solved
About the cured film of the black combination containing titanium nitride particle (nitrogen titanium particle) as mentioned above, in example The photomask of component parts or the black matrix of colour filter or imaging sensor periphery photomask such as solid-state imaging apparatus When, it is laminated sometimes on the substrate configured with electrodes such as electrode patterns to use.
The inventors of the present invention make the black combination containing titanium nitride particle (nitrogen titanium particle) recorded in patent document 1 Object, and cured film is formed in a manner of jacketed electrode on the substrate configured with electrode with this, to implement its evaluation.Its As a result, learning the type according to titanium nitride particle (nitrogen titanium particle), produced in the region contacted with the photomask of above-mentioned electrode It gets rusty, that is, corroding electrode sometimes.Also, it similarly, clearly arrives and forms consolidating for pattern form using above-mentioned black combination When changing film, the resolution ratio (patternability) of pattern is unsatisfactory for desired requirement.
Therefore, excellent the purpose of the present invention is to provide the anti-corrosive properties that can make electrode and excellent patternability to consolidate Change the composition of film.Also, the object of the invention is also to provide a kind of cured film, colour filter, photomask, solid-state imagers And image display device.
For solving the means of technical task
The inventors of the present invention have made intensive studies to realize the above subject, finally, it is found that by by nitrogen titanium The content of chlorine atom in particle is adjusted to defined numberical range, is able to solve the above subject, and complete the present invention.
That is, discovery is by can be realized above-mentioned purpose with flowering structure.
(1) a kind of composition contains the nitrogen titanium particle comprising chlorine atom,
The content of above-mentioned chlorine atom in above-mentioned nitrogen titanium particle is 0.001~0.3 mass %.
(2) composition according to (1), wherein using CuK alpha ray as when x-ray source, above-mentioned nitrogen titanium particle The peak from (200) face 2 θ of the angle of diffraction be more than 42.8 ° and 43.5 ° or less.
(3) composition according to (1) or (2), wherein the ratio of above-mentioned nitrogen titanium particle found out by BET method Surface area is 40~60m2/g。
(4) composition according to any one of (1) to (3), wherein the average primary grain of above-mentioned nitrogen titanium particle Diameter is 10~30nm.
(5) composition according to any one of (1) to (4), wherein described using transmission electron microscope contains In the photo observation of the primary particle image of titanium nitride particle,
In 100 observation objects 60 the above are spherical shapes.
(6) composition according to any one of (1) to (5), also contains two or more solvent.
(7) composition according to any one of (1) to (6), also contains dispersing agent.
(8) composition according to (7), wherein above-mentioned dispersing agent relative to above-mentioned nitrogen titanium particle containing than Example is 0.3 or less by quality ratio.
(9) composition according to any one of (1) to (8), also contains polymerizable compound.
(10) composition according to any one of (1) to (9), also contains polymerization initiator.
(11) composition according to any one of (1) to (10), wherein the solid component in above-mentioned composition is 10 ~40 mass %.
(12) composition according to any one of (1) to (11), wherein the content of above-mentioned nitrogen titanium particle is opposite It is 30~70 mass % in the total solid content of above-mentioned composition.
(13) composition according to any one of (1) to (12), also contains water,
The content of above-mentioned water is 0.1~1 mass % relative to above-mentioned composition gross mass.
(14) composition according to any one of (1) to (13), also contains dispersing agent,
Above-mentioned dispersing agent has selected from by polycaprolactone, poly- valerolactone, polymethyl acrylate and polymethyl methacrylate At least one kind of structure in the group of composition.
(15) a kind of cured film is obtained using composition described in any one of (1) to (14).
(16) a kind of colour filter has cured film described in (15).
(17) a kind of photomask has cured film described in (15).
(18) a kind of solid-state imager has cured film described in (15).
(19) a kind of image display device has cured film described in (15).
Invention effect
In accordance with the invention it is possible to provide the solidification that a kind of anti-corrosive properties that can make electrode are excellent and patternability is excellent The composition of film.Also, the present invention is capable of providing a kind of cured film, colour filter, photomask, solid-state imager and image and shows Device.
Specific embodiment
Hereinafter, the present invention will be described.
The numberical range in this specification, using "~" to indicate indicates the numerical value comprising the front and back for being recorded in "~" as under The range of limit value and upper limit value.
In the label of group (atomic group) in this specification, substitution and unsubstituted label are not recorded as without taking The group of Dai Ji is together also comprising having the group of the group of substituent group.For example, " alkyl " is not only comprising without substituent group Alkyl (unsubstituted alkyl), also comprising the alkyl (replacing alkyl) with substituent group.
In this specification, " activation light " or " radioactive ray " for example indicate bright-line spectrum, the excimer laser institute's generation of mercury lamp Far ultraviolet, extreme ultraviolet (EUV light), X-ray and electron ray of table etc..Also, in the present invention, light representations activate light or Radioactive ray." exposure " in this manual is closed, unless otherwise specified, then not only comprising the bright-line spectrum based on mercury lamp, standard point The exposure of far ultraviolet representated by sub- laser, X-ray, EUV light etc., the description based on the particles beams such as electron ray and ion beam It is also contained in exposure.
In this specification, " (methyl) acrylate " indicates acrylate and methacrylate, " (methyl) acrylic acid " Indicate that acrylic acid and methacrylic acid, " (methyl) acryloyl group " indicate acryloyl group and methylacryloyl, " (methyl) propylene Amide " indicates acrylamide and Methacrylamide.Also, in this specification, the meaning of " monomer " and " monomer (monomer) " It is identical.Monomer and oligomer and polymer different from the present invention refer to that weight average molecular weight is 2,000 compound below. In this specification, polymerizable compound refers to the compound with polymerizable group, can be monomer, is also possible to polymer.It is poly- Conjunction property group refers to group related with polymerization reaction.
[composition]
Composition of the invention contains the nitrogen titanium particle comprising chlorine atom, the above-mentioned chlorine in above-mentioned nitrogen titanium particle The content of atom is 0.001~0.3 mass %.
Composition according to the present invention, can make electrode anti-corrosive properties are excellent and cured film that patternability is excellent.
The inventors of the present invention have made intensive studies, as a result, confirming following content, that is, use containing comprising chlorine atom Composition of nitrogen titanium particle of the amount more than 0.3 mass % as the black of pigment composition, on the substrate configured with electrode When forming photomask, according to use environment condition, react generating salt with the moisture etc. in air by above-mentioned chlorine atom Thus acid causes the deterioration of electrod assembly sometimes.
On the other hand, discovery uses the content comprising chlorine atom less than the nitrogen titanium particle of 0.001 mass % as face When expecting the composition of ingredient, the optical concentration (OD) of film obtained is got higher, and has patternability downward trend.
Consider from above-mentioned viewpoint, by the way that the content of the chlorine atom in the nitrogen titanium particle contained by composition to be set as 0.001~0.3 mass %, be capable of forming electrode anti-corrosive properties are excellent and cured film that patternability is excellent.
< includes the nitrogen titanium particle > of chlorine atom
When manufacturing nitrogen titanium particle, gas-phase reaction method is usually utilized, specifically, electric furnace process and heat plasma can be enumerated Body method etc..In these manufacturing methods, the easily consistent angle of less angle, partial size and the higher angle of productivity are mixed into from impurity The consideration of the reasons such as degree, preferably hot plasma method.
As the production method of hot plasma, can enumerate DC arc discharge, multiphase arc discharge, high frequency (RF) etc. from Daughter and hybrid plasma body etc. are preferably to carry out the impurity of self-electrode to be mixed into less high-frequency plasma.As being based on The specific manufacturing method of the nitrogen titanium particle of hot plasma method, for example, can enumerate makes titanium valve by high-frequency thermal plasma End evaporation, using nitrogen as in carrier gas gatherer, by cooling procedure, nitrogenizes titanium powder, to synthesize nitrogen titanium particle Method etc..In addition, hot plasma method is not limited to the above method.
Also, by obtaining nitrogen titanium particle using hot plasma method, being easy will be using CuK alpha ray as X-ray 2 θ of the angle of diffraction (detailed content will carry out aftermentioned) at the peak from (200) face when source be adjusted to more than 42.8 ° and 43.5 ° with Under.
Wherein, it as the method for making nitrogen titanium particle contain chlorine atom, is not particularly limited.It can enumerate as an example It states in hot plasma method, is used together titanium tetrachloride with titanium powder, be further used as carrier gas circulation ammonia, thus synthesis includes The method of the nitrogen titanium particle of chlorine atom.
Also, when the content of the chlorine atom in nitrogen titanium particle is specified amount or more, preferably for example at 100~300 DEG C Heat treatment is carried out 5 minutes~72 hours (preferably to particle under (preferably 120~280 DEG C, more preferably 120~250 DEG C) 3~48 hours, more preferably 3~36 hours).By can reduce the chlorine for including in nitrogen titanium particle by heating The content of atom is adjusted to specified amount.
Titanium valve powder material (titanium particle) and titanium tetrachloride used in the manufacture of nitrogen titanium particle preferably have high-purity. Titanium valve powder material and titanium tetrachloride are not particularly limited, the titanium valve for the use of the purity of titanium elements being preferably 99.99% or more Powder material and titanium tetrachloride more preferably use 99.999% or more titanium valve powder material and titanium tetrachloride.
Titanium valve powder material (titanium particle) and titanium tetrachloride are sometimes with titanium atom used in the manufacture of nitrogen titanium particle Atom in addition.As other atoms that may include in titanium valve powder material, such as Fe atom and Si atom etc. can be enumerated.
Contain the Fe atomic time in titanium valve powder material and titanium tetrachloride, the content of Fe atom is relative to titanium valve powder material and tetrachloro Change the gross mass of titanium, preferably more than 0.001 mass %.The patternability of cured film is more excellent as a result,.Also, in titanium Dusty material and titanium tetrachloride contain Fe atomic time, total matter of the content of Fe atom relative to titanium valve powder material and titanium tetrachloride Amount, preferably less than 0.4 mass %.The anti-corrosive properties of the electrode based on cured film are more excellent as a result, (is more able to suppress cured film Corrosion to electrode).That is, the Fe for including in titanium valve powder material used in the manufacture for passing through nitrogen titanium particle and titanium tetrachloride Atom (more than 0.001 mass % and less than 0.4 mass %), can obtain effect of the invention within the above range more significantly Fruit.
Titanium valve powder material and titanium tetrachloride contain the Si atomic time, the content of Si atom relative to titanium valve powder material gross mass, Preferably more than 0.002 mass % and less than 0.3 mass %, more preferably 0.01~0.15 mass %, further preferably 0.02~0.1 mass %.It is more than 0.002 mass % by the content of Si atom, the patternability of cured film more improves.And And think, by the content of Si atom less than 0.3 mass %, the polarity on the most surface layer of nitrogen titanium particle obtained is stablized, Dispersing agent when dispersing nitrogen titanium particle is improved to the adsorptivity of nitrogen titanium particle, and nitrogen titanium particle does not divide It dissipates object to reduce, thus has the effect of inhibiting to generate particle.That is, titanium powder material used in the manufacture for passing through nitrogen titanium particle The Si atom for including in material and titanium tetrachloride within the above range, can obtain effect of the invention more significantly.
Also, the moisture phase in titanium valve powder material (titanium particle) and titanium tetrachloride used in the manufacture of nitrogen titanium particle For the gross mass of titanium valve powder material, preferably less than 1 mass %, more preferably less than 0.1 mass %, further preferably essence On do not include.Moisture in titanium valve powder material and titanium tetrachloride used in manufacture by nitrogen titanium particle is in above range It is interior, effect of the invention can be obtained more significantly.
Gross mass of the content of titanium atom (Ti atom) in nitrogen titanium particle relative to nitrogen titanium particle, preferably 50~85 mass %, more preferably 50~80 mass %, further preferably 50~75 mass %.Ti in nitrogen titanium particle The content of atom can be analyzed by ICP (high-frequency inductive coupling plasma body) ICP Atomic Emission Spectrophotometer method.
Gross mass of the content of nitrogen-atoms (N atom) in nitrogen titanium particle relative to nitrogen titanium particle, preferably 20~50 mass %, more preferably 20~45 mass %, further preferably 20~40 mass %.The content of nitrogen-atoms can lead to Inactive gas melting thermal conductivity method is crossed to be analyzed.
The content of oxygen atom in nitrogen titanium particle relative to nitrogen titanium particle gross mass, preferably 12 mass % with Under, more preferably 8 mass % or less.The content of oxygen atom can melt infrared absorption by inactive gas and be divided Analysis.
The content of chlorine atom in nitrogen titanium particle is 0.001~0.3 matter relative to nitrogen titanium particle gross mass Measure %.Wherein, preferably 0.005~0.3 mass %, more preferably 0.01~0.3 mass %, further preferably 0.1~0.3 Quality %, especially preferably 0.1~0.15 mass %.Content by chlorine atom is 0.001 mass % or more, the figure of cured film Case formative is excellent.Content by chlorine atom is 0.3 mass % hereinafter, the patternability of cured film is excellent, and is based on The anti-corrosive properties of the electrode of cured film are excellent.
Wherein, the content of the chlorine atom in nitrogen titanium particle is measured by ICP ICP Atomic Emission Spectrophotometer method.
Nitrogen titanium particle when CuK alpha ray to measure to X-ray diffraction spectra as x-ray source is originated from (200) face 2 θ of the angle of diffraction at peak be preferably more than 42.8 ° and 43.5 ° or less.Using containing the nitrogen titanium particle with this feature Composition becomes numerical value appropriate come the OD value of the cured film (for example, black matrix etc.) obtained, and patternability (resolution ratio) is more It is excellent.
As above-mentioned, 2 θ of the angle of diffraction at the peak from (200) face of nitrogen titanium particle is preferably more than 42.8 ° and 43.5 ° Hereinafter, more preferably 42.85~43.3 °, further preferably 42.9~43.2 °.
The case where nitrogen titanium particle includes titanium nitride (TiN) as principal component, is usually mixed into oxygen in its synthesis and grain When diameter is smaller, the oxidation of particle surface becomes that significantly, some oxygen atom can be contained.
Wherein, the oxygen amount for including in nitrogen titanium particle can get higher OD value (optical concentration) when less, therefore excellent Choosing.Also, nitrogen titanium particle does not preferably contain TiO as accessory ingredient2.Nitrogen titanium particle contains titanium oxide as accessory ingredient TiO2When, as the strongest peak of intensity, it is originated from Detitanium-ore-type TiO2(101) peak appears near 2 θ=25.3 °, is originated from golden red Stone-type TiO2(110) peak appears near 2 θ=27.4 °.But TiO2For white, become the light-proofness for reducing black matrix Main cause, therefore it is preferably decreased to degree not as peak and observed.
The crystallite dimension for constituting nitrogen titanium particle can be found out by the half-peak breadth at X-ray diffraction peak, strangled using thanking (Scherrer) formula is calculated.
As crystallite dimension, preferably 20nm or more, more preferably 20~50nm.It the use of crystallite dimension is 20nm's or more When nitrogen titanium particle forms black matrix, the transmitted light of cured film be in such as a length of 475nm of its spike blue below to bluish violet, The black matrix for having both higher light-proofness Yu ultraviolet line sensitivity can be obtained.
The specific surface area of nitrogen titanium particle can be found out by BET method, preferably 40~60m2/ g, more preferably 40~ 58m2/ g, further preferably 42~55m2/g.By the way that the specific surface area of nitrogen titanium particle is set as 40~60m2/ g, is obtained OD (optical concentration) value of the cured film obtained becomes more appropriate range, and patternability (resolution ratio) is more excellent, and combines The filterability of object is also excellent.
The average primary particle diameter of nitrogen titanium particle is preferably 10~30nm, more preferably 10~28nm, further preferably For 10~25nm, further preferably 10~20nm.By the way that the average primary particle diameter of nitrogen titanium particle is set as 10~30nm, OD (optical concentration) value of cured film obtained becomes range appropriate.Also, from the viscosity ageing stability of composition Viewpoint considers that the average primary particle diameter of nitrogen titanium particle is preferably 10nm or more.
In addition, the average primary particle diameter of nitrogen titanium particle refers in the present invention, transmission electron microscope can be passed through (for example, device that JEM-2100F type field emission type transmission electron microscope is manufactured according to JEOL Ltd.) observation particle, and from The number average particle diameter for the primary particle that photo obtained is found out.Specifically, including by the method preparation that embodiment is recorded The dispersion liquid of nitrogen titanium particle, and in such a way that its solid component becomes 1 mass % or so, by identical with dispersion liquid molten Agent is diluted, and dispersion liquid is added dropwise on carbon foil, and the transmission-type of the nitrogen titanium particle on carbon foil is present in after seeing drying Electron microscope image.The projected area of the primary particle of nitrogen titanium particle is found out by above-mentioned apparatus, is thus found out circle and is worked as Measure diameter.Using the arithmetic average of calculated equivalent circle diameter as primary particle size.More specifically, in order to find out average one Secondary partial size and after randomly selected 100 particle assay primary particle sizes, to excluding the 80 of maximum side 10 and minimum side 10 The primary particle size of a particle carries out arithmetic average to find out equivalent circle diameter.
Also, nitrogen titanium particle is observed in the photo of the primary particle image using above-mentioned transmission electron microscope In, 60 or more (in other words, 60% or more) are spherical shape in preferably 100 observation objects.Pass through used nitrogen titanium grain The above are spherical shape, OD (optical concentration) values of cured film obtained to become range appropriate for the 60% of son, and patternability (divides Resolution) it is more excellent.Also, by used nitrogen titanium particle 60% the above are spherical shape, the filterability of composition and viscous It is also excellent to spend ageing stability.
In addition, it is not necessarily positive ball that particle, which is that " spherical shape " refers to, in the present invention, such as it can be substantially spherical person and (throw Minor axis/draw ratio in X-Y scheme when shadow is 0.7~1 or so), ellipsoid of revolution.
Total solid content of the content of nitrogen titanium particle relative to composition, preferably 30~70 mass %, more preferably For 40~68 mass %, further preferably 42~65 mass %.By the content of nitrogen titanium particle in above-mentioned numberical range, Light splitting property (good OD value) is excellent, and the anti-corrosive properties of patternability (resolution ratio) and electrode are also excellent.
In addition, solid component indicates to constitute the ingredient of the cured film formed by composition in this specification, do not include molten Agent.For example, aftermentioned polymerizable compound is the ingredient for constituting cured film, even therefore liquid (liquid), be also contained in solid In body ingredient.
< dispersing agent >
Composition of the invention preferably comprises dispersing agent.Dispersing agent helps to improve the pigment such as above-mentioned nitrogen titanium particle Dispersibility.In the present invention, dispersing agent is the ingredient different from aftermentioned adhesive resin.
As dispersing agent, for example, can suitably select well known pigment dispersing agent come using.Wherein, preferably producing high-molecular Close object.
As dispersing agent, macromolecule dispersing agent can be enumerated (for example, polyamide-amide and its salt, polycarboxylic acids and its salt, high score Son amount unsaturated acid ester, modified polyurethane, modified poly ester, modified poly- (methyl) acrylate, (methyl) acrylic copolymer, naphthalene Sulfonic acid formaline condensates), polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivative etc..
High-molecular compound can be categorized further, as straight-chain macromolecule, terminal-modified type macromolecule, grafting according to its structure Type macromolecule and block type polymer.
High-molecular compound is adsorbed in nitrogen titanium particle and pigment as needed etc. by the surface of dispersion, hair Waving prevents by the effect of dispersion re-united.It is therefore preferable that for the terminal-modified of the fixed position for surface of pigments Type macromolecule, graft type macromolecule and block type polymer.
On the other hand, it is modified by the surface to nitrogen titanium particle, additionally it is possible to promote high-molecular compound to it Adsorptivity.
High-molecular compound preferably has the structural unit for having grafted chain.In addition, in this specification, " structural unit " Meaning is identical as " repetitive unit ".
High-molecular compound with the structural unit for having this grafted chain has affine with solvent by grafted chain Property, thus be the pigment such as nitrogen titanium particle dispersibility and through when after the excellent compound of dispersion stabilization.Also, it is logical It crosses the high-molecular compound for having the structural unit of grafted chain there are grafted chain and polymerizable compound or other can be simultaneously Resin etc. is affinity.As a result, becoming the residue not easily generated in alkali development.
If grafted chain is elongated, steric repulsion effect is improved and the dispersibility of pigment etc. is improved.On the other hand, if connecing Branch chain is too long, then declines to the adsorption capacity of the pigment such as nitrogen titanium particle, and the dispersibility of pigment etc. is in downward trend.Therefore, Grafted chain is preferably the grafted chain that the atomicity in addition to hydrogen atom is 40~10000, the original more preferably in addition to hydrogen atom The grafted chain that subnumber is 50~2000, the grafted chain that the atomicity further preferably in addition to hydrogen atom is 60~500.
Wherein, grafted chain indicates the root (atom being bonded from the group of main chain branch with main chain) of the main chain of copolymer To the end of the group from main chain branch.
Grafted chain preferably has polymer architecture, as this polymer architecture, such as can enumerate poly- (methyl) acrylic acid Ester structure (for example, poly- (methyl) acrylic acid structure), polyester construction, polyurethane structural, polyurea structure, polyamide structure and polyethers Structure etc..
In order to improve the interaction of grafted chain and solvent, and dispersibility is thus improved, grafted chain preferably has choosing At least one kind of grafted chain in the group of free polyester construction, polyether structure and poly- (methyl) acrylate structural composition, more preferably For at least any one the grafted chain with polyester construction and polyether structure.
As the huge monomer with this grafted chain, it is not particularly limited, it can be suitably using with reactive double bond The huge monomer of base.
Have the structural unit of grafted chain corresponding as with possessed by high-molecular compound, and suitable for synthesis high score The commercially available huge monomer of sub- compound, usable AA-6 (trade name, TOAGOSEI CO., LTD.), AA-10 (trade name, TOAGOSEI CO., LTD. manufacture), AB-6 (trade name, TOAGOSEI CO., LTD. manufacture), AS-6 (trade name, TOAGOSEI CO., LTD.), AN-6 (trade name, TOAGOSEI CO., LTD. manufacture), AW-6 (trade name, TOAGOSEI CO., LTD. is manufactured), AA-714 (trade name, TOAGOSEI CO., LTD. manufacture), AY-707 (trade name, TOAGOSEI CO., LTD. is manufactured), AY-714 (trade name, TOAGOSEI CO., LTD. manufacture), AK-5 (trade name, TOAGOSEI CO., LTD. manufacture), AK-30 (trade name, TOAGOSEI CO., LTD. manufacture), AK-32 (trade name, TOAGOSEI CO., LTD. Manufacture), Blemmer PP-100 (trade name, NOF CORPORATION. manufacture), Blemmer PP-500 (trade name, NOF CORPORATION. manufacture), Blemmer PP-800 (trade name, NOF CORPORATION. manufacture), Blemmer PP-1000 (trade name, NOF CORPORATION. manufacture), Blemmer 55-PET-800 (trade name, NOF CORPOR ATION. system Make), Blemmer PME-4000 (trade name, NOF CORPORATION. manufacture), Blem mer PSE-400 (trade name, NOF CORPORATION. manufacture), Blemmer PSE-1300 (trade name, NOF CORPORATION. manufacture), Blemmer 43PAPE-600B (trade name, NOF CORPORA TION. manufacture) etc..Wherein, it is preferable to use AA-6 (trade name, Toagosei.Company, Limited. manufacture), AA-10 (trade name, TOAGOSEI CO., LTD.), AB-6 (trade name, TOAGOSEI CO., LTD. manufacture), AS-6 (trade name, TOAGOSEI CO., LTD.), AN-6 (trade name, TOAGOSEI CO., LTD. is manufactured) and Blemmer PME-4000 (trade name, NOF CORPORATION. manufacture) etc..
Dispersing agent preferably has selected from by polycaprolactone, poly- valerolactone, polymethyl acrylate and polymethyl methacrylate At least one kind of structure in the group of composition.Moreover, these structures are more preferably used in combination of two or more.
Wherein, polycaprolactone structure refers to the structure for having the structure that open loop is carried out to 6-caprolactone as repetitive unit. Poly- valerolactone structure refers to the structure for having the structure that open loop is carried out to δ-valerolactone as repetitive unit.
As the concrete example of the dispersing agent with polycaprolactone structure, the j in following formula (1) and following formula (2) can be enumerated And the dispersing agent that k is 5.Also, as the concrete example of the dispersing agent with poly- valerolactone structure, can enumerate following formula (1) and under State the dispersing agent that j in formula (2) and k is 4.
As the concrete example of the dispersing agent with polymethyl acrylate structure, the X in following formula (4) can be enumerated5For hydrogen original Son, and R4For the dispersing agent of methyl.Also, it as the concrete example of the dispersing agent with polymethyl methacrylate structure, can lift X in following formula (4) out5For methyl, and R4For the dispersing agent of methyl.
High-molecular compound is preferably comprised as the structural unit with grafted chain with appointing in following formula (1)~formula (4) One expression structural unit, more preferably comprising with following formula (1A), following formula (2A), following formula (3A), following formula (3B) and The structural unit that any of following formula (4) indicates.
[chemical formula 1]
In formula (1)~formula (4), W1、W2、W3And W4Separately indicate oxygen atom or NH.W1、W2、W3And W4Preferably it is Oxygen atom.
In formula (1)~formula (4), X1、X2、X3、X4And X5Separately indicate the organic group of hydrogen atom or 1 valence.As X1、X2、X3、X4And X5, preferably separately it is hydrogen atom or carbon atom number (carbon from the viewpoint of the limitation in terms of synthesis Plain atomicity) 1~12 alkyl, be more preferably separately hydrogen atom or methyl, further preferably methyl.
In formula (1)~formula (4), Y1、Y2、Y3And Y4Separately indicate the linking group of divalent, the structure of linking group Aspect is not particularly limited.As with Y1、Y2、Y3And Y4The linking group of the divalent of expression, specifically, can enumerate following (Y-1) for~(Y-21) linking group etc..In structure shown in following, A, B respectively indicate with formula (1)~formula (4) in The bonding position of left-end point group, right end group.In structure shown in following, consider from the simplicity of synthesis, more preferably For (Y-2) or (Y-13).
[chemical formula 2]
In formula (1)~formula (4), Z1、Z2、Z3And Z4Separately indicate the organic group of 1 valence.The structure of organic group It is not particularly limited, specifically, alkyl, hydroxyl, alkoxy, aryloxy group, heteroaryloxy, alkane thioether group, aromatic sulfide can be enumerated Base, heteroaryl thioether group and amino etc..In these, as with Z1、Z2、Z3And Z4The organic group of expression is especially improved from dispersibility From the viewpoint of, it is however preferred to have the group of steric repulsion effect, preferably separately for carbon atom number 5 to 24 alkyl or Alkoxy, wherein be separately particularly preferably the branched alkyl groups of carbon atom number 5 to 24, the cyclic annular alkane of carbon atom number 5 to 24 The alkoxy of base or carbon atom number 5 to 24.In addition, the alkyl for including in alkoxy can be in straight-chain, branched and ring-type Either one or two of.
In formula (1)~formula (4), n, m, p and q are separately 1 to 500 integer.
Also, in formula (1) and formula (2), j and k separately indicate 2~8 integer.From the dispersion stabilization of composition And from the viewpoint of developability, formula (1) and j in formula (2) and k are preferably 4~6 integer, more preferably 5.
In formula (3), R3Indicate the alkylidene of branch or straight chain, the preferably alkylidene of carbon atom number 1~10, more preferably For the alkylidene of carbon atom number 2 or 3.When p is 2~500, there are multiple R3It can be same to each other also different.
In formula (4), R4Indicate that the organic group of hydrogen atom or 1 valence has no spy in structure as the organic group of 1 valence It does not limit.As R4, preferably enumerate hydrogen atom, alkyl, aryl and heteroaryl, more preferably hydrogen atom or alkyl.R4For alkyl When, as alkyl, the preferably straight-chain alkyl of carbon atom number 1~20, the branch-like alkyl of carbon atom number 3~20 or carbon atom The cyclic alkyl of number 5~20, the more preferably straight-chain alkyl of carbon atom number 1~20, further preferably carbon atom number 1~6 Straight-chain alkyl.In formula (4), when q is 2~500, there are multiple X in graft copolymer5And R4It can be same to each other also mutual It is not identical.
Also, high-molecular compound can have different structure of more than two kinds and the structural unit with grafted chain.That is, high It may include the mutually different structural unit indicated with formula (1)~formula (4) of structure, also, formula in the molecule of molecular compound It (1) can in the side chain include j and k in formula (1) and formula (2) when n, m, p and q respectively indicate 2 or more integer in~formula (4) In mutually different structure, formula (3) and formula (4), there are multiple R for intramolecular3、R4And X5It can be same to each other also different.
It is more excellent from the viewpoint of the dispersion stabilization of composition and developability as the structural unit indicated with formula (1) It is selected as the structural unit indicated with following formula (1A).
Also, as the structural unit indicated with formula (2), the viewpoint of dispersion stabilization and developability from composition is examined Consider, the structural unit more preferably indicated with following formula (2A).
[chemical formula 3]
In formula (1A), X1、Y1、Z1And the X in the meaning of n and formula (1)1、Y1、Z1And n is identical, preferred scope is also identical.Formula In (2A), X2、Y2、Z2And the X in the meaning of m and formula (2)2、Y2、Z2And m is identical, preferred scope is also identical.
Also, as the structural unit indicated with formula (3), the viewpoint of dispersion stabilization and developability from composition is examined Consider, the structural unit more preferably indicated with following formula (3A) or formula (3B).
[chemical formula 4]
In formula (3A) or (3B), X3、Y3、Z3And the X in the meaning of p and formula (3)3、Y3、Z3And p is identical, preferred scope also phase Together.
High-molecular compound more preferably has the structure list indicated with formula (1A) as the structural unit with grafted chain Member.
In high-molecular compound, the structural unit with grafted chain is (for example, the structure indicated with above-mentioned formula (1)~formula (4) Unit) with mass conversion, relative to the gross mass of high-molecular compound, preferably include with 2~90% range, more preferably with 5 ~30% range includes.If in the range comprising the structural unit with grafted chain, the dispersibility of nitrogen titanium particle Higher, developability when forming cured film is good.
Also, high-molecular compound preferably has different from the structural unit with grafted chain (that is, not being equivalent to has The structural unit of grafted chain) hydrophobic structure unit.Wherein, in the present invention, hydrophobic structure unit is that do not have acidic group (example Such as, carboxylic acid group, sulfonic group, phosphate, phenolic hydroxyl group etc.) structural unit.
Hydrophobic structure unit is preferably derived from the structure list for the compound (monomer) that (correspondence) ClogP value is 1.2 or more Member is more preferably originated from the structural unit for the compound that ClogP value is 1.2~8.Thereby, it is possible to more reliably show the present invention Effect.
ClogP value is the journey by that can obtain from Daylight Chemical Information System, Inc. The value that sequence " CLOGP " calculates.The program is provided through Hansch, fragmentapproach (referring to following documents) meter of Leo The value of " calculating logP " for calculating.Chemical structure is divided into portion according to the chemical structure of compound by Fragmentapproach Separation structure (segment) amounts to the logP contribution amount for being allocated in the segment, thus calculates the logP value of compound.Its detailed content note It is loaded in following documents.In the present invention, using pass through the calculated ClogP value of program CLOGP v4.82.
A.J.Leo,Comprehensive Medicinal Chemistry,Vol.4,C.Hansch, P.G.Sammnens,J.B.Taylor and C.A.Ramsden,Eds.,p.295,Pergamon Press, 1990C.Hansch&A.J.Leo.Substituent Constants For Corre lation Analysis in Chemistry and Biology.John Wiley&Sons.A.J.Leo.Calculating logPoct from structure.Chem.Rev.,93,1281-1306,1993.
LogP indicates the common logarithm of distribution coefficient P (Partition Coefficient), is indicated with quantitative numerical value The physics value how a certain organic compound distributes in the balance of oily (usually 1- octanol) and 2 phase systems of water, by following formula It indicates.
LogP=log (Coil/Cwater)
In formula, Coil indicates the molar concentration of the compound in oily phase, and Cwater indicates mole of the compound in water phase Concentration.
If the value of logP clips 0 and positive (plus) increases, then it represents that oil-soluble increases, if absolute value negative sense (minus) Increase, then it represents that water solubility increases, and has negative correlation with the water solubility of organic compound, the hydrophobe as estimation organic compound The parameter of property and utilize extensively.
High-molecular compound preferably has as hydrophobic structure unit selected from from the following general formula (i)~(iii) table The structural unit of one or more of the structural unit of monomer shown.
[chemical formula 5]
In above-mentioned formula (i)~(iii), R1、R2And R3Separately indicate hydrogen atom, halogen atom (for example, fluorine, chlorine, bromine Deng) or carbon atom number be 1~6 alkyl (for example, methyl, ethyl, propyl etc.).
R1、R2And R3Preferably hydrogen atom or carbon atom number are 1~3 alkyl, more preferably hydrogen atom or methyl.R2And R3 Especially preferably hydrogen atom.
X indicates oxygen atom (- O-) or imino group (- NH-), preferably oxygen atom.
L is the linking group of singly-bound or divalent.As the linking group of divalent, the fatty group of divalent can be enumerated (for example, sub- Alkyl, alkenylene, replaces alkenylene, alkynylene, replaces alkynylene substituted alkylene), the aromatic series base of divalent is (for example, sub- virtue Base, replace arlydene), the heterocycle of divalent, oxygen atom (- O-), sulphur atom (- S-), imino group (- NH-), substituted imido (- NR31, wherein R31For fatty group, aromatic series base or heterocycle), carbonyl (- CO-) and their combination etc..
The fatty group of divalent can have cyclic structure or branched structure.The carbon atom number of fatty group is preferably 1~20, More preferably 1~15, further preferably 1~10.Fatty group can be unsaturated aliphatic base, be also possible to saturated fat Race's base, but preferably representative examples of saturated aliphatic base.Also, fatty group can have substituent group.The example of substituent group can enumerate halogen atom, Aromatic series base and heterocycle etc..
The carbon atom number of the aromatic series base of divalent is preferably 6~20, and more preferably 6~15, further preferably 6~10.And And aromatic series base can have substituent group.The example of substituent group can enumerate halogen atom, fatty group, aromatic series base and heterocycle etc..
The heterocycle of divalent preferably has 5 member rings or 6 member rings as heterocycle.Other heterocycles, aliphatic can have been condensed on heterocycle Ring or aromatic ring.Also, heterocycle can have substituent group.As the example of substituent group, halogen atom, hydroxyl, oxo can be enumerated Base (=O), thio group (=S), imino group (=NH), substituted imido (=N-R32, wherein R32For fatty group, aromatic series Base or heterocycle), fatty group, aromatic series base and heterocycle.
L is preferably the linking group of singly-bound, alkylidene or the divalent comprising alkylene oxide structure.Alkylene oxide structure is more preferably Ethylene oxide structure or oxypropylene structure.Also, L may include the polyoxyalkylene structure for repeating the alkylene oxide structure comprising 2 or more. As polyoxyalkylene structure, preferably polyoxyethylene structure or polyoxypropylene structure.Polyoxyethylene structure is with-(OCH2CH2) n- table Show, n is preferably 2 or more integer, more preferably 2~10 integer.
As Z, can enumerate fatty group (for example, alkyl, replace alkyl, unsaturated alkyl and replace unsaturated alkyl), Aromatic series base (for example, aryl, substituted aryl, arlydene, substitution arlydene), heterocycle and their combination.In these groups It may include oxygen atom (- O-), sulphur atom (- S-), imino group (- NH-), substituted imido (- NR31, wherein, R31For aliphatic Base, aromatic series base or heterocycle) or carbonyl (- CO-).
Fatty group can have cyclic structure or branched structure.The carbon atom number of fatty group is preferably 1~20, more preferably It is 1~15, further preferably 1~10.Also comprising ring set alkyl, crosslinking ring type alkyl in fatty group, as ring set The example of alkyl includes dicyclohexyl, perhydro naphthalene, xenyl and 4- cyclohexyl phenyl etc..As crosslinking ring type hydrocarbon ring, example Such as, it can enumerate: pinane (pinane), camphane (bornane), norpinane (norpinane), norcamphane (norbornane) and double The 2 ring type hydrocarbon rings such as cyclooctane ring (bicyclic [2.2.2] octane ring, bicyclic [3.2.1] octane ring etc.)；High mine-laying alkane (homobledane), adamantane, tricyclic [5.2.1.02,6] decane and tricyclic [4.3.1.12,5] the 3 ring type hydrocarbon rings such as hendecane ring； Fourth Ring [4.4.0.12,5.17,10] the 4 ring type hydrocarbon rings such as dodecane, perhydro -1,4- methylene -5,8- methylene naphthalene nucleus etc..Also, Being crosslinked also includes condensed ring formula hydrocarbon ring in ring type hydrocarbon ring, for example, Perhydronaphthalene (decahydronaphthalene), perhydro anthracene, perhydro are luxuriant and rich with fragrance, perhydro strategic point, perhydro The condensed condensed ring for having multiple 5~8 yuan of cycloalkane rings such as fluorenes, perhydro print and perhydro flower ring.
With unsaturated aliphatic base phase ratio, fatty group is preferably representative examples of saturated aliphatic base.Also, fatty group, which can have, to be taken Dai Ji.The example of substituent group can enumerate halogen atom, aromatic series base and heterocycle.Wherein, fatty group does not have as substituent group Acidic group.
The carbon atom number of aromatic series base is preferably 6~20, and more preferably 6~15, further preferably 6~10.Also, virtue Fragrant race's base can have substituent group.The example of substituent group can enumerate halogen atom, fatty group, aromatic series base and heterocycle.Wherein, fragrant Fragrant race's base does not have acidic group as substituent group.
Heterocycle preferably has 5 member rings or 6 member rings as heterocycle.Can have been condensed on heterocycle other heterocycles, aliphatic ring or Aromatic ring.Also, heterocycle can have substituent group.As the example of substituent group, can enumerate halogen atom, hydroxyl, oxo base (= O), thio group (=S), imino group (=NH), substituted imido (=N-R32, wherein R32For fatty group, aromatic series base or miscellaneous Ring group), fatty group, aromatic series base and heterocycle.Wherein, heterocycle does not have acidic group as substituent group.
In above-mentioned formula (iii), R4、R5And R6Separately indicate hydrogen atom, halogen atom (for example, fluorine, chlorine, bromine etc.), carbon Alkyl (for example, methyl, ethyl, propyl etc.), Z or the L-Z that atomicity is 1~6.Wherein, the meaning of L and Z among the above L and Z is identical.As R4、R5And R6, preferably hydrogen atom or carbon atom number is 1~3 alkyl, more preferably hydrogen atom.
In the present invention, as the monomer indicated with above-mentioned general formula (i), preferably R1、R2And R3It is for hydrogen atom or methyl, L The linking group of singly-bound or alkylidene or the divalent comprising alkylene oxide structure, X be oxygen atom or imino group, Z be fatty group, The compound of heterocycle or aromatic series base.
Also, as the monomer indicated with above-mentioned general formula (ii), preferably R1It is alkylidene, Z for hydrogen atom or methyl, L For the compound of fatty group, heterocycle or aromatic series base.Also, as the monomer indicated with above-mentioned general formula (iii), preferably R4、R5And R6It is the compound of fatty group, heterocycle or aromatic series base for hydrogen atom or methyl, Z.
As the example of the representative compound indicated with formula (i)~(iii), can enumerate selected from esters of acrylic acid, methyl The free-radical polymerised compound of esters of acrylic acid and phenylethylene etc..
In addition, the example as the representative compound indicated with formula (i)~(iii), can refer to Japanese Unexamined Patent Publication 2013- The compound recorded in 0089~0093 section of No. 249417 bulletins, these contents are introduced into this specification.
In high-molecular compound, hydrophobic structure unit is excellent relative to the gross mass of high-molecular compound with mass conversion It is selected as including more preferably to include with 10~90% range with 20~80% range.Content can be realized in the above range Sufficient pattern is formed.
High-molecular compound can import the functional group that interaction can be formed with pigment such as nitrogen titanium particles.Wherein, High-molecular compound is preferably also comprising the structure list with the functional group that can form interaction with pigment such as nitrogen titanium particles Member.
As the functional group that can form interaction with pigment such as the nitrogen titanium particles, for example, acidic group, alkalinity can be enumerated Base, coordinating base and there is reactive functional group etc..
High-molecular compound preferably contains respectively with acidic group, basic group, coordinating base or when having reactive functional group There are the structural unit with acidic group, the structural unit with basic group, the structural unit with coordinating base or anti-comprising having The structural unit of answering property.
In particular, high-molecular compound further has the alkali solubilities such as carboxylic acid group base as acidic group, thus, it is possible to macromolecule Compound assigns the developability formed for the pattern based on alkali development.
That is, by importing alkali solubility base to high-molecular compound, in composition of the invention, as facilitating nitrogen titanium The high-molecular compound of the dispersing agent of the dispersion of the pigment such as particle can have alkali solubility.Combination containing this high-molecular compound The object composition excellent as the light-proofness of exposure portion, and the alkali-developable in unexposed portion is improved.
Also, there is the structural unit containing acidic group by high-molecular compound, high-molecular compound becomes easy and solvent Integration and the trend also improved as coating.
Speculate this is because acidic group in the structural unit with acidic group easily with the pigment phase interaction such as nitrogen titanium particle With high-molecular compound disperses with making the pigment stabilizers such as nitrogen titanium particle, and disperses the pigment such as nitrogen titanium particle The viscosity of high-molecular compound, high-molecular compound itself are also readily and stably dispersed.
Wherein, the structural unit with the alkali solubility base as acidic group can be and the above-mentioned structure list with grafted chain The identical structural unit of member is also possible to different structural units, but the structural unit with the alkali solubility base as acidic group is The structural unit (that is, be not equivalent to above-mentioned hydrophobic structure unit) different from above-mentioned hydrophobic structure unit.
As the functional group, that is, acidic group that can be interacted with pigment formation such as nitrogen titanium particles, such as there are carboxylic acid group, sulphur It is at least one kind of in acidic group, phosphate or phenolic hydroxyl group etc., preferably carboxylic acid group, sulfonic group and phosphate, for nitrogen titanium grain The adsorption capacity of the pigment such as son is well and the higher angle of dispersibility of coloring pigment considers, especially preferably carboxylic acid group.
That is, high-molecular compound is preferably also comprising at least one kind of structure list in carboxylic acid group, sulfonic group and phosphate Member.
High-molecular compound can have the one kind or two or more structural unit with acidic group.
High-molecular compound contains the structural unit with acidic group, and can be free of has, but containing sometimes, has the knot of acidic group The content of structure unit is with mass conversion, relative to the gross mass of high-molecular compound, preferably 5~80%, is based on alkali from inhibition From the viewpoint of the damage of the image intensity of development, more preferably 10~60%.
As functional group, that is, basic group of interaction can be formed with the pigment such as nitrogen titanium particle, for example, have primary amino group, Secondary amino group, tertiary amino, the heterocycle comprising N atom and amide groups etc. are good from the adsorption capacity for pigment such as nitrogen titanium particles And the higher angle consideration of dispersibility of pigment, preferably tertiary amino.High-molecular compound can have one kind or two or more These basic groups.
High-molecular compound contains the structural unit with basic group, and can be free of has, and containing sometimes, has basic group The content of structural unit is with mass conversion, relative to the gross mass of high-molecular compound, preferably 0.01% or more and 50% with Under, from the viewpoint of inhibiting obstruction developability, more preferably 0.01% or more and 30% or less.
As the functional group, that is, coordinating base that can be interacted with pigment formation such as nitrogen titanium particles and there is reactivity Functional group, such as acetoacetoxy groups, trialkoxysilyl, isocyanate group, acid anhydrides and acyl chlorides can be enumerated etc..From needle Good to the adsorption capacity of the pigment such as nitrogen titanium particle and pigment the higher angle consideration of dispersibility, preferably acetoacetyl oxygen Base.High-molecular compound can have these one kind or two or more groups.
High-molecular compound is containing the structural unit with coordinating base or has reactive functional group, can be free of Have, but containing sometimes, the content of these structural units is with mass conversion, relative to the gross mass of high-molecular compound, preferably 10% or more and 80% hereinafter, from inhibit hinder developability from the viewpoint of, more preferably 20% or more and 60% or less.
High-molecular compound in the present invention also has other than grafted chain and can be formed with pigment such as nitrogen titanium particles When the functional group of interaction, containing the various officials that can form interaction with pigment such as nitrogen titanium particles as mentioned above It can roll into a ball, be not particularly limited how these functional groups are imported into, but high-molecular compound preferably has selected from from following State the structural unit of one or more of structural unit of monomer of general formula (iv)~(vi) expression.
[chemical formula 6]
In general formula (iv)~general formula (vi), R11、R12And R13Separately indicate hydrogen atom, halogen atom (for example, fluorine is former Son, chlorine atom, bromine atom etc.) or carbon atom number be 1~6 alkyl (for example, methyl, ethyl, propyl etc.).
In general formula (iv)~general formula (vi), R11、R12And R13It is preferred that being separately hydrogen atom or carbon atom number is 1~3 Alkyl, more preferably separately be hydrogen atom or methyl.In general formula (iv), R12And R13It is particularly preferably respectively hydrogen atom.
X in general formula (iv)1Indicate oxygen atom (- O-) or imino group (- NH-), preferably oxygen atom.
Also, the Y in general formula (v) indicates methine or nitrogen-atoms.
Also, the L in general formula (iv)~general formula (v)1Indicate the linking group of singly-bound or divalent.Linking group as divalent Example, can enumerate divalent fatty group (for example, alkylidene, substituted alkylene, alkenylene, replace alkenylene, alkynylene and Replace alkynylene), the aromatic series base of divalent (for example, arlydene and replace arlydene), the heterocycle of divalent, oxygen atom (- O-), sulphur Atom (- S-), imino group (- NH-), substituted imino key (- NR31'-, wherein R31' it is fatty group, aromatic series base or heterocycle Base), carbonyl key (- CO-) and their combination etc..
The fatty group of divalent can have cyclic structure or branched structure.The carbon atom number of fatty group is preferably 1~20, More preferably 1~15, further preferably 1~10.With unsaturated aliphatic base phase ratio, fatty group is preferably representative examples of saturated aliphatic Base.Also, fatty group can have substituent group.As the example of substituent group, halogen atom, hydroxyl, aromatic series base and miscellaneous can be enumerated Ring group.
The carbon atom number of the aromatic series base of divalent is preferably 6~20, and more preferably 6~15, most preferably 6~10.Also, Aromatic series base can have substituent group.The example of substituent group can enumerate halogen atom, hydroxyl, fatty group, aromatic series base and heterocycle.
The heterocycle of divalent preferably has 5 member rings or 6 member rings as heterocycle.Other heterocycles, aliphatic can have been condensed in heterocycle 1 or more in ring or aromatic ring.Also, heterocycle can have substituent group.As the example of substituent group, halogen original can be enumerated Son, hydroxyl, oxo base (=O), thio group (=S), imino group (=NH), substituted imido (=N-R32, wherein R32For fat Race's base, aromatic series base or heterocycle), fatty group, aromatic series base and heterocycle.
L1The preferably linking group of singly-bound, alkylidene or the divalent comprising alkylene oxide structure.Alkylene oxide structure is more preferably Ethylene oxide structure or oxypropylene structure.Also, L1It may include the polyoxyalkylene knot for repeating the alkylene oxide structure comprising 2 or more Structure.As polyoxyalkylene structure, preferably polyoxyethylene structure or polyoxypropylene structure.Polyoxyethylene structure is with-(OCH2CH2) N- indicates that n is preferably 2 or more integer, more preferably 2~10 integer.
In general formula (iv)~general formula (vi), Z1It indicates that phase interaction can be formed with pigment such as nitrogen titanium particles other than grafted chain Functional group, preferably carboxylic acid group and tertiary amino, more preferably carboxylic acid group.
In general formula (vi), R14、R15And R16Separately indicate hydrogen atom, halogen atom (for example, fluorine atom, chlorine atom, Bromine atom etc.), carbon atom number be 1~6 alkyl (for example, methyl, ethyl and propyl etc.) ,-Z1Or L1-Z1.Wherein, L1And Z1's Meaning and L among the above1And Z1Identical, preference is also identical.As R14、R15And R16, preferably separately for hydrogen atom or The alkyl that carbon atom number is 1~3, more preferably hydrogen atom.
In the present invention, as the monomer indicated with general formula (iv), preferably R11、R12And R13Separately for hydrogen atom or Methyl, L1Linking group, the X of divalent for alkylidene or comprising alkylene oxide structure1For oxygen atom or imino group, Z1For carboxylic acid group's Compound.
Also, as the monomer indicated with general formula (v), preferably R11For hydrogen atom or methyl, L1For alkylidene, Z1For carboxylic acid Base, the compound that Y is methine.
Moreover, as the monomer indicated with general formula (vi), preferably R14、R15And R16Be separately hydrogen atom or methyl, L1It is the compound of carboxylic acid group for singly-bound or alkylidene, Z.
Hereinafter, showing the typical example of the monomer (compound) indicated with general formula (iv)~general formula (vi).
As the example of monomer, can enumerate methacrylic acid, crotonic acid, iso-crotonic acid, intramolecular has addition polymerization The reactant of the compound (for example, methacrylic acid 2- ethoxy) of double bond and hydroxyl and succinic anhydride, intramolecular have addition The reactant of the compound and phthalic anhydride of polymeric double bond and hydroxyl, intramolecular have addition polymerization double bond and hydroxyl Compound and the reactant of tetrahydroxy phthalic anhydride, intramolecular have the compound of addition polymerization double bond and hydroxyl with The reactant of trimellitic anhydride, intramolecular have addition polymerization double bond and the compound of hydroxyl and reacting for pyromellitic dianhydride Object, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4- vinylbenzoic acid, second Alkenyl phenol and 4- hydroxyphenylmethyl acryloyl etc..
From with the pigment such as nitrogen titanium particle interaction, dispersion stabilization and examine to the viewpoint of the impregnability of developer solution Consider, has the content of the structural unit for the functional group that can form interaction with pigment such as nitrogen titanium particles relative to macromolecule The gross mass of compound, the preferably 0.05 mass % of mass %~90, the more preferably 1.0 mass % of mass %~80, further Preferably 10 mass of mass %~70 %.
Moreover, in order to improve the various performances such as image intensity, high-molecular compound can not damage effect of the invention Under the premise of, further containing with grafted chain structural unit, hydrophobic structure unit and have can be with nitrogen titanium particle The different other structures unit with various functions of the structural unit for the functional group that equal pigment form interaction is (for example, tool There is the structural unit of functional group affinity with the decentralized medium for dispersion etc.).
As this other structures unit, such as it can enumerate and be originated from the freedom selected from vinyl cyanide and metering system nitrile etc. The structural unit of base polymerizable compound.
High-molecular compound is able to use a kind or these other structures units of more than two kinds, content are changed with quality Calculate, relative to the gross mass of high-molecular compound, preferably 0% or more and 80% hereinafter, especially preferably 10% or more and 60% or less.Content can maintain sufficient patternability within the above range.
The acid value of high-molecular compound is preferably 0mgKOH/g or more and 160mgKOH/g range below, more preferably 10mgKOH/g or more and 140mgKOH/g range below, further preferably 20mgKOH/g or more and 120mgKOH/g or less Range.
If high-molecular compound acid value be 160mgKOH/g hereinafter, if more effectively inhibit form cured film when development In pattern removing.Also, if the acid value of high-molecular compound is 10mgKOH/g or more, alkali-developable is better.And And if the acid value of high-molecular compound is 20mgKOH/g or more, it can more inhibit the heavy of the pigment such as nitrogen titanium particle It forms sediment, oversize grain number can be made less, can more improve the ageing stability of composition.
In the present invention, the acid value of high-molecular compound for example can be by the average content meter of the acidic group in high-molecular compound It calculates.Further, it is possible to be had by the content for changing composition, that is, acidic group structural unit containing high-molecular compound There is the resin of desired acid value.
Height when forming cured film, from the viewpoint of the inhibition and developability that pattern when development is removed, in the present invention Polystyrene scaled value of the weight average molecular weight of molecular compound as GPC (gel permeation chromatography) method of being based on, preferably 4, 000 or more and 300,000 hereinafter, more preferably 5, and 000 or more and 200,000 hereinafter, further preferably 6,000 or more and 100,000 hereinafter, especially preferably 10, and 000 or more and 50,000 or less.
GPC method is based on following method, that is, utilizes HLC-8020GPC (TOSOH CORPORATION. manufacture), as tubing string Use TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel Supe rHZ2000 (TOSOH CORPORATION manufacture, 4.6mmID × 15cm), THF (tetrahydrofuran) is used as eluat.
High-molecular compound can be synthesized according to well known method, the solvent used when as synthetic macromolecular compound, example Dichloroethanes, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethyl alcohol, propyl alcohol, butanol, glycol monoethyl ether, ethylene glycol list can such as be enumerated Ether, 2- methoxyethyl acetate, 1- methoxy-2-propanol, 1- methoxyl group -2- propyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate and ethyl lactate etc..These solvents can be independent Using can also mix two or more come using.
As the concrete example for the high-molecular compound that can be used in the present invention, Kusumoto Chemicals can be enumerated, Ltd. " DA-7301 " is manufactured, BYK Chemie company manufactures " Disperbyk-101 (polyamide-amide phosphate), 107 (carboxylic acids Ester), 110 (copolymers comprising acidic group), 111 (phosphate dispersing agents), 130 (polyamide), 161,162,163,164,165, 166,170,190 (high-molecular copolymer) ", " BYK-P104, P105 (high molecular weight unsaturation polycarboxylic acids) ", the manufacture of EFKA company " EFKA4047,4050~4010~4165 (polyurethane series), EFKA4330~4340 (block copolymer), 4400~4402 (change Property polyacrylate), 5010 (polyesteramides), 5765 (high molecular weight polycarboxylates), 6220 (fatty acid polyesters), 6745 (phthaleins Cyanines derivative), 6750 (azo pigments derivatives) ", Ajinomoto Fine-Techno Co., Inc. manufactures " AJISPER PB821, " (urethane is oligomeric by Floren TG-710 for PB822, PB880, PB881 ", KYOEISHA CHEMICAL CO., LTD manufacture Object) ", " Polyflow No.50E, No.300 (acrylic acid series copolymer) ", Kusumoto Chemicals, Ltd. manufacture " Disparlon KS-860,873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA- 705, DA-725 ", Kao Corporation manufacture " DEMOL RN, N (naphthalenesulfonic acid formalin condensation polymer), MS, C, SN-B (virtue Fragrant race's sulfonic acid formalin polycondensates) ", " Homogenol L-18 (polymeric polycarboxylic acid) ", " EMULGEN 920,930,935, 985 (ethylene nonyl phenyl ethers) ", " ACETAMIN 86 (stearylamine acetate) ", The Lubrinzol Corporatin Manufacture " SOLSPERSE 5000 (phthalocyanine derivates), 22000 (azo pigments derivatives), 13240 (polyesteramines), 3000, 12000,17000,20000,27000 (there is the macromolecule of function part in terminal part), 24000,28000,32000,38500 (graft copolymer) ", Nikko Chemicals CO., Ltd. manufacture " Nikkor T106 (polyoxyethylene sorbitol list oleic acid Ester), MYS-IEX (polyoxyl 40 stearate) ", Kawaken Fine Chemic als CO., Ltd. manufacture Hinoakuto T-8000E etc., Shin-Etsu Chemical CO., Ltd. manufacture poly- organic group siloxane polymer KP341, Yusho CO., Ltd. manufacture " W001: cationic system surfactant ", polyoxyethylene lauryl ether, polyoxyethylene are hard Rouge ether, polyoxyethylene oleyl ether, NONIN HS 240, ethylene nonyl phenyl ether, polyethylene glycol dilaurate, The nonionic surfactants such as polyglycol distearate, fatty acid esters of sorbitan, " W004, W005, W017 " etc. Anionic surfactant, MORISHITA&CO., LTD. manufacture " EFKA-46, EFKA-47, EFKA-47EA, EFKA polymerization Object 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", SAN NOPCO LIMITED manufacture The dispersion such as " Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 " macromolecules Agent, ADEKA CORPORATION manufacture " Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 " and Sanyo Chemical Indust ries, Ltd. system Make " Ionet (trade name) S-20 " etc..Also, Acrylicbase FFS-6752, Acrylicbase FFS- also can be used 187, Akurikyua-RD-F8 and Cyclomer P.
Also, as the commercially available product of amphoteric resin, such as BYK Additives&Instruments manufacture can be enumerated DISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、 DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、 DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno Co., AJISPER PB821 of Inc. manufacture, AJISPER PB822 and AJISPER PB881 etc..
These high-molecular compounds can be used alone, and also can be used in combination of two or more.
In addition, the concrete example as high-molecular compound, can refer to the 0127 of Japanese Unexamined Patent Publication 2013-249417 bulletin The high-molecular compound recorded in~0129 section, these contents are introduced into this specification.
Also, as dispersing agent, other than above-mentioned high-molecular compound, additionally it is possible to use Japanese Unexamined Patent Publication 2010- The graft copolymer on 0037~0115 section (0075~0133 section of column of corresponding US2011/0124824) of No. 106268 bulletins, These contents can be quoted and are introduced into this specification.
Also, other than above-mentioned, additionally it is possible to (corresponding using 0028~0084 section of Japanese Unexamined Patent Publication 2011-153283 bulletin US2011/0279759 0075~0133 section of column) comprising have acidic groups be bonded via linking group made of side chain knot The high-molecular compound of the composition of structure, these contents can be quoted and are introduced into this specification.
When composition contains dispersing agent, total solid content of the content of dispersing agent relative to composition, preferably 0.1~50 Quality %, more preferably 0.5~30 mass %.
Dispersing agent can be used alone a kind, can also be used in combination of two or more.When being used in combination of two or more, preferably total amount becomes above-mentioned Range.
< adhesive resin >
Composition of the invention preferably comprises adhesive resin.
As adhesive resin, it is preferable to use threadlike organic polymers.It, can be any as this threadlike organic polymers Ground uses well known polymer.In order to realize water development or alkalescent water development, it is solvable for preferably selecting to water or alkalescent water Property or bloating tendency threadlike organic polymers.Wherein, as adhesive resin, especially preferably alkali soluble resins (has and promotes The resin of alkali-soluble group).
It, can be from threadlike organic polymers and molecule is (preferably with (methyl) acrylic copolymer as adhesive resin Object or styrene based copolymer are the molecule of main chain) in promote to fit in the alkali soluble resins of alkali-soluble group at least one Work as selection.From the viewpoint of heat resistance, preferably polycarboxylated styrene system resin, polysiloxane series resin, (methyl) propylene Acid resin, (methyl) acrylamide resin, (methyl) acrylic acid/(methyl) acrylamine copolymer resin, from developability control From the viewpoint of system, preferably (methyl) acrylic resin, (methyl) acrylamide resin, (methyl) acrylic acid/(methyl) Acrylamine copolymer resin.
As promoting alkali-soluble group (hereinafter, also referred to acidic group), for example, can enumerate carboxyl, phosphate, sulfonic group and Phenolic hydroxyl group etc..Wherein, the group that preferably dissolves in organic solvent and can be developed by weak alkaline aqueous solution, as more excellent The resin of choosing can enumerate the alkali soluble resins with the structural unit from (methyl) acrylic acid.These acidic groups can be merely 1 Kind, it is also possible to two or more.
As adhesive resin, for example, free radical polyalcohol, such as Japanese Unexamined Patent Publication that there is carboxylic acid group in side chain can be enumerated Clear No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, The resin recorded in Japanese Unexamined Patent Application 54-92723, Japanese Unexamined Patent Application 59-53836 and Japanese Unexamined Patent Application 59-71048, That is, the monomer with carboxyl is independent or makes the resin of its copolymerization, the monomer with acid anhydrides individually or is copolymerized it and to acid anhydrides Unit is hydrolyzed or half-esterification or semi-amidation resin and is changed by unsaturated monocarboxylic and acid anhydrides to epoxy resin The epoxy acrylate etc. of property.As the example of the monomer with carboxyl, can enumerate acrylic acid, methacrylic acid, itaconic acid, bar Beans acid, maleic acid, fumaric acid and 4- carboxyl styrene etc. can enumerate maleic anhydride etc. as the example of the monomer with acid anhydrides. Also, it can also enumerate equally for the acid cellulose derivative that side chain has carboxylic acid group.In addition, to the polymerization with hydroxyl The product of object addition cyclic acid anhydride etc. is more useful.
Also, European Patent No. 993966, European Patent No. 1204000 and Japanese Unexamined Patent Publication 2001-318463 etc. The film-strength for the ethylidene ether modification polyethenol series adhesive resin with acidic group recorded in each bulletin and the balance of developability are excellent It is different, it is preferred.
Moreover, polyvinylpyrrolidone or polyethylene oxide etc. are more useful as water-soluble threadlike organic polymers.And And in order to improve the intensity of cured film, alcohol soluble nylon and 2,2- is bis--(4- hydroxyphenyl)-propane and epoxychloropropane it is anti- Answer object i.e. polyethers etc. also useful.
In particular, in these, (benzyl (methyl) acrylate/(methyl) acrylic acid/as needed for other addition polymerizations Vinyl monomer) copolymer and ((methyl) allyl acrylate/(methyl) acrylic acid/as needed for other addition polymerization second Alkene monomer) film-strength of copolymer, sensitivity and developability balancing good, be preferred.
As commercially available product, for example, can enumerate Acrylicbase FF-187, FF-426 (FUJIKURA KASEI CO., LTD. manufacture), Akurikyua-RD-F8 (NIPPON SHOKUBAI CO., LTD.) and DAICEL-ALLNEX LTD. manufacture Cyclomer P (ACA) 230AA etc..
In the manufacture of adhesive resin, for example, the method based on well known radical polymerization can be applied.This field skill Art personnel can be easy temperature, pressure, radical initiator of the setting by radical polymerization manufacture alkali soluble resins when The polymerizing conditions such as type and its amount and the type of solvent.
Also, as adhesive resin, it is also preferred that using comprising the structural unit with grafted chain and with acidic group (alkali soluble Property base) structural unit polymer.
The definition of structural unit with grafted chain and the structural unit possessed by above-mentioned dispersing agent with grafted chain It is identical, and preferred scope is also identical.
As acidic group, such as have carboxylic acid group, sulfonic group, phosphate or phenolic hydroxyl group etc., preferably carboxylic acid group, sulfonic group and It is at least one kind of in phosphate, more preferably carboxylic acid group.
As the structural unit with acidic group, preferably having to be selected to be originated from is indicated with the following general formula (vii)~general formula (ix) One or more of the structural unit of monomer structural unit.
[chemical formula 7]
In general formula (vii)~general formula (ix), R21、R22And R23Separately indicate hydrogen atom, halogen atom (for example, fluorine is former Son, chlorine atom, bromine atom etc.) or carbon atom number be 1~6 alkyl (for example, methyl, ethyl, propyl etc.).
In general formula (vii)~general formula (ix), R21、R22And R23It is preferred that be separately hydrogen atom or carbon atom number be 1~ 3 alkyl is more preferably separately hydrogen atom or methyl.In general formula (vii), R21And R23It is particularly preferably respectively that hydrogen is former Son.
X in general formula (vii)2Indicate oxygen atom (- O-) or imino group (- NH-), preferably oxygen atom.
Also, the Y in general formula (viii) indicates methine or nitrogen-atoms.
Also, the L in general formula (vii)~general formula (ix)2Indicate the linking group of singly-bound or divalent.Linker as divalent The example of group can enumerate the fatty group of divalent (for example, alkylidene, substituted alkylene, alkenylene, substitution alkenylene, alkynylene And replace alkynylene), the aromatic series base of divalent (for example, arlydene and replace arlydene), the heterocycle of divalent, oxygen atom (- O-), Sulphur atom (- S-), imino group (- NH-), substituted imino key (- NR41'-, wherein R41' it is fatty group, aromatic series base or heterocycle Base), carbonyl key (- CO-) and their combination etc..
The fatty group of divalent can have cyclic structure or branched structure.The carbon atom number of fatty group is preferably 1~20, More preferably 1~15, further preferably 1~10.It is more preferably full with unsaturated aliphatic base phase ratio about fatty group And fatty group.Also, fatty group can have substituent group.As the example of substituent group, halogen atom, hydroxyl, fragrance can be enumerated Race's base and heterocycle.
The carbon atom number of the aromatic series base of divalent is preferably 6~20, and more preferably 6~15, further preferably 6~10.And And aromatic series base can have substituent group.The example of substituent group can enumerate halogen atom, hydroxyl, fatty group, aromatic series base and heterocycle Base.
The heterocycle of divalent preferably has 5 member rings or 6 member rings as heterocycle.Other heterocycles, aliphatic can have been condensed on heterocycle 1 or more in ring or aromatic ring.Also, heterocycle can have substituent group.As the example of substituent group, halogen original can be enumerated Son, hydroxyl, oxo base (=O), thio group (=S), imino group (=NH), substituted imido (=N-R42, wherein R42For fat Race's base, aromatic series base or heterocycle), fatty group, aromatic series base and heterocycle.
L2The preferably linking group of singly-bound, alkylidene or the divalent comprising alkylene oxide structure.Alkylene oxide structure is more preferably Ethylene oxide structure or oxypropylene structure.Also, L2It may include the polyoxyalkylene knot for repeating the alkylene oxide structure comprising 2 or more Structure.As polyoxyalkylene structure, preferably polyoxyethylene structure or polyoxypropylene structure.Polyoxyethylene structure is with-(OCH2CH2) N- indicates that n is preferably 2 or more integer, more preferably 2~10 integer.
In general formula (vii)~general formula (ix), Z2For acidic group, preferably carboxylic acid group.
In general formula (ix), R24、R25And R26Separately indicate hydrogen atom, halogen atom (for example, fluorine atom, chlorine atom, Bromine atom etc.), carbon atom number be 1~6 alkyl (for example, methyl, ethyl, propyl etc.) ,-Z2Or L2-Z2.Wherein, L2And Z2's Meaning and L among the above2And Z2Identical, preferred example is also identical.As R24、R25And R26, separately preferably hydrogen atom Or carbon atom number is 1~3 alkyl, more preferably hydrogen atom.
In the present invention, as the monomer indicated with general formula (vii), preferably R21、R22And R23It is separately hydrogen atom Or methyl, L2Linking group, the X of divalent for alkylidene or comprising alkylene oxide structure2For oxygen atom or imino group, Z2For carboxylic acid group Compound.
Also, as the monomer indicated with general formula (vii), preferably R21For hydrogen atom or methyl, L2For alkylidene, Z2For Carboxylic acid group, the compound that Y is methine.
Moreover, as the monomer indicated with general formula (ix), preferably R24、R25And R26It is separately hydrogen atom or first Base, Z2For the compound of carboxylic acid group.
Above-mentioned adhesive resin can by with above-mentioned comprising having the dispersing agent of structural unit of grafted chain identical Method synthesis, also, its preferred acid number, weight average molecular weight are also identical.
Above-mentioned adhesive resin can have the one kind or two or more structural unit with acidic group.
The content of structural unit with acidic group is excellent relative to the gross mass of above-mentioned adhesive resin in terms of mass conversion 5~95% are selected as, from the viewpoint of the damage for inhibiting the image intensity based on alkali development, more preferably 10~90%.
Total solid content of the content of adhesive resin in composition of the invention relative to composition, preferably 0.1 ~30 mass %, more preferably 0.3~25 mass %.
Adhesive resin can be used alone a kind, can also be used in combination of two or more.When being used in combination of two or more, preferably total amount becomes Above range.
In composition of the invention, content ratio (dispersing agent/contain of the above-mentioned dispersing agent relative to above-mentioned nitrogen titanium particle Titanium nitride particle is (hereinafter, also referred to " D/P ".) mass ratio) it is preferably 0.3 hereinafter, more preferably 0.05~0.3, it is further excellent It is selected as 0.1~0.3.By the way that containing within the above range than D/P, the performance reproducibility of dispersion liquid is excellent, and the figure of cured film Case formative (resolution ratio) is also excellent.
< polymerizable compound >
Composition of the invention preferably comprises polymerizable compound.
Polymerizable compound preferably includes the compound of 1 or more the group with ethylenic unsaturated bond, more preferably For the compound with 2 or more, further preferably there are 3 or more, particularly preferably there are 5 or more.The upper limit is, for example, 15 It is a following.As the group with ethylenic unsaturated bond, for example, vinyl, (methyl) allyl and (methyl) propylene can be enumerated Acyl group etc..
Polymerizable compound for example can be monomer, prepolymer and oligomer and their mixture and their poly Any of chemical forms such as body, preferably monomer.
The molecular weight of polymerizable compound is preferably 100~3000, and more preferably 250~1500.
Polymerizable compound is preferably (methyl) acrylate compounds of 3~15 functions, more preferably 3~6 functions (methyl) acrylate compounds.
As monomer, the example of prepolymer, can enumerate unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, Crotonic acid, iso-crotonic acid, maleic acid etc.) and its esters, amides and their polymer, preferably unsaturated carboxylic acid with The ester and unsaturated carboxylic acid of aliphatic polybasic alcoholic compound and the amides of aliphatic polybasic amine compounds and theirs is more Aggressiveness.Also, esters of unsaturated carboxylic acids or acyl with the nucleophilic substitutions base such as hydroxyl, amino, sulfydryl can also be suitably used The addition reaction or above-mentioned esters of unsaturated carboxylic acids or acyl of amine and simple function or polyfunctional isocyanate's class or epoxies Amine and simple function or the dehydration condensation object of polyfunctional carboxylic acid etc..Also, it is also preferred that having isocyanate group, epoxy group The esters of unsaturated carboxylic acids or amides and simple function of equal electrophilicities substituent group or polyfunctional alcohols, amine, thio-alcohol Reactant, the esters of unsaturated carboxylic acids with the separation properties substituent group such as halogen radical or tosyl or amides and simple function or Polyfunctional alcohols, amine, thio-alcohol reactant.Also, can also replace above-mentioned unsaturated carboxylic acid, using unsaturated phosphonic acids, The styrene derivatives such as styrene and the compound group for being substituted by vinyl ethers, allyl ether etc..
As their particular compound, Japanese Unexamined Patent Publication 2009-288705 bulletin also can be suitably used in the present invention (0095)~(0108) section in the compound recorded.
In the present invention, as polymerizable compound, it is also preferred that comprising 1 or more the group with ethylenic unsaturated bond, And there is the compound of 100 DEG C or more of boiling point under normal pressure.As its example, for example, Japanese Unexamined Patent Publication 2013- can be referred to 0227 section of No. 29760 bulletins, the compound recorded in 0254~0257 section of Japanese Unexamined Patent Publication 2008-292970 bulletin, should Content is introduced into this specification.
Polymerizable compound is preferably dipentaerythritol triacrylate (as commercially available product, KAYARAD D-330； Nippon Kayaku CO., Ltd. manufacture), dipentaerythritol tetraacrylate is (as commercially available product, KAYARAD D-320； Nippon Kayaku CO., Ltd. manufacture), dipentaerythritol five (methyl) acrylate is (as commercially available product, KAYARAD D- 310；Nippon Kayaku CO., Ltd. manufacture), dipentaerythritol six (methyl) acrylate is (as commercially available product, KAYARAD DPHA；Nippon Kayaku CO., Ltd. manufacture, A-DPH-12E；Shin-Nakamura Chemical Co., Ltd manufacture) And these (methyl) acryloyl groups via glycol residue, diol residues structure (for example, by Sartomer company Inc. commercially available SR454, SR499).Their oligomer types can also be used.Also, NK ester A-TMMT can also be used (pentaerythritol tetraacrylate, Shin-Nakamura Chemical Co., Ltd manufacture) and KAYARAD RP-1040 (Nippon Kayaku CO., Ltd. manufacture) etc..
The mode of preferred polymeric compound described below.
Polymerizable compound can have the acidic groups such as carboxyl, sulfonic group and phosphate.As the polymerism chemical combination with acidic group Object, the preferably ester of aliphatic poly hydroxy compounds and unsaturated carboxylic acid, more preferably make non-aromatic carboxylic acid anhydrides and aliphatic The unreacted hydroxyl of poly hydroxyl compound is reacted to make it have the polymerizable compound of acidic group, further preferably should In ester, aliphatic poly hydroxy compounds is the compound of pentaerythrite and/or dipentaerythritol.As commercially available product, for example, can lift ARONIX TO-2349, M-305, M-510 and M-520 etc. of TOAGOSEI CO. out, LTD. manufacture.
It is 0.1~40mgKOH/g as the preferred acid number of the polymerizable compound with acidic group, more preferably 5~ 30mgKOH/g.If the acid value of polymerizable compound is 0.1mgKOH/g or more, the dissolution characteristics that develop are good, if 40mgKOH/g is hereinafter, then in manufacture and operate upper advantageous.Moreover, photopolymerization is functional and curability is excellent.
About polymerizable compound, the compound with caprolactone structure is also preferred embodiment.
As the compound with caprolactone structure, as long as having caprolactone structure in the molecule, it is not particularly limited, For example, can enumerate by making trimethylolethane, two trimethylolethanes, trimethylolpropane, two trimethylolpropanes, season The polyalcohols such as penta tetrol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylol melamine and (methyl) propylene Acid and 6-caprolactone are esterified come the modified multifunctional (methyl) acrylate of obtaining, 6-caprolactone.Wherein, it is however preferred to have With the compound for the caprolactone structure that the following general formula (Z-1) indicates.
[chemical formula 8]
In general formula (Z-1), 1~5 in all groups indicated with the following general formula (Z-2) of 6 R or 6 R for The group that the following general formula (Z-2) indicates, remaining as the group indicated with the following general formula (Z-3).
[chemical formula 9]
In general formula (Z-2), R1Indicate that hydrogen atom or methyl, m indicate 1 or 2 number, " * " is expressed as connecting key.
[chemical formula 10]
In general formula (Z-3), R1Indicate that hydrogen atom or methyl, " * " are expressed as connecting key.
Polymerizable compound with caprolactone structure is for example by Nippon Kayaku CO., and Ltd. is as KAYARAD DPCA series and it is commercially available, DPCA-20 (in above-mentioned formula (Z-1)~(Z-3), m=1, with number=2 for the group that formula (Z-2) indicates, R1The compound of all hydrogen atoms), DPCA-30 (same to formula, m=1, with the number=3, R for the group that formula (Z-2) indicates1It is all The compound of hydrogen atom), DPCA-60 (same to formula, m=1, with the number=6, R for the group that formula (Z-2) indicates1All hydrogen atoms Compound) and DPCA-120 (in formula, m=2, with the number=6, R for the group that formula (Z-2) indicates1The chemical combination of all hydrogen atoms Object) etc..
Polymerizable compound can also use the compound indicated with the following general formula (Z-4) or (Z-5).
[chemical formula 11]
In general formula (Z-4) and (Z-5), E separately indicates-((CH2)yCH2O)-or-((CH2)yCH(CH3) O)-, y Separately indicate that 0~10 integer, X separately indicate (methyl) acryloyl group, hydrogen atom or carboxyl.
In general formula (Z-4), (methyl) acryloyl group adds up to 3 or 4, m separately indicate 0~10 it is whole Number, the integer for adding up to 0~40 of each m.
In general formula (Z-5), (methyl) acryloyl group adds up to 5 or 6, n separately indicate 0~10 it is whole Number, the integer for adding up to 0~60 of each n.
In general formula (Z-4), m is preferably 0~6 integer, more preferably 0~4 integer.
Also, the integer of the total preferably 2~40 of each m, more preferably 2~16 integer, further preferably 4~8 Integer.
In general formula (Z-5), n is preferably 0~6 integer, more preferably 0~4 integer.
Also, the integer of the total preferably 3~60 of each n, more preferably 3~24 integer, further preferably 6~12 Integer.
Also, in general formula (Z-4) or general formula (Z-5)-((CH2)yCH2O)-or-((CH2)yCH(CH3) O)-it is preferably oxygen The form that the end of atom side is bonded with X.
It can be used alone a kind, can also be used in combination of two or more with the compound that general formula (Z-4) or general formula (Z-5) indicate.In particular, In general formula (Z-5), the form of the preferably 6 all acryloyl groups of X, 6 all acryloyl groups of X in general formula (Z-5) At least one in compound and 6 X is the mode of the mixture of the compound of hydrogen atom.By being set as this structure, Neng Gougeng Add raising developability.
Also, as total content of the compound indicated with general formula (Z-4) or general formula (Z-5) in polymerizable compound, Preferably 20 mass % or more, more preferably 50 mass % or more.
The compound indicated using general formula (Z-4) or general formula (Z-5) can be closed by the process as known process At, that is, by opening, the process for being bonded ethylene oxide or propylene oxide with pentaerythrite or dipentaerythritol； And (methyl) acryloyl chloride is for example made to react the process to import (methyl) acryloyl group with the terminal hydroxyl of open loop skeleton.Each work Sequence is well-known process, and those skilled in the art can be readily synthesized the compound indicated with general formula (Z-4) or (Z-5).
In the compound indicated with general formula (Z-4) or general formula (Z-5), more preferably pentaerythritol derivative and/or double seasons Penta tetraalcohol derivative.
Specifically, the compound indicated with following formula (a)~(f) can be enumerated, wherein preferably exemplary compounds (a), (b)、(e)、(f)。
[chemical formula 12]
[chemical formula 13]
As the commercially available product of the polymerizable compound indicated with general formula (Z-4), (Z-5), such as Sartomer can be enumerated 4 functional acrylates with 4 ethylene oxide chains, that is, SR-494, the Nippon Kayaku CO. of company Inc. manufacture, Ltd. the 6 functional acrylates i.e. DPCA-60 with 6 pentylidene oxygen (pentyleneoxy) chains that manufactures and have 3 it is different 3 functional acrylates, that is, TPA-330 etc. of butylene oxygen chain.
As polymerizable compound, it is also preferred that such as Japanese Patent Publication 48-41708 bulletin, Japanese Unexamined Patent Application 51-37193 The urethane acrylate class recorded in number bulletin, Japanese Patent Publication 2-32293 bulletin and Japanese Patent Publication 2-16765 bulletin With Japanese Patent Publication 58-49860 bulletin, Japanese Patent Publication 56-17654 bulletin, Japanese Patent Publication 62-39417 bulletin And the urethane compound class with ethylene oxide pastern bone frame recorded in Japanese Patent Publication 62-39418 bulletin.Also, pass through Use Japanese Unexamined Patent Application 63-277653 bulletin, Japanese Unexamined Patent Application 63-260909 bulletin and Japanese Unexamined Patent Publication 1-105238 Addition polymerization compounds recording in bulletin, having amino structure and sulfide based structural in the molecule, can obtain photosensitive The very excellent composition of speed.
As commercially available product, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku PulpCO., Ltd. can be enumerated Manufacture), UA-7200 (Shin-Nakamura Chemical Co., Ltd manufacture), DPHA-40H (Nippon Kayaku CO., Ltd. manufacture), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (KYOEISHA CHEMICAL CO., LTD manufacture) etc..
Also, preferred SP (solubility parameter) value of polymerizable compound used in the present invention is 9.50 or more, more preferably It is 10.40 or more, further preferably 10.60 or more.
In addition, about SP value, unless otherwise specified, then finding out (H.L.Hoy Journal by Hoy method in this specification Of Painting, 1970, Vol.42,76-118).Also, it for SP value, omits unit and shows, but its unit is cal1/ 2cm-3/2。
Also, from the viewpoint of reducing development residue, it is also preferred that composition includes the polymerism with Cardo skeleton Close object.
As the polymerizable compound with Cardo skeleton, it is however preferred to have the polymerism of 9,9- diaryl fluorene skeletons Close object, the compound more preferably indicated with following formula (Q3).
General formula (Q3)
[chemical formula 14]
In above-mentioned general formula (Q3), Ar11~Ar14Separately indicate the aryl of the phenyl ring comprising surrounding with dotted line.X1~ X4Separately indicate that the substituent group with polymerizable group, the carbon atom in above-mentioned substituent group can be exchanged for heteroatoms.A and B separately indicates that 1~5 integer, c and d separately indicate 0~4 integer.R1~R4It separately indicates to take Dai Ji, e, f, g and h separately indicate 0 or more integer, and the upper limit value of e, f, g and h are respectively from Ar11~Ar14It can The number for the substituent group having subtracts the value of a, b, c or d.Wherein, Ar11~Ar14Separately being as one of condensed ring includes With dotted line surround phenyl ring Ppolynuclear aromatic alkyl when, X1~X4And R1~R4It can separately be substituted by and be surrounded with dotted line Phenyl ring, also can use on behalf of the ring other than the phenyl ring surrounded with dotted line.
In above-mentioned general formula (Q3), Ar11~Ar14The aryl of the represented phenyl ring comprising being surrounded with dotted line is preferably carbon original The aryl of subnumber 6~14, the more preferably aryl (for example, phenyl, naphthalene) of carbon atom number 6~10, further preferably phenyl (being limited to the phenyl ring surrounded with dotted line).
In above-mentioned general formula (Q3), X1~X4The substituent group with polymerizable group is separately indicated, in above-mentioned substituent group Carbon atom can be exchanged for heteroatoms.As X1~X4The represented substituent group with polymerizable group, there is no particular restriction, But preferably with the fatty group of polymerizable group.
As with X1~X4The fatty group of represented polymerizable group, there is no particular restriction, but preferably polymerism The alkylidene that carbon atom number other than group is 1~12, the more preferably alkylidene of carbon atom number 2~10, further preferably The alkylidene of carbon atom number 2~5.
Also, there is X1~X4In the fatty group of represented polymerizable group, above-mentioned fatty group is exchanged for heteroatoms When, preferably replaced by-NR- (R is substituent group), oxygen atom or sulphur atom, non-conterminous-CH in more preferable above-mentioned fatty group2- Replaced by oxygen atom or sulphur atom, non-conterminous-CH in further preferred above-mentioned fatty group2Replaced by oxygen atom.It is preferred that having There is X1~X4It is exchanged for heteroatoms at the 1~2 of the fatty group of represented polymerizable group, is more preferably exchanged for heteroatoms 1 Place, further preferably and Ar11~Ar14The aryl of the represented phenyl ring comprising being surrounded with dotted line it is adjacent 1 at taken by hetero atom Generation.
As with X1~X4The polymerizable group for including in the fatty group of represented polymerizable group, preferably can The polymerizable group of free radical polymerization or cationic polymerization is enough carried out (hereinafter, being also referred to as radically polymerizable group group and sun Photopolymerizable group).
As radically polymerizable group group, it is able to use usually known radically polymerizable group group, as preferred poly- Conjunction property group, can enumerate the polymerizable group with the ethylenic unsaturated bond for being able to carry out free radical polymerization, specifically, can Enumerate vinyl, (methyl) acryloxy etc..Wherein, preferably (methyl) acryloxy, more preferably acryloxy.
As cationic polymerizable group, it is able to use usually known cationic polymerizable group, specifically, can Enumerate ester ring type ether, cyclic acetal base, annular lactone base, cyclic thioether base, spiro orthoester base and ethyleneoxy etc..Its In, preferably ester ring type ether or ethyleneoxy, especially preferably epoxy group, oxetanylmethoxy or ethyleneoxy.
Ar11~AR14Above-mentioned polymerizable group possessed by the substituent group for being included is preferably radically polymerizable group group.
Ar11~AR14In 2 or more comprising with polymerizable group substituent group, preferably Ar11~AR14In 2~4 Comprising the substituent group with polymerizable group, more preferable Ar11~AR14In 2 or 3 comprising with polymerizable group substitution Base, further preferred Ar11~AR14In 2 comprising with polymerizable group substituent group.
Ar11~Ar14The separately Ppolynuclear aromatic alkyl as one of condensed ring to include the phenyl ring surrounded with dotted line When, X1~X4It can be separately substituted by the phenyl ring surrounded with dotted line, other than also can use on behalf of the phenyl ring surrounded with dotted line Ring.
In above-mentioned general formula (Q3), a and b separately indicate 1~5 integer, preferably 1 or 2, more preferably a and b are equal It is 1.
In above-mentioned general formula (Q3), c and d separately indicate 0~5 integer, preferably 0 or 1, more preferably c and d are equal It is 0.
In above-mentioned general formula (Q3), R1~R4Separately indicate substituent group.As R1~R4Represented substituent group, and It is not particularly limited, for example, halogen atom, halogenated alkyl, alkyl, alkenyl, acyl group, hydroxyl, hydroxy alkyl, alcoxyl can be enumerated Base, aryl, heteroaryl and alcyl etc..R1~R4Represented substituent group is preferably alkyl, alkoxy or aryl, more preferably The alkoxy or phenyl of the alkyl of carbon atom number 1~5, carbon atom number 1~5, further preferably methyl, methoxyl group or phenyl.
In above-mentioned general formula (Q3), Ar11~Ar14It is separately the phenyl ring as one of condensed ring comprising being surrounded with dotted line Ppolynuclear aromatic alkyl when, R1~R4It can be separately substituted by the phenyl ring surrounded with dotted line, also can use on behalf of with dotted line packet Ring other than the phenyl ring enclosed.
In above-mentioned general formula (Q3), e, f, g and h separately indicate 0 or more integer, the upper limit value difference of e, f, g and h For from Ar11~Ar14The number for the substituent group that can have subtracts the value of a, b, c or d.
E, f, g and h are separately preferably 0~8, more preferably 0~2, further preferably 0.
Ar11~Ar14The separately Ppolynuclear aromatic alkyl as one of condensed ring to include the phenyl ring surrounded with dotted line When, e, f, g and h are preferably 0 or 1, more preferably 0.
As the compound indicated with above-mentioned formula (Q3), for example, [the 4- (2- acryloyloxyethoxy) of 9,9- bis- can be enumerated Phenyl] fluorenes etc..As the polymerizable compound with 9,9- diaryl fluorene skeleton, additionally it is possible to which it is preferable to use Japanese Unexamined Patent Publication 2010- The compounds that No. 254732 bulletins are recorded.
When composition of the invention contains polymerizable compound, the content of polymerizable compound is relative to the total solid of composition Body ingredient, preferably 0.1~40 mass %.Lower limit is for example more preferably 0.5 mass % or more, further preferably 1 mass % More than.The upper limit is for example more preferably 30 mass % hereinafter, further preferably 20 mass % or less.
Polymerizable compound can be independent a kind, can also be used in combination of two or more.When being used in combination of two or more, total amount preferably at For above range.
< polymerization initiator >
Composition of the invention preferably has polymerization initiator.
As polymerization initiator, there is no particular restriction, can suitably select from well known polymerization initiator, for example, excellent Choosing has photosensitive polymerization initiator (so-called Photoepolymerizationinitiater initiater).
Composition of the invention also contains Photoepolymerizationinitiater initiater and above-mentioned polymerism chemical combination other than nitrogen titanium particle When object, solidified by the irradiation of activation light or radioactive ray, therefore sometimes referred to as " photosensitive composite ".
As Photoepolymerizationinitiater initiater, as long as having the ability for the polymerization for causing polymerizable compound, there is no particular restriction, It can suitably be selected from well known Photoepolymerizationinitiater initiater.For example, it is preferable to for from ultraviolet range to luminous ray have sense The polymerization initiator of photosensitiveness.Also, the photosensitizer that polymerization initiator can be and be optically excited generates certain effects, and generates work The activating agent of free love base is also possible to the type according to monomer and causes the initiator of cationic polymerization.
Also, Photoepolymerizationinitiater initiater preferably comprise it is at least one kind of about 300nm~800nm (more preferably 330nm~ 500nm.) in the range of at least about 50 molar absorption coefficients compound.
As Photoepolymerizationinitiater initiater, for example, halogenation hydrocarbon derivative can be enumerated (for example, with triazine skeleton person, having and disliking two Azoles skeleton person etc.), the oxime compounds, organic peroxy such as acylphosphine compounds, hexa-aryl bi-imidazole, the 9 oxime derivate such as acylphosphine oxide Compound, thio-compounds, ketone compound, aromatic series salt, ketoxime ether, aminoacetophenone compounds and hydroxy acetophenone etc..Make For the above-mentioned halogenated hydrocarbon compound with triazine skeleton, if for example, Lin Dengzhu, Bull.Chem.Soc.Japan can be enumerated, 42, Compound, the Japanese Unexamined Patent Application 53- of compound, the record of No. 1388492 specifications of British patent that 2924 (1969) are recorded The compound of compound, the record of No. 3337024 specifications of Deutsche Bundespatent that No. 133428 bulletins are recorded is based on F.C.Schaef The J.Org.Chem. of er etc.；29, the change of 1527 (1964) are recorded compound, the record of Japanese Unexamined Patent Application 62-58241 bulletin Close the compound that object, the compound that Japanese Unexamined Patent Publication 5-281728 bulletin is recorded, Japanese Unexamined Patent Publication 5-34920 bulletin are recorded And the compound etc. recorded in No. 4212976 specifications of U.S. Patent No..
Also, from the viewpoint of exposure sensitivity, it is preferably selected from by trihalomethyl triaizine compounds, benzyl dimethyl Ketal compound, alpha-hydroxyacetone compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide compound, metallocene chemical combination Object, oxime compound, triarylimidazoles dimer, class compound, benzothiazole compound, benzophenone cpd, acetophenone Compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halogenated methyl oxadiazole compound and 3- aryl take For the compound in the group of coumarin compound composition.
Further preferably trihalomethyl triaizine compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide chemical combination Object, oxime compound, triarylimidazoles dimer, class compound, benzophenone cpd, acetophenone compound, particularly preferably For selected from by trihalomethyl triaizine compounds, α-aminoketone compound, oxime compound, triarylimidazoles dimer and benzophenone At least one kind of compound in the group of compound composition.
In particular, needing when making the photomask of solid-state imager using composition of the invention with sharp keen shape shape At fine pattern, therefore it is important for without residue developing together with curability in unexposed portion.From this point of view, especially It is preferable to use oxime compounds as Photoepolymerizationinitiater initiater.In particular, when forming fine pattern in solid-state imager, solidification exposure It is exposed in light using stepping, but the exposure machine is damaged by halogen sometimes, it is also necessary to inhibit the additive amount of Photoepolymerizationinitiater initiater It is lower, therefore, if considering these aspects, when forming the fine pattern such as solid-state imager, as Photoepolymerizationinitiater initiater, Particularly preferably use oxime compound.Also, it, being capable of more optimized color transfer by using oxime compound.
As the concrete example of Photoepolymerizationinitiater initiater, for example, the 0265 of Japanese Unexamined Patent Publication 2013-29760 bulletin can be referred to ~0268 section, which is incorporated into present specification.
As Photoepolymerizationinitiater initiater, hydroxy acetophenone compound, aminoacetophenone compounds and acyl can also be suitably used Base phosphine compound.More specifically, for example, the aminobenzene recorded in Japanese Unexamined Patent Publication 10-291969 bulletin can also be used The acylphosphanes series initiators recorded in No. 4225898 ethyl ketone series initiators, Japanese Patent No. bulletins.
As hydroxy acetophenone series initiators, it is able to use IRGACURE-184, DAROCUR-1173, IRGACURE- 500, IRGACURE-2959 and IRGACURE-127 (trade name: being BASF AG's manufacture).
As aminoacetophenone series initiators, it is able to use IRGACURE-907, IRGACURE-369 as commercially available product And IRGACURE-379EG (trade name: being BASF AG's manufacture).Aminoacetophenone series initiators, which can also use, absorbs wave The compound recorded in the matched Japanese Unexamined Patent Publication 2009-191179 bulletins of long wavelength optical light sources such as long and 365nm or 405nm.
As acylphosphanes series initiators, it is able to use IRGACURE-819 and the DAROCUR-TPO (commodity as commercially available product Name: being BASF AG's manufacture).
As Photoepolymerizationinitiater initiater, it may be more preferable to enumerate oxime compound.In particular, oxime series initiators are highly sensitive and polymerize Efficiency is higher, can independently be solidified with color material concentration, is easily designed as the concentration of color material higher therefore preferred.
As the concrete example of oxime compound, it is able to use compound, the day of the record of Japanese Unexamined Patent Publication 2001-233842 bulletin The compound that the compound and Japanese Unexamined Patent Publication 2006-342166 bulletin that this special open 2000-80068 bulletin is recorded are recorded.
In the present invention as can it is preferable to use oxime compound, for example, 3- Benzoyloxyimino fourth can be enumerated Alkane -2- ketone, 3- Acetyloxyimino butane -2- ketone, 3- propionyloxy iminobutanes -2- ketone, 2- Acetyloxyimino Pentane -3- ketone, 2- Acetyloxyimino -1- phenyl-propane -1- ketone, 2- Benzoyloxyimino -1- phenyl-propane -1- Ketone, 3- (4- tosyloxy) iminobutanes -2- ketone and 2- ethyoxyl carbonyloxy group imino group -1- phenyl-propane -1- ketone etc..
Also, it can also enumerate J.C.S.Perkin II (1979) pp.1653-1660, J.C.S.Perk in II (1979) pp.156-162, Journal of Photopolymer Science and Technology (nineteen ninety-five) Pp.202-232, the compound of Japanese Unexamined Patent Publication 2000-66385 bulletin record, Japanese Unexamined Patent Publication 2000-80068 bulletin, special table The compound etc. recorded in each bulletin of 2004-534797 bulletin and Japanese Unexamined Patent Publication 2006-342166 bulletin.
In commercially available product, it also may be preferable for use IRGACURE-OXE01 (BASF AG's manufacture), IRGACURE-OXE02 (BASF Company's manufacture).Also, it can also enough TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.'s manufacture), Adeka Arkls NCI-831 and Adeka Arkls NCI-930 (ADEKA COR PORATION manufacture).Further, it is possible to use N-1919 (ADEKA CORPORATION manufacture).
Also, as the oxime compound in addition to above-mentioned record, it may be used at the carbazole N Japanese Unexamined Patent Application Publications for being linked with oxime The compound recorded in 2009-519904 bulletin is imported with the U.S. Patent No. of miscellaneous substituent group at diphenylketone position The compound recorded in No. 7626957 bulletins, pigment position be imported with nitro Japanese Unexamined Patent Publication 2010-15025 bulletin and The compound of U.S. Patent Publication 2009-292039 record, the ketone recorded in published International patent 2009-131189 bulletin Oxime compound, the chemical combination recorded in No. 7556910 bulletins of United States Patent (USP) that same intramolecular contains triazine skeleton and oxime skeleton Object and 405nm with maximum absorption and to g ray source have good sensitivity Japanese Unexamined Patent Publication 2009-221114 public affairs Report the compound etc. recorded.
Such as can be preferably with reference to 0274~0275 section of Japanese Unexamined Patent Publication 2013-29760 bulletin, which introduces this theory In bright book.
Specifically, as oxime compound, the compound that is preferably indicated with following formula (OX-1).In addition, the N-O key of oxime The oxime compound that can be (E) body is also possible to the oxime compound of (Z) body, can also be the mixture of (E) body Yu (Z) body.
[chemical formula 15]
In general formula (OX-1), R and B separately indicate that the substituent group of monovalence, A indicate the organic group of divalent, Ar table Show aryl.
As in general formula (OX-1) with the substituent group of the R monovalence indicated, the preferably nonmetallic atom group of monovalence.
As the nonmetallic atom group of monovalence, can enumerate alkyl, aryl, acyl group, alkoxy carbonyl group, aryloxy carbonyl, heterocycle, Alkyl thiocarbonyl and thiocarbonyl aryl etc..Also, these groups can have 1 or more substituent group.Also, it is above-mentioned to take Dai Jike is further replaced by other substituent groups.
As substituent group, can enumerate halogen atom, aryloxy group, alkoxy carbonyl group or aryloxy carbonyl, acyloxy, acyl group, alkyl and Aryl etc..
As in general formula (OX-1) with the substituent group of the B monovalence indicated, preferably aryl, heterocycle, aryl carbonyl or miscellaneous Cyclocarbonyl.These groups can have 1 or more substituent group.As substituent group, substituent group above-mentioned can be illustrated.
As in general formula (OX-1) with the organic group of the A divalent indicated, preferably the alkylidene of carbon atom number 1~12, Cycloalkylidene or alkynylene.These groups can have 1 or more substituent group.As substituent group, substitution above-mentioned can be illustrated Base.
In the present invention, as Photoepolymerizationinitiater initiater, additionally it is possible to use the oxime compound with fluorine atom.As with fluorine original The concrete example of the oxime compound of son can enumerate compound, the Japanese Unexamined Patent Application Publication of the record of Japanese Unexamined Patent Publication 2010-262028 bulletin The compound that the compound 24,36~40 and Japanese Unexamined Patent Publication 2013-164471 bulletin that 2014-500852 bulletin is recorded are recorded (C-3) etc..The content is introduced into this specification.
In the present invention, as Photoepolymerizationinitiater initiater, additionally it is possible to use the compound indicated with the following general formula (1) or (2).
[chemical formula 16]
In formula (1), R1And R2Separately indicate the alkyl of carbon atom number 1~20, the ester ring type of carbon atom number 4~20 The aralkyl of alkyl, the aryl of carbon atom number 6~30 or carbon atom number 7~30, R1And R2When for phenyl, phenyl is bonding each other And fluorenyl is formed, R3And R4Separately indicate hydrogen atom, the alkyl of carbon atom number 1~20, carbon atom number 6~30 aryl, The aralkyl of carbon atom number 7~30 or the heterocycle of carbon atom number 4~20, X indicate singly-bound or carbonyl.
In formula (2), R1、R2、R3And R4Meaning and formula (1) in R1、R2、R3And R4It is identical, R5Expression-R6、-OR6、- SR6、-COR6、-CONR6R6、-NR6COR6、-OCOR6、-COOR6、-SCOR6、-OCSR6、-COSR6、-CSOR6,-CN, halogen atom Or hydroxyl, R6Indicate the alkyl of carbon atom number 1~20, the aryl of carbon atom number 6~30, carbon atom number 7~30 aralkyl or The heterocycle of carbon atom number 4~20, X indicate that singly-bound or carbonyl, a indicate 0~4 integer.
In above-mentioned formula (1) and formula (2), R1And R2It is separately preferably methyl, ethyl, n-propyl, isopropyl, hexamethylene Base or phenyl.R3Preferably methyl, ethyl, phenyl, tolyl or xylyl.R4Preferably the alkyl of carbon atom number 1~6 or Phenyl.R5Preferably methyl, ethyl, phenyl, tolyl or naphthalene.X is preferably singly-bound.
As the concrete example of the compound indicated with formula (1) and formula (2), for example, Japanese Unexamined Patent Publication 2014-137466 can be enumerated The compound recorded in the paragraph 0076~0079 of number bulletin.The content is introduced into this specification.
It is described below can in the present invention it is preferable to use oxime compound concrete example, but the present invention is not limited to this A bit.
[chemical formula 17]
In the present invention, as Photoepolymerizationinitiater initiater, additionally it is possible to use the oxime compound with benzofuran skeleton.
As concrete example, the OE-01~OE-75 recorded in WO2015/036910 bulletin can be enumerated.
Also, it as commercially available polymerization initiator, is not particularly limited, can also enumerate BASF JAPAN LTD. manufacture IRGACURE OXE 01 (1.2- acetyl caproyl, 1- [4- (thiophenyl)-, 2- (O- benzoyl oxime)]), 02 (second of IRGACURE OXE Ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl oxime)), 2- (acetoxyl group imido Ylmethyl) thioxanthene-9-one, O- acyl group oxime compound is (for example, ADEKA CORPORATION ADEKAOPTOMER N- 1919, Adeka Arkls NCI-831), Adeka ArklsNCI-930, IRGACURE-OXE03, IRGACURE-OXE04 etc., These contents are introduced into this specification.
Oxime compound is preferably the wavelength region in 350nm~500nm with the oxime compound of maximum absorption wavelength, more excellent It is selected as the oxime compound that there is maximum absorption wavelength in the wavelength region of 360nm~480nm, especially preferably 365nm and 405nm The higher oxime compound of absorbance.
In oxime compound, about the molar absorption coefficient in 365nm or 405nm, from the viewpoint of sensitivity, preferably 1,000~300,000, more preferably 2,000~300,000, further preferably 5,000~200,000.
The molar absorption coefficient of compound can utilize well known method, for example, it is preferable to pass through UV, visible light spectrophotometric Meter (Varian company manufacture Cary-5spectrophotometer), using ethyl acetate solvent, with the concentration of 0.01g/L into Row measurement.
Photoepolymerizationinitiater initiater used in the present invention can combine as needed two or more come using.
When composition of the invention contains polymerization initiator, the content of polymerization initiator is relative to the total solid in composition Ingredient, preferably 0.1~30 mass %, more preferably 1~25 mass %, further preferably 1~10 mass %.Of the invention Composition can only include a kind of polymerization initiator, also may include two or more.When comprising two or more, total amount preferably becomes upper State range.
< solvent >
Composition of the invention preferably comprises solvent, further preferably organic solvent.
As the example of organic solvent, for example, acetone, methyl ethyl ketone, hexamethylene, ethyl acetate, dichloroethylene, four can be enumerated Hydrogen furans, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, Acetylacetone,2,4-pentanedione, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethylene glycol list Isopropyl ether, ethylene glycol monomethyl ether acetate, 3- methoxypropanol, methoxyethoxy ethanol, diethylene glycol monomethyl ether, diethyl two Alcohol list ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, dihydroxypropane single-ether acetic acid Ester, 3- ethoxyl ethyl propionate (Ethyl 3-ethoxypropionate), 3- methoxy propyl acetate, N, N- dimethyl formyl Amine, dimethyl sulfoxide, gamma-butyrolacton, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate etc., but it is not limited to this A bit.
Composition of the invention can contain a kind of organic solvent, can also contain organic solvent of more than two kinds, but from adjust liquid sheet It is able to suppress when the composition of invention from the point of view of the partial size variation of nitrogen titanium particle, it is organic molten to preferably comprise two or more Agent.
When containing organic solvent of more than two kinds, preferably by selected from by above-mentioned 3- ethoxypropanoate, 3- ethoxy-propionic acid Ethyl ester, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- methoxy methyl propionate, 2-HEPTANONE, Cyclohexanone, cyclopentanone, ethylcarbitol acetate, acetate of butyl carbitol, propylene glycol monomethyl ether, 3- ethoxyl ethyl propionate And two or more composition in the group of propylene glycol methyl ether acetate composition.
When composition of the invention contains organic solvent, as the content of organic solvent, relative to the gross mass of composition, Preferably 10~90 mass %, more preferably 60~90 mass %.When comprising organic solvent of more than two kinds, preferred its total amount As above range.
< water >
Composition of the invention can contain water.Water can be added deliberately, can also be by adding in composition of the invention Each ingredient for including and inevitably contain in the composition.
The content of water relative to composition gross mass, preferably 0.1~1 mass %, more preferably 0.1~0.8 mass %, Further preferably 0.1~0.4 mass %.Within the above range by the content of water, patternability when cured film is made (resolution ratio) is excellent, and the anti-corrosive properties of electrode material are also excellent.Also, by the way that the content of water is set as relative to composition gross mass 0.1~1 mass % can more reduce the grain amount in composition, and the viscosity ageing stability of composition is also more excellent.
< other compositions >
It may include the other compositions in addition to above-mentioned ingredient in composition of the invention.
Hereinafter, each ingredient is described in detail.
(silane coupling agent)
Silane coupling agent refers to the change with hydrolization group and the functional group in addition to the hydrolization group in the molecule Close object.In addition, the hydrolization groups such as alkoxy and silicon atom bonding.
Hydrolization group refers to, and silicon atom Direct Bonding, and can pass through hydrolysis and/or condensation reaction generates silicon The substituent group of oxygen alkane key.As hydrolization group, for example, halogen atom, alkoxy, acyloxy and alkenyloxy group can be enumerated.It is water-disintegrable When group has carbon atom, carbon atom number is preferably 6 hereinafter, more preferably 4 or less.Especially preferably 4 or less carbon atom number Alkoxy or the alkenyloxy group below of carbon atom number 4.
Also, in order to improve the adaptation between substrate and cured film, silane coupling agent does not preferably include fluorine atom and silicon It is (wherein, water-disintegrable not include fluorine atom, silicon atom more preferably for atom (except the silicon atom that wherein, hydrolization group is bonded) Except the silicon atom that group is bonded), the alkylidene that is replaced by silicon atom, 8 or more carbon atom number straight chained alkyl and carbon atom The branched alkyl of 3 or more number.
Silane coupling agent preferably has the group indicated with formula below (Z).* bonding position is indicated.
*-Si-(RZ1)3... formula (Z)
In formula (Z), RZ1It indicates hydrolization group, is as defined above and states.
Silane coupling agent preferably has in the group being made of (methyl) acryloxy, epoxy group and oxetanylmethoxy 1 kind or more of curability functional group.Curability functional group can directly and silicon atom bonding, can also be former via linking group and silicon Sub-key is closed.
In addition, the preferred embodiment as the curability functional group for including in above-mentioned silane coupling agent, can also enumerate free radical Polymerizable group.
There is no particular restriction for the molecular weight of silane coupling agent, considers from operational viewpoint, and 100~1000 the case where is more, From effect of the invention it is more excellent from the point of view of, preferably 270 or more, more preferably 270~1000.
One of preferred embodiment as silane coupling agent can enumerate the silane coupling agent X indicated with formula (W).
RZ2-Lz-Si-(RZ1)3... formula (W)
RZ1It indicates hydrolization group, is as defined above and states.
RZ2It indicates curability functional group, is as defined above and states, preferred scope is also described above.
Lz indicates the linking group of singly-bound or divalent.It, can as the linking group of divalent when Lz indicates the linking group of divalent Enumerate the substitutive alkylidene of halogen atom, the substitutive arlydene of halogen atom ,-NR12-、-CONR12-、-CO-、-CO2-、 SO2NR12-、-O-、-S-、-SO2And their combination.Wherein, being preferably selected from can use by the halogen atom of carbon atom number 2~10 At least one kind of in the group of the alkylidene in generation and the halogen atom of carbon atom number 6~12 substitutive arlydene composition includes these Group with selected from by-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12,-O- ,-S- and SO2It is at least one kind of in the group of composition The combined group of group more preferably includes the substitutive alkylidene of the halogen atom ,-CO of carbon atom number 2~102-、-O-、- CO-、-CONR12Or the combined group of these groups.Wherein, above-mentioned R12Indicate hydrogen atom or methyl.
As silane coupling agent X, N- β-aminoethyl-γ-aminopropyl-methyl dimethoxysilane (Shin-Etsu can be enumerated Chemical CO., Ltd. trade name KBM-602), N- β-aminoethyl-γ-aminopropyl-trimethoxy silane (Shin-Etsu Chemical CO., Ltd. trade name KBM-603), N- β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical CO., Ltd. manufacture trade name KBE-602), γ-aminopropyl-trimethoxy silane (Shin-Etsu Chemical CO., Ltd. manufacture trade name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical CO., Ltd. Manufacture trade name KBE-903), 3- methacryloxypropyl trimethoxy silane (Shin-Etsu Chemical CO., Ltd. manufacture trade name KBM-503), glycidoxy octyl trimethoxy silane (Shin-Etsu Chemical CO., Ltd. Manufacture trade name KBM-4803) etc..
As other preferred embodiments of silane coupling agent, can enumerate at least has silicon atom, nitrogen-atoms, solidification in the molecule Property functional group, and there is silane coupling agent Y with the hydrolization group of silicon atom bonding.
Silane coupling agent Y has at least one silicon atom in the molecule, silicon atom can with atom below, take It is bonded for base.These can be identical atom, substituent group, can also be different.Bonding atom, substituent group can enumerate hydrogen original Son, halogen atom, hydroxyl, the alkyl of carbon atom number 1 to 20, alkenyl, alkynyl, aryl, the ammonia that can be replaced with alkyl and/or aryl Base, silicyl, the alkoxy of carbon atom number 1 to 20 and aryloxy group etc..These substituent groups can be further by silicyl, alkene Base, alkynyl, aryl, alkoxy, aryloxy group, thio alkoxy, amino, the halogen atom, sulphonyl that can be replaced with alkyl and/or aryl Amido, alkoxy carbonyl, amide groups, urea base, ammonium, alkyl ammonium group, carboxyl or its salt, sulfo group or its salt etc..
In addition, being bonded at least one hydrolization group on silicon atom.Hydrolization group, which is as defined above, to be stated.
It may include the group indicated with above-mentioned formula (Z) in silane coupling agent Y.
Silane coupling agent Y has the nitrogen-atoms of at least one or more in the molecule, and nitrogen-atoms is preferably with secondary amino group or tertiary ammonia The form of base exists, that is, nitrogen-atoms preferably has at least one organic group as substituent group.In addition, the structure as amino, Intramolecular can be present in the form of nitrogenous heterocyclic part-structure, also can be used as the presence of the substituted-aminos such as aniline.
Wherein, as organic group, alkyl, alkenyl, alkynyl, aryl or their combination can be enumerated.These can be further Silicyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy group, sulphur can be enumerated as the substituent group that can be imported with substituent group For alkoxy, amino, halogen atom, sulfoamido, alkoxy carbonyl, carbonyl oxygroup, amide groups, urea base, alkylene oxide group, ammonium Base, alkyl ammonium group, carboxyl or its salt, sulfo group etc..
Also, nitrogen-atoms is bonded preferably via arbitrary organo linking group with curability functional group.As preferably having Machine linking group can enumerate the substituent group that can imported into above-mentioned nitrogen-atoms and organic group bonded thereto.
The curability functional group for including in silane coupling agent Y, which is as defined above, to be stated, and preferred scope is also described above.
In silane coupling agent Y, the curability functional group of at least one or more can have in a molecule, but also can use tool There is the mode of 2 or more curability functional groups, from the viewpoint of sensitivity, stability, preferably there are 2~20 curability Functional group further preferably has 4~15, most preferably in the molecule with the mode of 6~10 curability functional groups.
There is no particular restriction for the molecular weight of silane coupling agent X and silane coupling agent Y, can enumerate above range (preferably 270 More than).
The content of silane coupling agent in composition of the invention is relative to the total solid content in composition, preferably 0.1~10 mass %, more preferably 0.5~8 mass %, further preferably 1.0~6 mass %.
Composition of the invention can include individually a kind of silane coupling agent, also may include two or more.Composition include 2 kinds with On silane coupling agent when, as long as its amount within the above range.
(ultraviolet absorbing agent)
It may include ultraviolet absorbing agent in composition of the invention.Thereby, it is possible to pattern form is set as more excellent (essence Shape carefully).
As ultraviolet absorbing agent, it is able to use salicylate system, benzophenone series, enumerate BTA system, substituted acrylonitrile System, triazine system ultraviolet absorbing agent.As their concrete example, the 0137 of Japanese Unexamined Patent Publication 2012-068418 bulletin can be used The compound of~0142 section (0251~0254 section of corresponding US2012/0068292) can quote these contents and introduce this In specification.
Furthermore, it also may be preferable for use diethylamino-phenylSulphon base system ultraviolet absorbing agent (DAITO CHE MICAL CO., LTD. manufacture, trade name: UV-503) etc..
As ultraviolet absorbing agent, it can enumerate and be illustrated in 0134~0148 section of Japanese Unexamined Patent Publication 2012-32556 bulletin Compound.
Composition of the invention may include ultraviolet absorbing agent, and when can also not include, but include, ultraviolet absorbing agent contains Measure the total solid content relative to composition, preferably 0.001~15 mass %, more preferably 0.01~10 mass %, into one Step is preferably 0.1~5 mass %.
(surfactant)
Various surfactants can be contained from the viewpoint of more improving coating about composition of the invention.Make For surfactant, can be used fluorine system surfactant, nonionic surfactants, cationic system surfactant, yin from The various surfactants such as subsystem surfactant and silicone-based surfactant.
By making to contain fluorine system surfactant in composition of the invention, characteristics of liquids when being prepared into coating fluid is (outstanding Its, mobility) more improve, so as to more improve the uniformity of coating thickness and save fluidity.That is, containing fluorine using application The interfacial tension decline for being the coating fluid of the composition of surfactant when forming film, to be applied between face and coating fluid, to The wetability for being applied face is improved, and is improved to the coating in the face that is applied.Therefore, thickness can more preferably be formed not The film of lesser uniform thickness.
Fluorine containing ratio in fluorine system surfactant is preferably 3~40 mass %, more preferably 5~30 mass %, especially Preferably 7~25 mass %.The fluorine system surfactant of fluorine containing ratio in the range the thickness of coated film uniformity and Save fluidity aspect effectively, the dissolubility in composition is also good.
As fluorine system surfactant, for example, Megaface F171, Megaface F172, Megaface can be enumerated F173、Megaface F176、Megaface F177、Megaface F141、Megaface F142、Megaface F143、 Megaface F144、Megaface R30、Megaface F437、Megaface F475、Megaface F479、Megaface F482, Megaface F554, Megaface F780, RS-72-K (more than, DIC CORPORATION manufacture), Fluorado FC430, Fluorado FC431, Fluorado FC171 (more than, 3M Japan Limited manufacture), Surflon S-382, Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-1068、 Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (more than, ASAHI GLASS CO., LTD. is manufactured), PF636, PF656, PF6320, PF6520 and PF7002 (OMNOVA SOLUTIONS INC. manufacture) etc.. Fluorine system surfactant can also use the chemical combination recorded in 0015~0158 section of Japanese Unexamined Patent Publication 2015-117327 bulletin Object.As fluorine system surfactant, additionally it is possible to block polymer is used, as concrete example, for example, Japanese Unexamined Patent Publication can be enumerated The compound recorded in 2011-89090 bulletin.
Fluorine system surfactant also can be it is preferable to use following fluorine-containing polymer compound, and it includes be originated to have fluorine atom (methyl) acrylate compounds repetitive unit and be originated from 2 or more (preferably 5 or more) alkylene oxide group it is (excellent Be selected as ethyleneoxy, propenyloxy group) (methyl) acrylate compounds repetitive unit, following compounds are also used as the present invention Used in fluorine system surfactant illustrate.
[chemical formula 18]
The weight average molecular weight of above compound is preferably 3,000~50,000, for example, 14,000.
Also, can also there will be the fluoropolymer of olefinic unsaturated group to be used as fluorine system surfactant in side chain.Make For concrete example, the change recorded in 0050~0090 section and 0289~0295 section of Japanese Unexamined Patent Publication 2010-164965 bulletin can be enumerated Close object, such as Megaface RS-101, RS-102, RS-718K and RS-72-K etc. of DIC CORPORATION manufacture.
As nonionic surfactants, specifically, glycerol, trimethylolpropane, trimethylolethane can be enumerated And their ethoxylate and propoxylate (for example, glycerol propoxylate, glycerol ethoxylate etc.), polyoxy second Alkene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, NONIN HS 240, ethylene nonyl phenyl Ether, polyethylene glycol dilaurate, polyglycol distearate, fatty acid esters of sorbitan be (BASF AG's manufacture Pluronic L10, L31, L61, L62,10R5,17R2,25R2, TETRONIC 304,701,704,901,904,150R1 and SOLSPERSE 20000 (The Lubrizol Corporatin manufacture)) etc..Also, Wako Pure can also be used NCW-101, NCW-1001 and NCW-1002 of Chemical Industries, Ltd. manufacture.
As cationic system surfactant, specifically, can enumerate phthalocyanine derivates (trade name: EFKA-745, MORISHITA&CO., LTD. manufacture), organic siloxane polymer KP341 (Shin-Etsu Chemical CO., Ltd. system Make), (methyl) acrylic acid series (co) polymer Polyflow No.75, No.90, No.95 (KYOEISHA CHEMICAL CO., LTD manufacture) and W001 (Yusho CO., Ltd. manufacture) etc..
As anionic surfactant, specifically, W004, W005, W017 (Yusho CO., Ltd. system can be enumerated Make) and Sandetto BL (Sanyo Chemical Industries, Ltd. manufacture) etc..
As silicone-based surfactant, for example, Toray Silicone DC3PA, Toray Silicone can be enumerated SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (more than, Dow Corning Toray CO., Ltd. manufacture), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (more than, Momentive Performance Materials Inc. manufacture), KP341, KF6001, KF6002 (more than, Shin-Etsu ChemicalCO., Ltd. manufacture), BYK307, BYK323 and BYK330 (more than, BYK Additives&Instruments system Make) etc..
Surfactant can be used only a kind, can also combine two or more.The content of surfactant is relative to of the invention The total solid content of composition, preferably 0.001~2.0 mass %, more preferably 0.005~1.0 mass %.
In addition to the above ingredients, following component can also further be added in composition of the invention.For example, can enumerate quick Agent, altogether sensitizer, crosslinking agent, curing accelerator, filler, thermosetting accelerator, polymerization inhibitor, plasticizer, diluent, sense Grease agent, moreover, can also be added as needed to the adhesion promoter of substrate surface and other auxiliary agent classes (for example, electric conductivity grain Son, filler, defoaming agent, fire retardant, levelling agent, removing promotor, antioxidant, fragrance, surface tension regulator and chain turn Move agent etc.) etc. well known to additive.
These ingredients (can for example be corresponded to reference to the paragraph 0183~0228 of Japanese Unexamined Patent Publication 2012-003225 bulletin No. 2013/0034812 specification of U.S. Patent Application Publication No. 0237 > of <~<, 0309 >), Japanese Unexamined Patent Publication 2008- Paragraph 0101~0102, paragraph 0103~0104, the paragraph 0107~0109, Japanese Unexamined Patent Publication of No. 250074 bulletins The equal record of the paragraph 0159~0184 of 2013-195480 bulletin, these contents are introduced into this specification.
(colorant)
Composition of the invention can also use the colorant other than above-mentioned nitrogen titanium particle (hereinafter, being also referred to as " Toner ".).Colorant for example uses to adjust the coloration of composition, can will nitrogenize in the range of OD value does not decline A part of titanium replaces with colorant.As this colorant, can enumerate pigment (black organic pigment and colored organic pigments Organic pigment and inorganic pigment) and dyestuff etc..
As colorant, it is preferable to use pigment.The mark in the transmissivity of the range of 400~700nm of wavelength is easily manufactured as a result, The quasi- lesser film of deviation.In particular, easily being manufactured when using black pigment (black organic pigment and black inorganic pigment) as pigment The standard deviation of the transmissivity of above range is 10% film below.
((pigment))
As pigment, known various pigment can be enumerated.
As colored organic pigments, following organic pigment can be enumerated.But the present invention is not limited to these.
Colour Index (C.I.) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31, 32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83, 86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119, 120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156, 161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182, 185,187,188,193,194,199,213,214 etc.,
C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61, 62,64,71,73 etc.,
C.I. 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48 of paratonere: 4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90, 105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177, 178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242, 246,254,255,264,270,272,279 etc.,
C.I. pigment Green 7,10,36,37,58,59 etc.,
C.I. pigment violet 1,19,23,27,32,37,42 etc.,
C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80 etc.,
Also, as viridine green, additionally it is possible to which using the Number of Halogen Atoms in molecule be averagely 10~14, bromine atom is flat Equal 8~12, the zinc halide phthalocyanine color that chlorine atom is averagely 2~5.As concrete example, International Publication No. 2015/ can be enumerated The compound recorded in No. 118720.
These organic pigments can combine a variety of use individually or in order to improve colour purity.
Black pigment is able to use various well known black pigments.For example, carbon black can be enumerated or described below containing black Metallo organic pigment.As organic pigment containing ferrous metal, can enumerate comprising selected from by Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Metal oxide, the metal nitride of one kind or two or more metallic element in the group of Ti and Ag composition.These can only make With a kind, also, can also as mixture of more than two kinds come using.Also, it can be by being further combined it to black pigment The inorganic pigment of his tone, to be prepared into desired light-proofness.The specific inorganic face used as that can combine The example of material, for example, it is brilliant to enumerate zinc white, white lead, lithopone, titanium oxide, chromium oxide, iron oxide, precipitability barium sulfate and weight Mountain flour, lead is red, iron oxide red, chrome yellow, zinc yellow (a kind of zinc yellow, 2 kinds of zinc yellow), ultramarine blue, Prussian blue (ferric potassium ferrocyanide) zirconium Lime color, praseodymium yellow, chromium titan yellow, chrome green, peacock, Victoria green, barba hispanica (with Prussian blue unrelated), Vanadium zirconium blue, chrome tin pink, manganese It is red, orange red etc..In particular, this can not only be used alone in order to show the light-proofness in ultraviolet to infrared wider wavelength domain A little black pigments or other tones, can also mix a variety of pigment come using.
Black pigment is preferably that carbon black, titanium are black, from the viewpoint of the light-proofness with ultraviolet to infrared wider wavelength domain Consider, especially preferably titanium is black.Black titanium is the black particles with titanium atom.Preferably low order titanium oxide or titanium oxynitride etc.. Though being not particularly limited, as titanium oxynitride, it is able to use such as No. 2008/123097 bulletin of International Publication, Japanese Unexamined Patent Publication 2009- 58946, the oxynitriding of Japanese Unexamined Patent Publication 2010-14848, Japanese Unexamined Patent Publication 2010-97210 and Japanese Unexamined Patent Publication 2011-2274670 etc. Titanium, further, it is possible to use the mixture of such as titanium oxynitride of Japanese Unexamined Patent Publication 2010-95716 and titanium carbide.In order to improve dispersion Property, inhibit coherency etc., the surface of titanium black track producing particle can be modified as needed.Can by silica, titanium oxide, germanium oxide, Aluminium oxide, magnesia, zirconium oxide cladding, also, can also carry out passing through as shown in Japanese Unexamined Patent Publication 2007-302836 bulletin The processing of lyophobic dust.In order to adjust dispersibility, coloring etc., the black composite oxygen containing a kind of Cu, Fe, Mn, V, Ni etc. of titanium The black pigments such as compound, cobalt oxide, iron oxide, carbon black, or contained with combination of more than two kinds.
The manufacturing method black as titanium has and heat also by mixture of the reducing atmosphere to titanium dioxide and Titanium Former method (Japanese Unexamined Patent Application 49-5432 bulletin), in the reducing atmosphere comprising hydrogen to the high-temperature water by titanium tetrachloride Method (Japanese Unexamined Patent Application 57-205322 bulletin) that solution is restored the ultra rme titanium dioxide that obtains, in the presence of ammonia Method (the Japanese Unexamined Patent Application 60-65069 bulletin, Japanese Unexamined Patent Application 61- of high temperature reduction are carried out to titanium dioxide or titanium hydroxide No. 201610 bulletins), make vfanadium compound be attached to titanium dioxide or titanium hydroxide and in the presence of ammonia carry out high temperature reduction side Method (Japanese Unexamined Patent Application 61-201610 bulletin) etc..But the present invention is not limited to these.
There is no particular restriction for the black specific surface area of titanium, but measured by BET (Brunauer, Emmett, Teller) method Value is preferably 5m2/ g or more 150m2/ g is hereinafter, more preferably 20m2/ g or more 120m2/ g or less.
The example of the commercially available product black as titanium can enumerate titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M- T (trade name: Mitsubishi Materials Corporation manufacture), TilackD (trade name: Ako Kasei CO., Ltd. manufacture) etc..
The average primary particle diameter of above-mentioned black pigment is preferably 5nm or more, more preferably 10nm or more.From identical viewpoint Consider, as the upper limit, preferably 10 μm hereinafter, more preferably 1 μm hereinafter, further preferably 100nm or less.Black pigment Average primary particle diameter is set as the value measured by the following method.It is set as, will include black face by propylene glycol methyl ether acetate The mixed liquor of material is diluted to 80 times, to dilution obtained, utilizes the value of dynamic light scattering determination.In the measurement, it is set as Using NIKKISO CO., LTD. manufactures the average grain diameter that Microtrac (trade name) UPA-EX150 obtain.
Moreover, it is also preferred that contain comprising titanium is black and Si atom it is black as titanium by dispersion.
In the form, black titanium is in the composition as the pigment contained by dispersion, by the Si atom in dispersion With Ti atom containing than (Si/Ti) in terms of mass conversion, preferably 0.05 or more, more preferably 0.05~0.5, it is further excellent It is selected as 0.07~0.4.
Wherein, it is above-mentioned by dispersion include titanium it is black be primary particle state titanium it is black, be condensate (offspring) The titanium of state it is black both.
It, can be with the following method in order to change by the Si/Ti (for example, being set as 0.05 or more) of dispersion.
Firstly, obtaining dispersion by dispersing titanium oxide and silicon dioxide granule using dispersion machine, and in high temperature (example Such as, 850~1000 DEG C) under reduction treatment is carried out to the dispersion, thus to obtain using titanium black track producing particle as principal component and Si is contained With Ti by dispersion.Above-mentioned reduction treatment can also carry out under the atmosphere of the reducibility gas such as ammonia.
As titanium oxide, TTO-51N (trade name: Ishihara Sangyo Kaisha, Ltd. manufacture) etc. can be enumerated.
The titanium oxide made by plasma method, partial size is less than commercially available titanium oxide microparticle, therefore can preferably make With (with reference to the record of Japanese metallography meeting will No. 1 (1999) 74-81 of volume 63).
As the commercially available product of silicon dioxide granule, can enumerate AEROSIL (registered trademark) 90,130,150,200,255, 300,380 (trade names: Evonik Japan CO., Ltd. manufacture) etc..
Dispersing agent also can be used in the dispersion of titanium oxide and silicon dioxide granule.Dispersion above-mentioned can be enumerated as dispersing agent The dispersing agent illustrated in one column of agent.
Above-mentioned dispersion can carry out in a solvent.As solvent, water, organic solvent can be enumerated.It can enumerate above-mentioned organic molten The solvent illustrated in one column of agent.
Si/Ti be for example adjusted to 0.05 with first-class titanium is black can be for example, by Japanese Unexamined Patent Publication 2008-266045 bulletin Paragraph (0005) and paragraph (0016)~(0021) in record method production.
By will include that titanium is black and Si atom by dispersion Si atom and Ti atom containing being adjusted than (Si/Ti) For range appropriate (for example, 0.05 or more), when using forming photomask comprising the composition by dispersion, the shape of photomask The residue from composition outside at region is reduced.In addition, residue includes to be originated from the compositions such as titanium black track producing particle, resin component Ingredient.
Although the reasons why residue is reduced is still not clear, infer as follows: being had by dispersion become small as described above The trend (for example, partial size is 30nm or less) of partial size, and this is increased by the ingredient comprising Si atom of dispersion, and thus film is whole The adsorptivity of body and substrate reduces, and the uncured composition (in particular, titanium is black) when this helps to improve photomask formation is shown Shadow removal.
Also, the light-proofness of the black light relative to the wavelength region throughout wide scope of the ultraviolet light to infrared light of titanium is excellent, Therefore using it is above-mentioned comprising titanium is black and Si atom by dispersion, (Si/Ti in terms of mass conversion, preferably 0.05 or more is divided Granular media) photomask to be formed plays excellent light-proofness.
In addition, can for example utilize Japanese Unexamined Patent Publication than (Si/Ti) with containing for Ti atom by the Si atom in dispersion The method (1-1) or method (1-2) recorded in 0033 section of 2013-249417 bulletin measures.
Also, contain in the photomask obtained to composition is solidified by dispersion, judge this by dispersion Si atom and Ti atom containing whether being 0.05 or more than (Si/Ti) when, utilize Japanese Unexamined Patent Publication 2013-249417 bulletin The method (2) recorded in 0035 section.
Comprising titanium is black and Si atom by dispersion, titanium is black, and to be able to use above-mentioned titanium black.
Also, this is by dispersion, can be black together with titanium in order to adjust dispersibility, coloring etc., combine a kind or 2 kinds with On composite oxides, cobalt oxide, iron oxide, carbon black, nigrosine comprising Cu, Fe, Mn, V, Ni etc. etc. black pigment, and As by dispersion.
At this point, preferably comprising, titanium is black to account for all 50 mass % or more by dispersion by dispersion.
Also, this is by dispersion, can within the scope of the effect of the invention in order to adjust light-proofness etc., root It is black together and with other colorants (organic pigment or dyestuff etc.) with titanium according to needs.
Hereinafter, the opposite material used by the dispersion importing Si atomic time is described.Si atom is imported to by dispersion When, use the substances containing Si such as silica.
As workable silica, precipitated silica, fumed silica, colloidal silicon dioxide, conjunction can be enumerated At silica etc., can suitably select these come using.
Moreover, light-proofness is more excellent if the partial size of silicon dioxide granule is the partial size less than film thickness when forming photomask It is different, therefore it is preferable to use the silica of particle type as silicon dioxide granule.In addition, the silica as particle type Example, for example, the silica recorded in 0039 section of Japanese Unexamined Patent Publication 2013-249417 bulletin, these contents can be enumerated It is introduced into this specification.
Also, as pigment, additionally it is possible to use tungsten compound and metal boride.
Tungsten compound and metal boride are higher relative to infrared ray (light that wavelength is about 800~1200nm) absorption (that is, the light-proofness (shielding) relative to infrared ray is higher), and relative to the lower infrared shield material of visible absorption. Therefore, photosensitive composite of the invention can be formed in infrared region by containing tungsten compound and/or metal boride Light-proofness is higher and visible light region in the higher pattern of translucency.
Also, tungsten compound and metal boride are directed to the exposure than being used to form image, high-pressure sodium lamp, KrF and ArF etc. The light of the more shortwave of visibility region used in light absorbs also smaller.
As tungsten compound, tungsten oxide based compound, tungsten boride based compound, tungsten sulfide based compound etc. can be enumerated, The tungsten oxide based compound preferably indicated with the following general formula (composition formula) (I).
MxWyOz……(I)
M indicates that metal, W indicate that tungsten, O indicate oxygen.
0.001≤x/y≤1.1
2.2≤z/y≤3.0
As the metal of M, for example, can enumerate alkali metal, alkaline-earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi etc., preferably For alkali metal.The metal of M can be a kind, be also possible to two or more.
M is preferably alkali metal, more preferably Rb or Cs, further preferably Cs.
It is 0.001 or more by x/y, can sufficiently shields infrared ray, is 1.1 hereinafter, can reliably avoid by it Impurity phase is generated in tungsten compound.
It is 2.2 or more by z/y, can more improves the chemical stability as material, is 3.0 hereinafter, energy by it Enough sufficiently shielding infrared rays.
As the concrete example of the tungsten oxide based compound indicated with above-mentioned general formula (I), Cs can be enumerated0.33WO3、 Rb0.33WO3、K0.33WO3、Ba0.33WO3Deng preferably Cs0.33WO3Or Rb0.33WO3, more preferably Cs0.33WO3。
Tungsten compound is preferably particle.The average primary particle diameter of tungsten particle is preferably 800nm hereinafter, more preferably 400nm Hereinafter, further preferably 200nm or less.By average primary particle diameter in this range, tungsten particle is not easy since light scatters Visible light is shielded, therefore the translucency in visible light region can be reliably achieved.From the viewpoint of avoiding light from scattering, put down Equal primary particle size is smaller the more preferred, but considers that the average primary particle diameter of tungsten particle is logical from reasons such as handling easiness when manufacture It is often 1nm or more.
Also, tungsten compound is able to use two or more.
Tungsten compound can be obtained as commercially available product, when tungsten compound is, for example, tungsten oxide based compound, tungsten oxide system Compound can by inactive gas atmosphere or reducibility gas atmosphere to tungsten compound carry out heat-treating methods come It obtains and (refers to No. 4096205 bulletins of Japanese Patent No.).
Also, tungsten oxide based compound also can be used as such as Sumitomo Metal Mining CO., Ltd. manufacture The dispersion of the tungsten particle such as YMF-02 obtains.
Also, as metal boride, lanthanum boride (LaB can be enumerated6), boronation praseodymium (PrB6), neodymium boride (NdB6), boronation Cerium (CeB6), yttrium boride (YB6), titanium boride (TiB2), zirconium boride (ZrB2), hafnium boride (HfB2), vanadium boride (VB2), tantalum boride (TaB2), chromium boride (CrB, CrB2), molybdenum boride (MoB2、Mo2B5, MoB), tungsten boride (W2B5) etc. it is one kind or two or more, it is excellent It is selected as lanthanum boride (LaB6)。
Metal boride is preferably particle.The average primary particle diameter of metal boride particle is preferably 800nm hereinafter, more excellent 300nm is selected as hereinafter, further preferably 100nm or less.By average primary particle diameter in this range, metal boride particle Become to be not easy to interdict visible light since light scatters, can more reliably realize the translucency in visible light region.From keeping away From the viewpoint of exempting from light scattering, average primary particle diameter is smaller the more preferred, but considers from the reasons such as handling easiness when manufacture, gold The average primary particle diameter for belonging to boride microparticle is usually 1nm or more.
Also, metal boride is able to use two or more.
Metal boride can be obtained as commercially available product, such as can also be used as Sumitomo Metal Mining CO., the dispersion of the metal borides particle such as KHF-07AH of Ltd. manufacture obtains.
((dyestuff))
As dyestuff, for example, can be used Japanese Unexamined Patent Application 64-90403 bulletin, Japanese Unexamined Patent Application 64-91102 bulletin, Japanese Unexamined Patent Publication 1-94301 bulletin, Japanese Unexamined Patent Publication 6-11614 bulletin, spy step on No. 2592207, United States Patent (USP) 4808501 Number specification, No. 5667920 specifications of United States Patent (USP), No. 505950 specifications of United States Patent (USP), Japanese Unexamined Patent Publication 5-333207 Bulletin, Japanese Unexamined Patent Publication 6-35183 bulletin, Japanese Unexamined Patent Publication 6-51115 bulletin, Japanese Unexamined Patent Publication 6-194828 bulletin The pigment Deng disclosed in.If being distinguished as chemical structure, it is able to use pyrazole azo compound, pyrroles's methylene chemical combination Object, aniline azo-compound, triphenylmethane compound, anthraquinone compounds, benzal compound, oxonols (oxonol) chemical combination Object, Pyrazolotriazole azo-compound, pyridone monoazo compound, cyanine compound, phenothiazine compounds, pyrrolo-pyrazole first Group with imine moiety etc..Also, as dyestuff, pigment polymer can be used.As pigment polymer, Japanese Unexamined Patent Publication can be enumerated The compound recorded in 2011-213925 bulletin, Japanese Unexamined Patent Publication 2013-041097 bulletin.
Composition of the invention can be other than colorant, also according to needing comprising extender pigment.As this constitution face Material, such as barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white and water can be enumerated Talcum etc..These extender pigments can be used alone or mix two or more come using.The usage amount of extender pigment is relative to coloring 100 mass parts of agent, usually 0~100 mass parts, preferably 5~50 mass parts, more preferably 10~40 mass parts.The present invention In, colorant and extender pigment can according to circumstances be modified its surface by polymer to use.
Colorant can be used alone a kind, can also be used in combination of two or more.As colorant, can containing red, blue, yellow, The Colored organic pigments such as green and purple.And with light-proofness pigment (specifically, nitrogen titanium particle) and Colored organic pigments When, relative to light-proofness pigment, it is preferable to use the Colored organic pigments of 1~40 mass %.It is excellent from the viewpoint of adjustment tone It selects and uses red pigment and light-proofness pigment, although being not particularly limited, as red pigment, preferably paratonere 254.And And from the viewpoint of improving light-proofness, yellow uitramarine and light-proofness pigment is preferably used in combination, although being not particularly limited, makees For yellow uitramarine, preferably pigment yellow 150.
When composition of the invention contains colorant, total solid content of the content of colorant relative to composition, preferably For 20~80 mass %, more preferably 30~70 mass %, further preferably 35~60 mass %.
(pigment derivative)
Composition of the invention can contain pigment derivative.As pigment derivative, pass through acid for example, can enumerate and have Property base, basic group or phthalimide methyl replace organic pigment a part structure compound.
As the organic pigment for constituting pigment derivative, diketopyrrolo-pyrrole system pigment, azo system face can be enumerated Material, anthraquione pigmentss, Kui acridone system pigment, dioxazine pigment, purple cyclic ketones system pigment, is pigment, sulphur at phthualocyanine pigment Indigo system pigment different draw diindyl beautiful jade system pigment, different draws diindyl beautiful jade ketone system pigment, quinophthalone system pigment, intellectual circle system pigment, metal complex system Pigment etc..
Also, as acidic groups possessed by pigment derivative, preferably sulfonic group, carboxylic acid group and its quaternary ammonium salt base, into One step is preferably carboxylic acid group and sulfonic group, especially preferably sulfonic group.As basic group possessed by pigment derivative, preferably Amino, especially preferably tertiary amino.
As the concrete example of pigment derivative, for example, following compounds can be enumerated.Also, it can refer to Japanese Unexamined Patent Publication 2011- 0162~0183 section of record of No. 252065 bulletins, the content are introduced into this specification.
[chemical formula 19]
When composition of the invention contains pigment derivative, gross mass of the content of pigment derivative relative to colorant, Preferably 1~30 mass %, further preferably 3~20 mass %.Composition of the invention can be only derivative comprising a kind of pigment Object also may include two or more.When comprising two or more, preferably its total amount becomes above range.
The preparation method > of < composition
Composition of the invention can by well known mixed method (for example, blender, homogenizer, high-pressure emulsification device, Wet crushing mill, wet type dispersion machine) above-mentioned various composition is mixed to prepare.
In order to remove foreign matter or reduction defect etc., composition of the invention is preferably filtered with filter.As filter, only If the device for filtration applications etc. all the time, then especially can not limitedly use.For example, can enumerate (poly- based on PTFE Tetrafluoroethene) etc. the polyolefin resins such as polyamide resins, polyethylene, the polypropylene (PP) such as fluororesin, nylon it is (including highly dense Degree, super high molecular weight) etc. filter.In these raw material, preferably polypropylene (including high density poly propylene), nylon.
The aperture of filter is conveniently 0.1~7.0 μm of degree, preferably 0.2~2.5 μm of degree, more preferably 0.2~ 1.5 μm of degree, further preferably 0.3~0.7 μm.By setting it as the range, the filtering blocking of pigment, and energy are able to suppress It is enough reliably to remove the fine foreign matters such as the impurity for including in pigment or condensation product.
When using filter, different filters can be combined.At this point, the filtering by the 1st filter can only carry out 1 time, It can carry out 2 times or more.Different filters are combined come the aperture and the 1st filtering when carrying out 2 times or more filterings, after the 2nd time Aperture compare, it is preferably identical or bigger.Also, it also can be combined in the 1st filter in aperture different in above range.This The aperture at place can refer to the nominal value of filter manufacturer's.As commercially available filter, for example, can be from by NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. (former Mykrolis Corpration) or KITZ It is selected in the various filters of the offers such as MICRO FILTER CORPORATION.
2nd filter is able to use the filter of the formation such as material identical with above-mentioned 1st filter.2nd filter Aperture is conveniently 0.2~10.0 μm of degree, preferably 0.2~7.0 μm of degree, further preferably 0.3~6.0 μm of degree.
The solid component of composition of the invention is preferably 10~40 mass %, more preferably 12~35 mass %.Pass through The solid component of composition is 10 mass % or more, and the light-proofness of cured film more improves.Also, by the solid of composition at Be divided into 40 mass % hereinafter, composition through when viscosity stability become more good.
[cured film (photomask)]
Cured film of the invention is obtained using combinations of the above object.
Above-mentioned cured film preferably has surface relief structure.By so, it is possible to reduce photomask or there is photomask Light shield layer reflectivity.About the concaveconvex structure, there can be concaveconvex structure on itself surface of photomask, it can also be Other layers are set on photomask to assign concaveconvex structure.The shape of surface relief structure is not particularly limited, and surface roughness is excellent It is selected as 0.55 μm or more 1.5 μm of ranges below.
The reflectivity of photomask is preferably 5% hereinafter, more preferably 3% hereinafter, especially preferably 2% or less.
The method of production surface relief structure is not particularly limited, and the layer that can be in photomask or in addition to this includes Lithography process or the etching or sputtering, nano-imprint method etc. of the method or utilization exposure development of machine filler or inorganic filler, to screening The surface of light film or layer in addition to this carries out roughened method.
Also, the method as the reflectivity for reducing above-mentioned cured film can also be enumerated and be set on photomask than that described above It sets low the method for index layer or the method or example of the layer (for example, high refractive index layer) of multiple and different refractive index is further set Such as the method for the formation low optical concentration layer and high optics concentration layer recorded in Japanese Unexamined Patent Publication 2015-1654 bulletin.
It mainly include above-mentioned nitrogen titanium particle in cured film of the invention.Cured film of the invention is preferably used as shading Film, specifically, it is preferable that being used as the imaging sensors periphery photomask (frames such as ccd image sensor or cmos image sensor Photomask).
Hereinafter, the case where cured film is used as imaging sensor periphery photomask is illustrated as an example.It will solidification When film is used as imaging sensor periphery photomask, it can enumerate and form imaging sensor periphery photomask in colour filter, this is applied In the mode of ccd image sensor or cmos image sensor.That is, can scheme in colour filter and ccd image sensor or CMOS The region abutted as frame regions such as sensors constitutes above-mentioned cured film.
Colour filter with imaging sensor periphery photomask of the invention is using combinations of the above object (in particular, above-mentioned Photosensitive composite) and formed.The pattern of the imaging sensor periphery photomask obtained using composition of the invention is formed Property and the anti-corrosive properties of electrode are excellent.
When as imaging sensor periphery photomask, as the film thickness of photomask, it is not particularly limited, from more efficiently From the viewpoint of obtaining based on effect of the invention, the film thickness after drying is preferably 0.2 μm or more 50 μm hereinafter, more preferably 0.5 μm or more 30 μm hereinafter, further preferably 0.7 μm or more 20 μm or less.Also, as the size of photomask (one side Length), from more efficiently obtaining based on from the viewpoint of effect of the invention, preferably 0.001mm or more 5mm is hereinafter, more Preferably 0.05mm or more 4mm is hereinafter, further preferably 0.1mm or more 3.5mm or less.
The manufacturing method > of < cured film
Then, there is no particular restriction for the manufacturing method of cured film of the invention (photomask), can use well known method. Hereinafter, as representative examples, being described in detail to the method for the cured film of manufacture pattern-like.
Manufacturing method about pattern-like cured film of the invention on substrate, characterized by comprising: be coated with the present invention Composition come formed composition layer (coated film) process (hereinafter, suitably referred to as " composition layer formation process ".)；Via The process that mask is exposed said combination nitride layer is (hereinafter, suitably referred to as " exposure process ".)；And to the group after exposure Nitride layer is closed to be developed to form the process of the cured film of pattern-like (hereinafter, suitably referred to as " developing procedure ".).
Specifically, directly or via other layers, composition of the invention is coated on substrate to form composition layer (composition layer formation process), is exposed via defined mask pattern, only makes the composition layer being irradiated by light partially cured (exposure process) forms the cured film of the pattern-like comprising pixel by being developed (developing procedure) with developer solution.
Hereinafter, being illustrated to each process.
(composition layer formation process)
In composition layer formation process, composition of the invention is coated on substrate to form composition layer (coated film).
As substrate, for example, alkali-free glass, soda-lime glass, Pyrex (registered trademark) glass for liquid crystal display device etc. Glass, quartz glass and to they adhere to transparent conductive films glass, for the photo-electric conversion element substrate of solid-state imager etc. (for example, silicone substrate etc.), CCD (Charge Coupled Device) substrate and CMOS (Complementary Metal-Oxide Semiconductor) substrate etc..
Also, it, can be at this in order to improve adherency with upper layer, prevent the diffusion of substance or the planarization of substrate surface On a little substrates, priming coat is set as needed.
As the coating method for being coated with composition of the invention on substrate, slot coated method, ink-jet method, spin coating can be applied The various coating methods such as method, cast coating method, rolling method, screen printing.
When manufacturing the colour filter with imaging sensor periphery photomask, as the coating film thickness of composition, from resolution ratio From the viewpoint of developability, preferably 0.35 μm or more 2.0 μm hereinafter, more preferably 0.40 μm or more 1.5 μm or less.
The composition on substrate is coated on usually at 70 DEG C or more 110 DEG C hereinafter, in 4 minutes 2 minutes or more or less degree Under conditions of be dried.Thereby, it is possible to form composition layer.
(exposure process)
In exposure process, the composition layer (coated film) formed in composition layer formation process is exposed via mask Light only makes the coated film being irradiated by light partially cured.
It is preferred that being exposed by the irradiation of activation light or radioactive ray, particularly preferably penetrated using g ray, h ray, i The ultraviolet lights such as line, more preferably high-pressure sodium lamp.Exposure intensity is preferably 5~1500mJ/cm2, more preferably 10~1000mJ/ cm2。
(developing procedure)
Then exposure process carries out alkali development processing (developing procedure), makes the light irradiated portion in exposure process in buck It is eluted in solution.The part (the coating membrane part being irradiated by light) of photocuring is only remained as a result,.
It preferably will not be to substrate when making the colour filter with imaging sensor periphery photomask as developer solution Circuit etc. brings organic alkaline developer of damage.As development temperature, usually 20~30 DEG C, developing time is 20~90 seconds.
As alkaline aqueous solution, for example, inorganic system's developer solution and organic system developer solution can be enumerated.Develop as inorganic system Liquid can be enumerated sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium metasilicate, sodium metasilicate, be dissolved into concentration and be 0.001~10 mass %, the preferably alkaline aqueous solution of 0.01~1 mass %.As organic system developer solution, can enumerate ammonia Water, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, sends pyridine, 1,8- at ethamine The organic basic compounds such as diazabicyclo-[5.4.0] -7- endecatylene, being dissolved into concentration is 0.001~10 mass %, excellent It is selected as the alkaline aqueous solution of 0.01~1 mass %.In alkaline aqueous solution, such as the water such as suitable methanol, ethyl alcohol can also be added Solubleness organic solvent and/or surfactant etc..In addition, when using developer solution comprising this alkaline aqueous solution, usually aobvious Movie queen cleans (flushing) with pure water.
As developing method, such as sheathed dip-type developing method and spray developing method etc. can be utilized.
In addition, in the manufacturing method of the colour filter with cured film of the invention combinations of the above nitride layer shape can be being carried out After process, exposure process and developing procedure, as needed, comprising by heating and/or exposing to being formed by cured film Carry out cured curing process.
(colour filter, photomask)
The cured film formed using composition of the invention can be preferably used as the pixel black matrix or such as of colour filter In imaging sensor periphery as described above photomask (frame photomask) or aftermentioned image display device or sensor module Various parts in the photomask applied.
(colour filter)
It is solid that colour filter can be preferred for CCD (charge coupled cell) or CMOS (complementary metal oxide film semiconductor) etc. Body photographing element, particularly suitable for such as more than high-resolution CCD of 1,000,000 pixels or CMOS etc..Colour filter can for example configure It is used between the acceptance part of each pixel and the lenticule for optically focused for constituting CCD or CMOS.Also, colour filter can have Such as flowering structure, that is, in the space for being for example divided into clathrate by next door, embedment forms the cured film of each colored pixels.At this time Next door relative to each colored pixels be preferably low-refraction.As the example of the photographic element with this structure, can enumerate The device recorded in Japanese Unexamined Patent Publication 2012-227478 bulletin, Japanese Unexamined Patent Publication 2014-179577 bulletin.
As long as colour filter of the invention has above-mentioned cured film, form is not particularly limited.
In colour filter, above-mentioned cured film can for example be preferably used as the pixel black matrix or as described above of colour filter Imaging sensor periphery photomask (frame photomask).
(photomask)
Photomask is capable of forming in the various parts in image display device or sensor module (for example, infrared cut of light Filter, the peripheral part of solid-state imager, wafer scale lens peripheral part, solid-state imager back side etc.) etc. use.
Also, photomask can also be formed as band shading at least part on the surface of infrared cut of light filter The infrared cut of light filter of film.
There is no particular restriction for the thickness of photomask, preferably 0.2~25 μm, more preferably 1.0~10 μm.It is above-mentioned with a thickness of Average thickness is the value for measuring any 5 points or more of thickness of photomask and they being carried out with arithmetic average.
The reflectivity of photomask is preferably 10% hereinafter, more preferably 8% hereinafter, further preferably 6% hereinafter, especially Preferably 4% or less.In addition, the reflectivity of photomask is that the light of 400~700nm is made to be incident in photomask with 5 ° of incident angle, Its reflectivity is measured by Hitachi High-Technologies Corporation. optical splitter UV4100 (trade name) Value.
(solid-state imager)
Solid-state imager of the invention has above-mentioned cured film (colour filter, photomask etc.).As solid of the invention The structure of photographing element as long as having above-mentioned cured film, and as the structure that solid-state imager functions, then has no spy It does not limit, such as can enumerate such as flowering structure.
For such as flowering structure: having on substrate and constitute solid-state imager (ccd image sensor, cmos image sensor Deng) sensitive area multiple transfer electrodes comprising photodiodes and polysilicon etc., on photodiodes and transfer electrode With the photomask being only open to the acceptance part of photodiodes, have on photomask to cover photomask front and photoelectricity two The unit protection film being made of silicon nitride etc. that the mode of polar body acceptance part is formed has colour filter on unit protection film.
Furthermore, it is also possible to be that there is optically focused mechanism (close to the side of substrate) on unit protection layer and under colour filter (for example, lenticule etc..It is same as below) structure, on colour filter with the structure etc. of optically focused mechanism.Also, colour filter can also It has the following structure, that is, have to form the cured film of each colored pixels being for example divided into the space of clathrate to be embedded to by next door. Next door at this time is preferably low-refraction relative to each colored pixels.It, can as the example of the photographic device with this structure Enumerate the device recorded in Japanese Unexamined Patent Publication 2012-227478 bulletin and Japanese Unexamined Patent Publication 2014-179577 bulletin.
(image display device)
Cured film (colour filter, photomask etc.) of the invention can be used in liquid crystal display device or ORGANIC ELECTROLUMINESCENCE DISPLAYS The image display devices such as device.
The detailed content of definition or each display device for display device, such as it is recorded in " electronic display unit (Zuo Zuo The clear husband of wood writes, Kogyo Chosakai Publishing CO., Ltd.1990 distribution) ", " display device (and she blow along chapter work, Sangyo Tosho Publishing Co., Ltd. the Heisei first year issues) " etc. in.Also, for liquid crystal display device, such as Be recorded in " second generation LCD Technology (Uchida Tatsuo edits, Kogyo Chosakai Publishing Co., Ltd.1994 distribution) ".Liquid crystal display device of the invention can be applied, and there is no particular restriction, such as can be applied to above-mentioned The liquid crystal display device for the various modes recorded in " second generation LCD Technology ".
When colour filter in the present invention is applied to liquid crystal display device, form is not particularly limited.
Hereinafter, being described in detail to the case where colour filter of the invention is applied to liquid crystal display device.
Colour filter of the invention can be used for the liquid crystal display device of colored TFT (Thin Film Transistor) mode. For the liquid crystal display device of colored TFT mode, such as it is recorded in " color TFT-LCD display (KYORITSU SHUPPAN CO., LTD.1996 is issued) ".Moreover, colour filter of the invention can also be applied to IPS (In Plane Switching) etc. The visual angles such as the pixels partitioning schemes such as transverse electric field driving method, MVA (Multi-domain Vertical Alignment) are expanded Big liquid crystal display device or STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend) etc..
Also, the colour filter in the present invention can also be used to bright and fine COA (Color-filterOn Array) mode.About the liquid crystal display device of COA mode, requirement characteristic for colour filter, in addition to common as the aforementioned It is required that also requiring the requirement characteristic for interlayer dielectric sometimes, that is, low-k and stripper patience other than characteristic.This The light resistance of the colour filter of invention etc. is excellent, therefore is capable of providing that resolution ratio is higher and the COA mode of long durability of backside protective sheet excellent Liquid crystal display device.In addition, resin coating can be arranged on color-filter layer in order to meet the requirement characteristic of low-k.
For these image display patterns, for example, be recorded in " EL, PDP, LCD display-technology and market it is newest dynamic To-(TORAY Research Center, Inc. investigate department and issue for 2001) " page 43 etc..
Liquid crystal display device of the invention, can also be by electrode base board, light polarizing film, phase other than colour filter of the invention The various parts such as poor film, backlight, spacer or compensation film for angular field of view are constituted.Colour filter of the invention can be applied to as known in these The liquid crystal display device that component is constituted.For these components, such as it is recorded in " the liquid crystal display periphery material chemistry system of ' 94 Product market (island Itou Kentaro CMC-Group.1994 distribution) ", " status and vision of the future (last volume) in 2003 liquid crystal connection market (the good Ji Fuji Chimera Research Institute, Inc. of table, issuing for 2003) ".
About backlight, it is recorded in SID meeting Digest 1380 (2005) (A.Konno et.al), monthly magazine is shown Page 25~30 (Yagi spark gap is grand bright) in page 18~24 (island health is abundant) in device in December, 2005 number, monthly magazine display in December, 2005 number Deng.
Also, cured film of the invention be able to use in personal computer, tablet computer, mobile phone, smart phone or The portable devices such as digital camera；The OA such as multi-function printer or scanner (Office Autom ation) equipment；Monitoring is taken the photograph Shadow machine, bar code reader and Automated Teller Machine (ATM), high speed camera or the industry such as certification in person authenticated using facial image Use equipment；Vehicle-mounted camera apparatus；The medical camera apparatus such as endoscope, capsule endoscope or conduit；Biological body sensor, life Object sensor (Biosensor), military investigation camera, relief map camera, meteorology or oceanographic observation camera, land resources Investigate astronomy or deep space target optical filter or the mould used in space equipments such as exploration camera etc. in camera or universe The light-blocking member or light shield layer of block.Moreover, cured film of the invention can be used in the antireflection portion of above-mentioned optical thin film or module Part or anti-reflection layer.
Also, cured film of the invention can also be used in miniature LED (Light Emitting Diode) or miniature The purposes such as OLED (Organic Light Emitting Diode).Although being not particularly limited, in addition to miniature LED or miniature Other than optical filter or optical thin film used in OLED, also preferably for assigning the portion of shade function or anti-reflective function Part.
As the example of miniature LED and miniature OLED, Japanese Unexamined Patent Application Publication 2015-500562 bulletin and Japanese Unexamined Patent Application Publication can be enumerated The device recorded in 2014-533890 bulletin.
Also, cured film of the invention can also be used to the purposes such as quantum dot displays.Although being not particularly limited, remove Other than optical filter used in quantum dot displays and optical thin film, also preferably for assigning shade function and counnter attack Penetrate the component of function.
As the example of quantum dot displays, it is special that U.S. Patent Application Publication No. 2013/0335677, the U.S. can be enumerated Benefit application discloses No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203 and U.S. Patent Application Publication The display recorded in No. 2014/0035960.
Embodiment
Hereinafter, the present invention is described in more detail according to embodiment.Material shown in embodiment below, usage amount, ratio Example, process content, processing step etc. can then be suitably changed without departing from spirit of the invention.The scope of the present invention as a result, It should not restrictively be explained by embodiment described below.
Hereinafter, the present invention is described in detail using embodiment.But the present invention is not limited to this.In addition, removing Non- otherwise indicated, then " part ", " % " are quality criteria.
[composition]
Hereinafter, being illustrated first to each ingredient for including in composition when the composition of preparation Examples and Comparative Examples.
< nitrogen titanium particle >
As nitrogen titanium particle, nitrogen titanium particle TiN-1~TiN-19 of following manufacture has been used.
(nitrogen titanium particle TiN-1)
Utilize the device for the black composite particles manufacturing device recorded in Fig. 1 according to International Publication No. 2010/147098 Nitrogen titanium particle TiN-1 is manufactured.
In black composite particles manufacturing device, the higher-order of oscillation coil of plasma torch applies about 4MHz and about The high frequency voltage of 80kVA supplies argon gas 50L/min and nitrogen 50L/ from plasma gas supply source as plasma gas The mixed gas of min makes to generate argon-nitrogen plasma flame in plasma torch.Also, from being sprayed for material feeding apparatus The carrier gas of gas supply source supply 10L/min.
Also, by as the titanium tetrachloride of particle raw material 1 (liquid), as the liquefied ammonia (Ube of particle raw material 2 Industries, Ltd. manufacture), as particle raw material 3 Ti powder particle (TOHO TECHNICAL SERVICE CO., LTD. manufacture, " TC-200 "), it is supplied together with carrier gas, that is, argon gas in the hot plasma flame to plasma torch, makes it It is evaporated in hot plasma flame, and with gas phase state high degree of dispersion.In addition, each flow proportional (body of particle raw material 1~3 Product ratio) as shown in table 1.
Also, it supplies as by gas supply device to the indoor gas of chamber, has used nitrogen.The indoor stream of chamber at this time Speed is set as 5m/sec, and supply amount is set as 1000L/min.Also, the pressure in cyclone separator is set as 50kPa, also, will be from The speed of chamber towards cyclone separator supply titanium particle is set as 10m/s (average value).
Then, using Ltd.Narahashi Seisakusho is used to manufacture Laboratory Kiln as calcining furnace L/K implements to be heat-treated to particle.Specifically, as atmosphere gas, with 100mL/min to calcining furnace supply nitrogen, and Heat treatment in 0.2 hour is carried out at 240 DEG C.
So obtain nitrogen titanium particle TiN-1.
To nitrogen titanium particle TiN-1 obtained, titanium (Ti) atom, chlorine are determined by ICP ICP Atomic Emission Spectrophotometer method (Cl) content of atom.In addition, Seiko Instruments Inc. manufacture is utilized about ICP ICP Atomic Emission Spectrophotometer method ICP emission spectrophotometer " SPS3000 " (trade name).
Also, about the content of nitrogen-atoms, utilize HORIBA, oxygen, the nitrogen analysis device " EMGA-620W/C " of LTD. manufacture (trade name) is measured, and is melted thermal conductivity method by inactive gas and calculated.Show the result in table 1.
Also, for aftermentioned nitrogen titanium particle TiN-2~TiN-19, also with identical as nitrogen titanium particle TiN-1 Method, determine the content of Ti atom, Cl atom, nitrogen-atoms.In addition, the surplus in each particle is to be originated from present in particle The impurity such as oxygen, the metallic element of oxide.
Show the result in table 1 and table 2.
About the X-ray diffraction of nitrogen titanium particle TiN-1, powdered sample is fitted into aluminum standard specimen holder, It is measured by wide-angle x-ray diffraction (Rigaku Corporation manufacture, trade name " RU-200R ").As measurement Condition, x-ray source are set as CuK alpha ray, and output is set as 50kV/200mA, and slit system is set as 1 ° of -1 ° of -0.15mm-0.45mm, Measurement step-length (2 θ) is set as 0.02 °, and scanning speed is set as 2 °/minute.
Also, determine the angle of diffraction (2 θ) at the peak from TiN (200) face.Also, passes through the half-peak breadth at the peak, utilize Xie Le (Scherrer) formula, has found out the crystallite dimension of constituent particle.Show the result in table 1.
In addition, for nitrogen titanium particle TiN-2~TiN-19 below, with identical with nitrogen titanium particle TiN-1 Method determines 2 θ of the angle of diffraction and crystallite dimension.Show the result in table 1 and table 2.
The measurement of average primary particle diameter about nitrogen titanium particle TiN-1 utilizes transmission electron according to the above method Microscope (Transmission Electron Microscope；TEM it) is determined.Also, it is real simultaneously with said determination Applied particle shape observation, as a result, confirm 100 observation object nitrogen titanium particle in 60 the above are spherical shapes. These results are shown in table 1.In addition, the shape about particle observes evaluation, when measure object is 60% the above are when spherical shape, " spherical shape " is shown as in table.When the quantity of spherical particle is less than the 60% of measure object, it is shown as that " spherical shape is less than in table 60% ".Also, when being recorded as " cube " in table, indicate that the quantity of the particle of cube is 60% or more of measure object.Separately Outside, cube is not limited to be observed to the particle of cube, and the polyhedron at observable angle is also used as cube to be surveyed It is fixed.
In addition, for nitrogen titanium particle TiN-2~TiN-19 below, also according to and nitrogen titanium particle TiN-1 phase With method measure average primary particle diameter, further progress shape observation.Show the result in table 1 and table 2.
About the specific surface area of nitrogen titanium particle TiN-1, using nippon-bel CO., Ltd. manufacture high-precision is complete certainly Dynamic gas adsorbing device (" BELSORP " 36) after carrying out vacuum outgas at 100 DEG C, measures N2The liquid nitrogen temperature of gas Adsorption isotherm under (77K) analyzes the thermoisopleth by BET method to have found out specific surface area.Show the result in table 1.
In addition, for nitrogen titanium particle TiN-2~TiN-19 below, with identical with nitrogen titanium particle TiN-1 Method has found out specific surface area.
Show the result in table 1 and table 2.
(nitrogen titanium particle TiN-2)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 1, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-2.
(nitrogen titanium particle TiN-3)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 1, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-3.
(nitrogen titanium particle TiN-4)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 1, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-4.
(nitrogen titanium particle TiN-5)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 1, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-5.
(nitrogen titanium particle TiN-6)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat The indoor flow velocity of manage bar part, chamber is set as shown in table 1, in addition to this, with method identical with nitrogen titanium particle TiN-1 manufacture Nitrogen titanium particle TiN-6.
(nitrogen titanium particle TiN-7)
The indoor flow velocity of chamber is set as shown in table 1, in addition to this, in method identical with nitrogen titanium particle TiN-6 Nitrogen titanium particle TiN-7 is manufactured.
(nitrogen titanium particle TiN-8)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat The indoor flow velocity of manage bar part, chamber is set as shown in table 1, in addition to this, with method identical with nitrogen titanium particle TiN-1 manufacture Nitrogen titanium particle TiN-8.
(nitrogen titanium particle TiN-9)
The indoor flow velocity of chamber is set as shown in table 1, in addition to this, in method identical with nitrogen titanium particle TiN-8 Nitrogen titanium particle TiN-9 is manufactured.
(nitrogen titanium particle TiN-10)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 1, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-10.
(nitrogen titanium particle TiN-11)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 2, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-11.In addition, particle raw material 3 is not used in TiN-11.
(nitrogen titanium particle TiN-12)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 2, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-12.In addition, particle raw material 1 and 2 is not used in TiN-12.
(nitrogen titanium particle TiN-13)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 2, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-13.In addition, the heat treatment temperature of nitrogen titanium particle TiN-13 is set as 250 DEG C.
(nitrogen titanium particle TiN-14)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 2, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-14.
(nitrogen titanium particle TiN-15)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 2, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-15.
(nitrogen titanium particle TiN-16)
Heat treatment condition is set as shown in table 2, in addition to this, with method system identical with nitrogen titanium particle TiN-15 Nitrogen titanium particle TiN-16 is made.
(nitrogen titanium particle TiN-17)
Particle raw material 1~3 used in the manufacture of nitrogen titanium particle TiN-1 particle and its flow proportional are set as such as table Shown in 2, in addition to this, nitrogen titanium particle TiN-17 has been manufactured in method identical with nitrogen titanium particle TiN-1.
(nitrogen titanium particle TiN-18)
Particle raw material 1~3 used in the manufacture of nitrogen titanium particle TiN-1 particle and its flow proportional are set as such as table Shown in 2, in addition to this, nitrogen titanium particle TiN-18 has been manufactured in method identical with nitrogen titanium particle TiN-1.
(nitrogen titanium particle TiN-19)
At particle raw material 1~3 and its flow proportional used in the manufacture of nitrogen titanium particle TiN-1 particle and heat Manage bar part is set as shown in table 2, in addition to this, has manufactured nitrogen titanium grain in method identical with nitrogen titanium particle TiN-1 Sub- TiN-19.
Above-mentioned nitrogen titanium particle TiN-1~nitrogen titanium particle TiN-19 manufacturing condition transitivity is shown in following tables 1 and table 2.
In addition, being heat treatment other than nitrogen titanium particle TiN-11, TiN-12, TiN-13 and TiN-14 in table 240 DEG C of temperature.
< dispersing agent >
As dispersing agent, dispersant A~E with flowering structure has been used.In dispersant A, B, D, recorded in each structural unit Numerical value indicate relative to all structural units each structural unit quality %.Also, in dispersing agent C, in each structural unit The numerical value (a~e) of record indicates the molar ratio of each structural unit relative to all structural units, and x and y indicate connective number.And And in dispersing agent E, the quantity with Z connection is indicated with the numerical value recorded in the linking group of Z connection.
[chemical formula 20]
[chemical formula 21]
< adhesive resin >
As adhesive resin, adhesive resin A and B below has been used.
Adhesive resin A (Akurikyua RD-F8 NIPPON SHOKUBAI CO., LTD. manufacture, with reference to following knots Structure)
Adhesive resin B (Cyclomer P (ACA) 230AA DAICEL CORPORATION manufacture)
[chemical formula 22]
< polymerizable compound >
Polymerizable compound M1 (Nippon Kayaku CO., Ltd. manufacture, trade name " KAYARAD ", with reference to following Structure)
[chemical formula 23]
PET-30 (pentaerythritol triacrylate, Nippon Kayaku CO., Ltd. manufacture)
< polymerization initiator >
OXE-02:Irgacure OXE02 (trade name, BASF JAPAN LTD. manufacture)
OXE-03:Irgacure OXE03 (trade name, BASF JAPAN LTD. manufacture)
N-1919: trade name, ADEKA CORPORATION manufacture
IRGACURE-907: trade name, BASF JAPAN LTD. manufacture
< solvent >
PGMEA: propylene glycol methyl ether acetate
Cyclopentanone
Butyl acetate
3- ethoxyl ethyl propionate
Distill butyl acetate
Distill cyclopentanone
In addition, having used as above-mentioned distillation butyl acetate and distillation cyclopentanone to commercially available butyl acetate and cyclopentanone Carry out the solvent of distilation.
< polymerization inhibitor >
P methoxy phenol
< surfactant >
F-1: following mixtures (weight average molecular weight (Mw)=14000)
[chemical formula 24]
The preparation > of < pigment dispersion
Firstly, by blender (IKA COMPANY manufactures EUROSTAR), by nitrogen titanium particle, dispersing agent and solvent Mixing 15 minutes, to obtain dispersion.Then, to dispersion obtained, Shinmaru Enterprises is used The NPM-Pilot of Corporation manufacture, carries out decentralized processing, to obtain pigment dispersion under the following conditions.
(dispersion condition)
Pearl diameter: φ 0.05mm, (NIKKATO CORPORATION manufactures YTZ)
Microballon filling rate: 65 volume %
Grind peripheral speed: 10m/sec
Separator peripheral speed: 13m/s
Carry out the mixing liquid measure of decentralized processing: 15kg
Circular flow (pump supply amount): 90kg/hour
Treatment fluid temperature: 19~21 DEG C
Cooling water: water
The processing time: 22 hours
The preparation > of < composition
Then, above-mentioned dispersible pigment dispersion, adhesive resin, polymerizable compound, polymerization initiator and molten are mixed and stirred for Each composition of Examples and Comparative Examples shown in following Table 3~table 5 thereby is achieved in agent.The each group of Examples and Comparative Examples The content (quality %) for closing each ingredient for including in object is shown in 3~table of table 5.
In addition, with dispersing agent relative to the solid component in the ratio ((mass ratio) D/P) of nitrogen titanium particle, composition Amount of moisture (quality %, measuring method described below in concentration (quality %), composition.), the pigment concentration in solid component The mode that (quality %) becomes ratio shown in each Examples and Comparative Examples of 3~table of table 5 is prepared for each composition.
(measurement of the amount of moisture in composition)
The amount of moisture of each composition about Examples and Comparative Examples, by former in Karl Fischer method as measurement The MKV-710 (trade name, KYOTO ELECTRONICS MANUFACTURING CO., LTD. manufacture) of reason is determined.It will As a result it is shown in 3~table of table 5.
[evaluation test]
Each evaluation test below has been carried out to each composition of Examples and Comparative Examples.
< degassing >
Colour filter frame has been made using each composition of Examples and Comparative Examples.
Specifically, on the semiconductor substrate for imagining imaging sensor on 8 inches of substrates to constitute, after prebake conditions Film thickness becomes 1.5 μm of mode, and the compositions of spin coating Examples and Comparative Examples forms film.Then, in 720 μm of cross, vertical 520 μm periphery configuration be capable of forming 250 μm of width, 200 μm of beam overall photomask binary mask, utilize i x ray exposure x device (FPA-3000+i5, Canon Inc. manufacture) is exposed (light exposure 500mJ/cm2) after, further progress development.
For the semiconductor substrate obtained with multiple colour filter frames, it is cut into the size of 10mm × 10mm, is led to The Cl amount in thermal desorption spectrum analysis method (TDS) detection degassing is crossed, and is evaluated according to following benchmark.Measurement is cancelled in backstage Source in total amount of gas evolved (detecting total ionic current values) until mass number 1 to 199 when the counting from Atmospheric components for including Counting intensity ratio from the peak position of Cl, and evaluated according to following benchmark.Vacuum degree when measuring is set as 1 × 10- 7Torr or less.
" A ": in degassing 1L, Cl amount is 10ppm or less
" B ": in degassing 1L, Cl amount is more than 10ppm and 50ppm or less
" C ": in degassing 1L, Cl amount is more than 50ppm and 100ppm or less
" D ": in degassing 1L, Cl amount is more than 100ppm
The number > of < particle
It is prepared by PGMEA and above-mentioned composition is diluted to 500 times of sample solution, analyzed by flow-type particle picture Device (trade name " FPIA-3000 ", Malvern Instruments Ltd manufacture), which determines in sample solution 10ml, includes 10 μm of dimensions above particle quantity.
< OD value >
On the glass plate (EagleXG, Corning Inc. manufacture) of thickness 0.7mm, 10cm square, become with film thickness The compositions of 1.0 μm of revolving speed spin coating Examples and Comparative Examples forms film, on hot plate by 100 DEG C, the heat of 2min at Reason obtains desciccator diaphragm.For substrate obtained, pass through spectrophotometer U-4100 (Hitachi High- Technologies Corporation. manufacture) measurement OD, it measures wavelength region 400nm and becomes minimum OD into 1200nm Value, and evaluated according to following benchmark.
" A ": minimum OD is 4.2 or more
" B ": minimum OD is 3.8 more than and less than 4.2
" C ": minimum OD is 3.5 more than and less than 3.8
" D ": minimum OD is less than 3.5
< filterability >
To the composition of Examples and Comparative Examples, capsule filters DFA (NIHON PALL LTD. manufacture, nylon hole are utilized 0.45 μm of diameter, 2inch), carry out the evaluation of filterability.In addition, filter combination under conditions of flow 400ml/min 16kg, and evaluated according to benchmark below.
" A ": 16kg whole has been filtered.
" B ": after having filtered 12kg more than and less than 16kg, flow becomes less than 400mL/min.
" C ": after having filtered 8kg more than and less than 12kg, flow becomes less than 400mL/min.
" D ": it has filtered and has been less than after 8kg, flow becomes less than 400mL/min.
< composition through when viscosity stability (CM through when stablize) >
After the composition of Examples and Comparative Examples is saved 30 days at 23 DEG C, saved at 7 DEG C 9 months.Later Using E type viscosimeter (TOKI SANGYO CO., LTD. manufacture, trade name " R85 shape viscosimeter "), with revolving speed 10rpm, 23 DEG C Condition determine the viscosity for saving each composition of front and back, and thickening rate is calculated by following formula.Evaluation criteria is as follows.
(thickening rate)=(through when after viscosity)-(just adjust liquid after viscosity)/(just adjust liquid after viscosity)
" A ": thickening rate is less than 3%
" B ": thickening rate is 3% more than and less than 5%
" C ": thickening rate is 5% more than and less than 10%
" D ": thickening rate is 10% or more
< patternability (resolution ratio) >
It is formd on image sensing device substrate using the composition of Examples and Comparative Examples by spin coater Film.Then, to film obtained, the prebake conditions processing of 100 DEG C, 2min has been carried out on hot plate.Then, it is penetrated using i Line exposing device (FPA, Canon Inc. manufacture), is exposed the film by the processing of above-mentioned prebake conditions, further progress Development, thus the acceptance part outer peripheral portion on substrate forms the photomask other than cladding cutting line and electrode portion, and in base 20 alignment marks with 20 μm of line width are formed on plate.
It is formed by the number of alignment mark using optical microphotograph sem observation, has thus carried out the evaluation of resolution ratio.
" A ": 20 labels are formd.
" B ": 19 labels are formd.
" C ": 18 labels are formd.
" D ": 17 or less are labeled as.
The anti-corrosive properties > of < electrode
It is formd on image sensing device substrate using the composition of Examples and Comparative Examples by spin coater Film.Then, the device substrate after being formed to film obtained has carried out 100 DEG C, at the prebake conditions of 2min on hot plate Reason.Then, using i x ray exposure x device (FPA-3000+i5, CanonInc. are manufactured), to the painting by the processing of above-mentioned prebake conditions Film is exposed, and further progress development, thus the acceptance part outer peripheral portion on substrate forms cladding cutting line and electrode portion Photomask in addition.Moreover, having carried out heat treatment (the rear baking of 220 DEG C, 5min using heating plate to photomask obtained Roasting process).
By the wafer with photomask obtained, (ESPEC CORP. in the environment of 110 DEG C of temperature, humidity 90%RH Manufacture HAST testing machine EHS-411M) after preservation 3 days, to 300 electrode pads being formed on wafer, pass through optical microphotograph Mirror (Olympus Corporation manufacture, trade name " LEXT OLS4500 ") observes the generation state of the rust of electrode pattern, And the evaluation of the anti-corrosive properties of electrode is carried out according to following benchmark.
" A ": variation is not observed
" B ": the corrosion of electrode is 2 or less
" C ": the corrosion of electrode is more than 2 and 10 or less
" D ": the corrosion of electrode is more than 10
By the above evaluation test evaluation result is shown in table 3~table 5.
In addition, the mixed proportion of M1 and PET-30 are 5:5 by quality ratio in embodiment 33.
As shown in 3~table of table 5, the content by the chlorine atom in nitrogen titanium particle is shown in 0.001~0.3 matter In the range of measuring % (in other words, the 10 mass ppm of mass ppm~3000), can make electrode anti-corrosive properties are excellent and pattern shape Become second nature (resolution ratio) excellent cured film (embodiment).
If also, the content for showing the chlorine atom in nitrogen titanium particle is more than 0.3 mass % (in other words, 3000 matter Measure ppm), then the anti-corrosive properties of patternability (resolution ratio) and electrode are poor (comparative example 1, comparative example 2).
If also, the content for showing the chlorine atom in nitrogen titanium particle (in other words, is less than less than 0.001 mass % 10 mass ppm), then the poor situation of patternability (resolution ratio) (comparative example 3, comparative example 4).
Also, by the comparison with embodiment 17~21, confirm the content of water relative to composition gross mass be 0.1~ When 1 mass % (preferably 0.1~0.8 mass %, more preferably 0.1~0.4 mass %), the patternability of cured film (divides Resolution) it is more excellent with the anti-corrosive properties of electrode material.Also, it confirms by the way that the content of water to be set as relative to composition gross mass 0.1~1 mass % can more reduce the grain amount in composition, and the viscosity ageing stability of composition is also more excellent.
Also, by the comparison of embodiment 26 and embodiment 27, when to confirm D/P be 0.3 or less, the pattern shape of cured film Become second nature (resolution ratio) it is more excellent.
By the comparison of embodiment 26,31 and 32, the content of nitrogen titanium particle is confirmed relative to the total solid of composition When body ingredient is 30~70 mass %, the anti-corrosive properties of light splitting property (good OD value), patternability (resolution ratio) and electrode are more It is excellent.
Also, the comparison for passing through embodiment 6~9, confirms the specific surface area of nitrogen titanium particle found out by BET method For 40~60m2When/g, light splitting property (good OD value) and patternability (resolution ratio) are more excellent.Also, confirm filterability Also excellent.
Also, by the comparison of embodiment 10~14, confirm using CuK alpha ray as when x-ray source, nitrogen titanium grain When 2 θ of the angle of diffraction at the peak from (200) face of son is more than 42.8 ° and 43.5 ° or less, light splitting property (good OD value) and pattern Formative (resolution ratio) is more excellent.
Also, by the comparison of embodiment 12~15, the average primary particle diameter for confirming nitrogen titanium particle is 10~ When 30nm, light splitting property (good OD value) is more excellent.Also, the viscosity ageing stability for confirming composition is also excellent.Also, When the average primary particle diameter for confirming nitrogen titanium particle is 10nm or more, the viscosity ageing stability of composition is excellent.
Also, the comparison for passing through embodiment 12 and embodiment 16, confirm nitrogen titanium particle utilizes transmission electron In the shape of microscopical primary particle, when spherical ratio is 60 mass % or more, light splitting property (good OD value) and pattern Formative (resolution ratio) is more excellent.Also, filterability and the viscosity ageing stability for confirming composition are also excellent.
In embodiment 1, surfactant F-1 is not used and is evaluated in the same way in addition to this.Evaluation knot Fruit learns and can get result same as Example 1.
The preparation > of < carbon black dispersion (CB dispersion liquid)
In the preparation of above-mentioned pigment dispersion, instead of nitrogen titanium particle, carbon black (trade name " Color Black has been used S170 ", Degussa-H ü ls AG manufacture, average primary particle diameter 17nm, BET specific surface area 200m2/ g, pass through channel black mode system The carbon black made), in addition to this, dispersion is made in the same way, and obtain carbon black dispersion.
In the preparation of the composition of embodiment 1, instead of with the nitrogen titanium particle TiN-1 in composition containing 19 mass % The dispersible pigment dispersion that adds of mode, used the dispersible pigment dispersion containing nitrogen titanium particle TiN-1 and above-mentioned CB dispersion liquid Mixture " the nitrogen titanium particle TiN-1 in composition: carbon black=15:4 (mass ratio) in composition.In composition The total content of nitrogen titanium particle TiN-1 and carbon black is 19 mass %.", in addition to this, combination is prepared in the same way Object, and evaluated using the composition.Evaluation result is learnt and can get light-proofness same as Example 1.
The preparation > of < color pigment dispersion (PY dispersion liquid)
In the preparation of above-mentioned pigment dispersion, instead of nitrogen titanium particle, 150 (Hangzhou of pigment yellow has been used Star-up Pigment CO., Ltd. manufacture, 6150 pigment yellow 5GN of trade name), in addition to this, production point in the same way Object is dissipated, to obtain color pigment dispersion (PY dispersion liquid).
In the preparation of the composition of embodiment 1, instead of with the nitrogen titanium particle TiN-1 in composition containing 19 mass % The dispersible pigment dispersion that adds of mode, used the dispersible pigment dispersion containing nitrogen titanium particle TiN-1 and above-mentioned PY dispersion liquid Mixture " the nitrogen titanium particle TiN-1 in composition: the pigment yellow 150=17:2 (mass ratio) in composition.Composition In nitrogen titanium particle TiN-1 and pigment yellow 150 total content be 19 mass %.", in addition to this, in the same way Composition is prepared, and is evaluated using the composition.Evaluation result learns and can get light-proofness same as Example 1, And it can get further black film.

Claims (19)

1. a kind of composition contains the nitrogen titanium particle comprising chlorine atom,
The content of the chlorine atom in the nitrogen titanium particle is 0.001~0.3 mass %.
2. composition according to claim 1, wherein
Using CuK alpha ray as when x-ray source, 2 θ of the angle of diffraction at the peak from (200) face of the nitrogen titanium particle be more than 42.8 ° and 43.5 ° or less.
3. composition according to claim 1 or 2, wherein
The specific surface area of the nitrogen titanium particle found out by BET method is 40~60m2/g。
4. composition according to any one of claim 1 to 3, wherein
The average primary particle diameter of the nitrogen titanium particle is 10~30nm.
5. composition according to any one of claim 1 to 4, wherein
In photo observation using the primary particle image of the nitrogen titanium particle of transmission electron microscope, 100 sights Examining in object 60, the above are spherical shapes.
6. composition according to any one of claim 1 to 5 also contains solvent of more than two kinds.
7. composition according to any one of claim 1 to 6, also contains dispersing agent.
8. composition according to claim 7, wherein
The dispersing agent is 0.3 or less relative to the content ratio of the nitrogen titanium particle by quality ratio.
9. composition according to any one of claim 1 to 8, also contains polymerizable compound.
10. composition according to any one of claim 1 to 9, also contains polymerization initiator.
11. composition according to any one of claim 1 to 10, wherein
Solid component in the composition is 10~40 mass %.
12. composition according to any one of claim 1 to 11, wherein
Total solid content of the content of the nitrogen titanium particle relative to the composition is 30~70 mass %.
13. composition according to any one of claim 1 to 12, also contains water,
The content of the water is 0.1~1 mass % relative to the composition gross mass.
14. composition according to any one of claim 1 to 13, also contains dispersing agent,
The dispersing agent has to be selected to be made of polycaprolactone, poly- valerolactone, polymethyl acrylate and polymethyl methacrylate Group at least one kind of structure.
15. a kind of cured film is obtained using composition described in any one of any one of claims 1 to 14 14.
16. a kind of colour filter, with the cured film described in claim 15.
17. a kind of photomask, with the cured film described in claim 15.
18. a kind of solid-state imager, with the cured film described in claim 15.
19. a kind of image display device, with the cured film described in claim 15.
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CN114269555A (en) * 2019-09-06 2022-04-01 富士胶片株式会社 Composition, film, structure, color filter, solid-state imaging element, and image display device
CN115280238A (en) * 2020-03-06 2022-11-01 富士胶片株式会社 Photosensitive composition, cured film, color filter, light-shielding film, optical element, solid-state imaging element, infrared sensor, and headlight unit

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CN109073799B (en) 2021-03-09
WO2017169584A1 (en) 2017-10-05
CN113031398A (en) 2021-06-25
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JP6698820B2 (en) 2020-05-27

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