CN106662815A - Negative light-sensitive resin combination, resin cured film, next door and optical element - Google Patents
Negative light-sensitive resin combination, resin cured film, next door and optical element Download PDFInfo
- Publication number
- CN106662815A CN106662815A CN201580038938.5A CN201580038938A CN106662815A CN 106662815 A CN106662815 A CN 106662815A CN 201580038938 A CN201580038938 A CN 201580038938A CN 106662815 A CN106662815 A CN 106662815A
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- Prior art keywords
- ink
- next door
- agent
- compound
- acid
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- 229920005989 resin Polymers 0.000 title claims abstract description 207
- 239000011347 resin Substances 0.000 title claims abstract description 207
- 230000003287 optical effect Effects 0.000 title claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 221
- 239000002253 acid Substances 0.000 claims abstract description 131
- 239000010408 film Substances 0.000 claims abstract description 126
- 239000003513 alkali Substances 0.000 claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000002096 quantum dot Substances 0.000 claims abstract description 30
- 239000010409 thin film Substances 0.000 claims abstract description 25
- -1 amine compound Chemical class 0.000 claims description 132
- 150000001875 compounds Chemical class 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 54
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 32
- 125000001153 fluoro group Chemical group F* 0.000 claims description 32
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000007870 radical polymerization initiator Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 abstract description 39
- 239000000178 monomer Substances 0.000 abstract description 19
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- 238000005401 electroluminescence Methods 0.000 description 38
- 238000001723 curing Methods 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
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- 238000006243 chemical reaction Methods 0.000 description 23
- 210000004027 cell Anatomy 0.000 description 22
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- 239000000126 substance Substances 0.000 description 11
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- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical group C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 7
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- 125000002091 cationic group Chemical group 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
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- 238000007639 printing Methods 0.000 description 6
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- 239000002994 raw material Substances 0.000 description 6
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 6
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical class ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000007874 V-70 Substances 0.000 description 5
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
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- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
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- 239000005871 repellent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical class CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229950004288 tosilate Drugs 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- YEIGUXGHHKAURB-UHFFFAOYSA-N viridine Natural products O=C1C2=C3CCC(=O)C3=CC=C2C2(C)C(O)C(OC)C(=O)C3=COC1=C23 YEIGUXGHHKAURB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
Abstract
The present invention provide next door upper surface have it is good refuse ink and can reduce the negative light-sensitive resin combination for manufacturing optical element (organic EL element, quantum dot displays, tft array, thin-film solar cells) etc. of the residue of opening portion, upper surface have the good resin cured film used for optical elements for refusing ink, fine and high precision pattern can be formed next door used for optical elements and the above-mentioned optical element with the next door.Offer negative light-sensitive resin combination, the cured film formed using the negative light-sensitive resin combination and next door and above-mentioned optical element, the negative light-sensitive resin combination is characterised by, containing the alkali soluble resin with photo-curable or base soluble monomer, Photoepolymerizationinitiater initiater, acid producing agent, acid as curing agent and ink agent is refused, the optical element has multiple points and the next door positioned between consecutive points in substrate surface.
Description
Technical field
The present invention relates to be used for Production Example such as organic EL element, quantum dot displays, tft array, thin-film solar cells
Negative light-sensitive resin combination, resin cured film, next door and optical element Deng optical element, in particular to organic
EL element, quantum dot displays, tft array and thin-film solar cells etc..
Background technology
In organic EL (Electro-Luminescence) element, quantum dot displays, TFT (Thin Film
Transistor) in the manufacture of the optical element such as array, thin-film solar cells, using sometimes will be luminous by ink-jet (IJ) method
The method of the organic layers such as layer or inorganic layer pattern printing into putting.In the method, the profile along the point to be formed arranges next door,
Ink of the injection containing organic layer or the material of inorganic layer in the subregion (hereinafter also referred to as " opening portion ") surrounded by the next door
And be dried and/or heat, it is consequently formed the point of desired pattern.
When carrying out pattern printing by ink-jet (IJ) method, in order to prevent the ink between consecutive points mixing and formed
When even spread ink, next door upper surface need have refuses ink.On the other hand, surrounded by the next door comprising next door side
Point formation opening portion is needed with ink-receptive.Therefore, there is the next door for refusing ink in order to obtain upper surface, it is known that a kind of
Method using next door corresponding with the pattern of point is formed by photoetching process containing the photosensitive polymer combination for refusing ink agent.
In addition, in the optical elements such as such organic EL element, the product higher in order to obtain precision in recent years, for example
Propose a kind of can formation in patent document 1 to refuse the excellent film of ink, tumbling property of ink and then can be formed fine
Pattern photosensitive polymer combination.In patent document 1, made by using the photosensitive polymer combination of following (1) or (2)
It is the photosensitive polymer combination for forming next door, and obtains as ink agent is refused containing special fluororesin wherein
Effect is stated, the photosensitive polymer combination of (1) contains acid producing agent and acid as curing agent, and the acid as curing agent is that have 2
The compound of the reactive group that can be crosslinked with acidic-group above, the photosensitive polymer combination of (2) contain light
Radical polymerization initiator and free-radical crosslinking agent, the free-radical crosslinking agent is that have the ethylenic double bond and not of more than 2
Compound with acidic-group.
However, in organic EL element, quantum dot displays, tft array, the manufacture of thin-film solar cells, from raising
From the viewpoint of production efficiency, classify as to containing the photosensitive polymer combination for refusing ink agent, being particularly in patent document 1
(2) photosensitive polymer combination requires more high-sensitivity.Therefore, for such photosensitive polymer combination, if only increasing
Plus the amount of radical initiator, then can high-sensitivity, even if with low light exposure also can be formed upper surface have refuse ink
Property next door, but there are problems that live width easily thicker, patternability be deteriorated it is such.
In addition, for example in patent document 2, as the adaptation of high sensitivity, high-resolution and its solidfied material and substrate
It is excellent and with the negative light-sensitive resin combination for being capable of alkali development of excellent elastic recovery characteristics, it is proposed that a kind of organic
EL element photosensitive composite, containing hydrophilic matrix tablets (A), polyfunctional monomer (B), cationically polymerizable compound
(C), hydrolysable silanes compound (D), optical free radical polymerization initiator (E), acid producing agent (F).However, in patent document 2
Composition is difficult to high-sensitivity, and liquid-repellant is not enough.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2004-277494 publications
Patent document 2:Japanese Unexamined Patent Publication 2012-014931 publications
The content of the invention
The present invention makes to solve the above problems, it is therefore intended that in order to keep production efficiency well
While form fine and high precision pattern using the next door for obtaining, there is provided a kind of next door upper surface has good refuses ink
Property and the residue of opening portion can be reduced and then the flexible application (Flexible of plastic base can be also suitable for use with
Application) for the Production Example such as light such as organic EL element, quantum dot displays, tft array, thin-film solar cells
Learn the negative light-sensitive resin combination of element.
The resin cured film of ink is well refused present invention aim at providing a kind of upper surface and having and by upper table
Face has good refuse ink and can form fine and high precision pattern and then can also be suitable for use with plastics base
Such as organic EL element, quantum dot displays, tft array, the thin-film solar cells of the flexible application of plate etc. are used for optical elements
Next door.
The object of the invention also resides in offer to be had in the opening portion even spread ink divided by next door and precision well
The optical elements such as the organic EL element of the point of formation, quantum dot displays, tft array and thin-film solar cells, particularly wrap
Optical element containing the flexible application for having used plastic base.
The present invention provide the negative light-sensitive resin combination of composition with following [1]～[9], resin cured film, every
Wall and optical element.
[1] a kind of negative light-sensitive resin combination, it is characterised in that containing the alkali soluble resin with photo-curable
Or base soluble monomer (A), optical free radical polymerization initiator (B), light acid producing agent (C), acid as curing agent (D) and with fluorine atom
Refuse ink agent (E).
[2] according to the negative light-sensitive resin combination of [1], it is characterised in that further containing compound (F), the change
Compound (F) has the unsaturated double-bond of more than 2 and does not have any one of acidic-group and fluorine atom in intramolecular.
[3] according to the negative light-sensitive resin combination of [1] or [2], wherein, the acid as curing agent (D) is selected from trimerization
At least a kind in cyanamide based compound, urea based compound and epoxy based compound.
[4] according to the negative light-sensitive resin combination of any one of [1]～[3], for manufacturing organic EL element, quantum
Point display, tft array or thin-film solar cells.
[5] a kind of resin cured film, it is characterised in that using the negative photosensitive resin of any one of above-mentioned [1]～[4]
Composition and formed.
[6] a kind of next door, is created as the next door of the shape of multiple subregions that substrate surface is divided into a formation, its
It is characterised by, is made up of the resin cured film of [5].
[7] a kind of optical element, is the optical element for having multiple points and the next door positioned between consecutive points in substrate surface,
Characterized in that, the next door is formed by the next door of [6].
[8] according to the optical element of [7], wherein, the optical element is organic EL element, quantum dot displays, TFT battle arrays
Row or thin-film solar cells.
[9] according to the optical element of [7] or [8], wherein, the point is formed by ink-jet method.
In accordance with the invention it is possible to provide a kind of for Production Example such as organic EL element, quantum dot displays, tft array, thin
The negative light-sensitive resin combination of the optical elements such as film solar cell, it passes through to keep production efficiency well, while
To next door upper surface there is good ink of refusing, and the residue of opening portion is reduced, thus, it is possible to form micro- using next door
The pattern of thin and high precision, and then, additionally it is possible to it has been suitable for use with the flexible application of plastic base.
The resin cured film of the present invention has good ink of refusing in upper surface, and next door has good refusing in upper surface
Ink and fine and high precision pattern can be formed, can be suitably used for organic EL element, quantum dot displays,
Tft array, thin-film solar cells etc., particularly comprising the optical element of the flexible application for having used plastic base.
The optical element of the present invention is that have in the opening portion even spread ink divided by next door and the good landform of precision
Into point optical element, specifically organic EL element, quantum dot displays, tft array, thin-film solar cells etc..
According to the present invention, even the optical element comprising the flexible application for having used plastic base, it is also possible to realize the effect above.
Description of the drawings
Figure 1A is the process chart of the manufacture method in the next door for schematically showing embodiments of the present invention.
Figure 1B is the process chart of the manufacture method in the next door for schematically showing embodiments of the present invention.
Fig. 1 C are the process charts of the manufacture method in the next door for schematically showing embodiments of the present invention.
Fig. 1 D are the process charts of the manufacture method in the next door for schematically showing embodiments of the present invention.
Fig. 2A is the process chart of the manufacture method of the optical element for schematically showing embodiments of the present invention.
Fig. 2 B are the process charts of the manufacture method of the optical element for schematically showing embodiments of the present invention.
Specific embodiment
In this specification, following term is used respectively with following implications.
" (methyl) acryloyl group " is the general name of " methylacryloyl " and " acryloyl group ".(methyl) acryloxy,
(methyl) acrylic acid, (methyl) acrylate, (methyl) acrylamide and (methyl) acrylic resin are also taken this as the standard.
Sometimes the group shown in formula (x) is abbreviated as into group (x).Sometimes the compound shown in formula (y) is abbreviated as into chemical combination
Thing (y).Here, formula (x), formula (y) represent any formula.
" resin constituted with certain composition based on " or " based on the resin of certain composition " refer to the ratio of the composition
Example is accounted for more than 50 mass % relative to resin total amount.
" side chain " is that the carbon for constituting main chain is bonded in the repetitive formed by carbon atom constitutes the polymer of main chain
Group beyond atom, hydrogen atom or halogen atom.
Formed in the composition that " total solid content of photosensitive polymer combination " refers to contained by photosensitive polymer combination
The composition of cured film described later, can be obtained by photosensitive polymer combination is heated into 24 hours removing solvents at 140 DEG C
Residue obtain.Should illustrate, total solid content amount can also be calculated by inventory.
The film being made up of the solidfied material of the composition with resin as principal component is referred to as into " resin cured film ".Sense will be coated with
The film of photosensitive resin composition is referred to as " film ", and the film for being dried it is referred to as into " desciccator diaphragm ".Solidify " desciccator diaphragm "
Obtained from film be " resin cured film ".In addition, also " resin cured film " is referred to as " cured film " sometimes.
Resin cured film can also be the form in next door, and the next door is formed as the region division of regulation into multiple subregions
Shape.For example following " ink " is injected in the opening portion in the subregion divided by next door, i.e. being surrounded by next door, is formed " point ".
" ink " is the rear term with optical function and/or the liquid of Electricity Functional such as to be referred to as being dried, solidify.
In the optical elements such as organic EL element, quantum dot displays, tft array, thin-film solar cells, colour filter, sometimes for work
For the point of various inscapes, pattern printing is carried out by ink-jet (IJ) method with ink using the point formation." ink " is included should
Ink used in purposes.
" refusing ink " is the property for repelling above-mentioned ink, with both water repellency and oil repellent.Refuse ink for example may be used
To be evaluated by the way that contact angle during ink is added dropwise." ink-receptive " is the property contrary with ink is refused, same with ink is refused
Sample ground can be evaluated by the way that contact angle during ink is added dropwise.Or can be by the way that oil during ink is added dropwise with stipulated standard evaluation
The degree (the moistening autgmentability of ink) of the moistening extension of ink is evaluating ink-receptive.
" point " represents the Minimum Area for being capable of light modulation in optical element.Organic EL element, quantum dot displays,
In the optical elements such as tft array, thin-film solar cells, colour filter, in white and black displays, 1 point=1 pixel, in colored display
When, such as 3 points (R (red), G (green), B (indigo plant) etc.)=1 pixels." optical element " is used as the term comprising electronic device.
" percentage (%) " represents in case of no particular description quality %.
Hereinafter, embodiments of the present invention are illustrated.
[negative light-sensitive resin combination]
The negative light-sensitive resin combination of the present invention is characterised by containing the alkali soluble resin with photo-curable
Or base soluble monomer (A), optical free radical polymerization initiator (B), light acid producing agent (C), acid as curing agent (D) and with fluorine atom
The negative light-sensitive resin combination for refusing ink agent (E).In this manual, acid as curing agent (D) is referred in the presence of acid
The curing agent reacted with the acidic-group such as carboxylic acid, phenolic hydroxyl group.The negative light-sensitive resin combination of the present invention can be closed
It is used to manufacture the optical elements such as organic EL element, quantum dot displays, tft array, thin-film solar cells, colour filter suitablely,
Significant effect particularly can be expected in organic EL element, quantum dot displays, tft array, thin-film solar cells.
Generally, negative light-sensitive resin combination is solidified by exposure, forms cured film.Now, if by sheltering
The exposure portion and non-exposed portion of regulation shape are formed, then non-exposed portion does not solidify, and can optionally be removed with alkaline developer.Its
As a result, it is possible to make cured film become the form in the next door of the shape that predetermined region is divided into multiple subregions.
The negative light-sensitive resin combination of the present invention is utilized in above-mentioned exposure portion and produced by optical free radical polymerization initiator (B)
Raw free radical makes alkali soluble resin or base soluble monomer (A) be polymerized and is solidified to form cured film.Here, alkali-soluble
Resin or base soluble monomer (A) do not contain fluorine atom.Refuse ink agent (E) and form cured film by having with fluorine atom
During migrate to the property of upper surface (upper surface animal migration), migrate to the ink agent (E) of refusing of upper surface and be fixed on cured film
Upper surface.
Here, in the Raolical polymerizable using light, cured film is easier by oxygen with the face of atmosphere
Caused response inhabitation.In the negative light-sensitive resin combination of the present invention, light acid producing agent (C) produces acid by exposure,
Acid as curing agent (D) in the presence of the acid with the reaction of the acidic-group such as the carboxylic acid of alkali soluble resin or base soluble monomer (A)
And solidify.In addition, being additionally considered that now acid as curing agent (D) is reacted with each other and contributes to solidification.The curing reaction and radical polymerization
Reaction is different, is not affected by oxygen.Therefore, using the negative light-sensitive resin combination of the present invention, cured film is obtained, especially
It is the curability of the alkali soluble resin or base soluble monomer (A) of cured film upper surface and refuses the stationarity of ink agent (E)
The cured film that improve.Even if in addition, having obtained that also there is the curability equal with conventional cured film, especially for low light exposure
It is the cured film of the curability with upper surface.
As described above, in the negative light-sensitive resin combination of the present invention, by will be anti-using the radical polymerization of light
Should be combined with the curing reaction in the presence of the acid produced using light, the solidification inside cured film also can fully enter
OK.Accordingly, as exposure portion cured portion for development when alkaline developer caused by erosion, peel off have patience.Therefore, expose
Light portion is not easy to be affected in long-time is developed, therefore, it is favourable for the removing etc. of the residue of opening portion.
The present invention negative light-sensitive resin combination further as needed containing compound (F) (hereinafter also referred to as
" crosslinking agent (F) "), mercaptan compound (G) (hereinafter also referred to as " mercaptan compound (G) "), phosphate cpd (H), polymerization inhibitor
(I), solvent (J), colouring agent (K), other any conditions, the compound (F) has the unsaturation of more than 2 double in intramolecular
Key and have any one of acidic-group and fluorine atom, the mercaptan compound (G) in 1 molecule have more than 3
Sulfydryl.
(alkali soluble resin or base soluble monomer (A))
To alkali soluble resin label symbol (AP), to base soluble monomer label symbol (AM), illustrate respectively.Should
Explanation is given, in the following description, also be they are referred to sometimes " alkali soluble resin (A) ".
Alkali soluble resin (A) has photo-curable.In addition, alkali soluble resin (A) does not have fluorine atom.In minus sense
In photosensitive resin composition, by exposure, optical free radical polymerization initiator (B) produces free radical, and light acid producing agent (C) is produced
Acid.Now, using above-mentioned free radical polymerisation in its own to alkali soluble resin (A) there is, and in the presence of above-mentioned acid
Lower and acid as curing agent (D) reacts and is crosslinked, and thus cures sufficiently.Should illustrate, alkali soluble resin (A) each other will not be because of acid
And react.
The solidification of the exposure portion of negative light-sensitive resin combination is sufficiently carried out as mentioned above.It is so that exposure portion is abundant
Exposure portion obtained by solidification will not easily be removed by alkaline developer.Further, since alkali soluble resin (A) is that alkali is solvable, because
This, can optionally remove the non-exposed portion of uncured negative light-sensitive resin combination with alkaline developer.As a result, energy
Cured film is enough set to form the form in the next door of the shape that predetermined region is divided into multiple subregions.
As alkali soluble resin (AP), there is the photonasty tree of acidic-group and ethylenic double bond preferably in 1 molecule
Fat.Alkali soluble resin (AP) is produced by having ethylenic double bond in the molecule using above-mentioned optical free radical polymerization initiator (B)
Raw free radical is polymerized.Alkali soluble resin (AP) passes through have acidic-group in the molecule, in above-mentioned smooth acid producing agent
(C) reacted with acid as curing agent (D) in the presence of the acid for producing.In addition, by with acidic-group, in alkali-soluble.
As acidic-group, can enumerate:Carboxyl, phenolic hydroxyl group, sulfo group and phosphate etc., they can be used alone 1
Kind, it is also possible to and use two or more.
As ethylenic double bond, can enumerate:(methyl) acryloyl group, pi-allyl, vinyl, ethyleneoxy and ethylene oxy
The double bond with addition polymerization such as base alkyl.They can be used alone or two or more kinds may be used.Should illustrate,
Part or all for the hydrogen atom that ethylenic double bond has also can be replaced by alkyl such as methyl.
As the alkali soluble resin (AP) with ethylenic double bond, can enumerate:Comprising the side chain with acidic-group
With the resin (A-1) of the side chain with ethylenic double bond and be imported with acidic-group and ethylenic double bond in the epoxy
Resin (A-2).They can be used alone or two or more kinds may be used.
As such alkali soluble resin (AP), it is possible to use International Publication No. 2014/046209 is (hereinafter referred to as
WO2014/046209) such as [0108th], [0126] section, International Publication No. 2014/069478 (hereinafter referred to as
WO2014/069478 the material for example described in [0067th] [0085] section).
As alkali soluble resin (AP), from the stripping that can suppress cured film when developing high-resolution point is obtained
Pattern aspect, from point for it is linear when pattern linearity it is good in terms of, from being readily obtained smooth cured film table
From the aspect of face, resin (A-2) is preferably used.Should illustrate, the linearity of pattern well refers to the edge in the next door for obtaining
Non-notch etc. and it is linear.
As resin (A-2), particularly preferably in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolacs
Type epoxy resin, cresol novolak type epoxy resin, tris-phenol type epoxy resin, the epoxy resin with naphthalene skeleton,
Acidic-group has been directed respectively in the epoxy resin such as the epoxy resin with biphenyl backbone, fluorenyl replacement bisphenol A type epoxy resin
With the resin of ethylenic double bond.
The quantity of the ethylenic double bond that alkali soluble resin (AP) has in 1 molecule preferably average more than 3, it is especially excellent
Select more than 6.If the quantity of ethylenic double bond is more than the lower limit of above range, easily to exposed portion and unexposed portion
The alkali solubility for dividing gives difference, can form fine pattern with less light exposure.
The matter average molecular weight (Mw) preferably 1.5 × 10 of alkali soluble resin (AP)3～30 × 103, particularly preferred 2 × 103~
15×103.In addition, number-average molecular weight (Mn) preferably 500～20 × 103, particularly preferred 1.0 × 103～10 × 103.If matter is divided equally
Son amount (Mw) and number-average molecular weight (Mn) for the lower limit of above range more than, then solidification when exposing is abundant, if above-mentioned model
Below the higher limit enclosed, then developability is good.
Should illustrate, in this manual, number-average molecular weight (Mn) and matter average molecular weight (Mw) unless otherwise specified,
Then refer to by gel permeation chromatography, value obtained from being measured as standard substance using polystyrene.
The acid number preferably 10～300mgKOH/g of alkali soluble resin (AP), particularly preferred 30～150mgKOH/g.If sour
It is worth for above range, then the developability of minus photosensitive composite becomes good.
As base soluble monomer (AM), the monomer (A- for example with acidic-group and ethylenic double bond is preferably used
3).Acidic-group and ethylenic double bond are same with alkali soluble resin (AP).It is also excellent for the acid number of base soluble monomer (AM)
Choosing and the same scope of alkali soluble resin (AP).
As monomer (A-3), 2,2,2- tri- acryloyloxymethyl ethyl phthalic acids etc. can be enumerated.
Contained alkali soluble resin or base soluble monomer (A) can be used alone in negative light-sensitive resin combination
1 kind, it is also possible to and use two or more.
Alkali soluble resin or base soluble monomer (A's) in the total solid content of negative light-sensitive resin combination contains
Proportional preferably 5～80 mass %, particularly preferred 10～60 mass %.If content ratio is above range, negative-type photosensitive
The photo-curable and developability of resin combination is good.
(optical free radical polymerization initiator (B))
The present invention optical free radical polymerization initiator (B) as long as with using active ray produce free radical light freedom
The compound of base polymerization initiator function is just not particularly limited.Hereinafter, also by optical free radical polymerization initiator (B) referred to as
" Photoepolymerizationinitiater initiater (B) ".
As Photoepolymerizationinitiater initiater (B), can enumerate:WO2014/046209 such as [0130th], [0131] section,
Photoepolymerizationinitiater initiater for example described in [0089th] [0090] section of WO2014/069478 etc..
In Photoepolymerizationinitiater initiater (B), if by benzophenone, aminobenzoic acids and aliphatic amine and other free radicals
Initiator is used together, then sometimes manifest sensitization effect and it is preferred that.Photoepolymerizationinitiater initiater (B) can be used alone, it is also possible to
And use two or more.
The content ratio preferably 0.1 of the Photoepolymerizationinitiater initiater (B) in the total solid content of negative light-sensitive resin combination
～50 mass %, more preferably 0.5～30 mass %, particularly preferred 1～15 mass %.If content ratio is in above range, bear
The photo-curable and developability of type photosensitive polymer combination is good.
(acid producing agent (C))
Light acid producing agent (C) produces sour compound just without especially limit as long as decomposing by irradiating active ray
System.Generally, can produce as light acid from the photosensitive polymer combination of alkali soluble resin for having used cationic polymerization type
Arbitrary compound is selected to use in the compound that raw agent is used.Hereinafter, also by light acid producing agent (C), referred to as " acid is produced
Agent (C) ".
As described above, in the negative light-sensitive resin combination of the present invention, the acid generated by acid producing agent (C) is participated in
State the combination of the acid as curing agent (D) of alkali soluble resin (A) and following explanation.
Acid producing agent (C) is irradiated by active ray and decomposes and produce acid.As the active ray, specifically, can be with
Enumerate the high-energy rays such as ultraviolet light, X-ray, electron beam.Using negative light-sensitive resin combination manufacture it is used for optical elements every
During wall, exposure preferably uses i rays (365nm), h rays (405nm) and g rays (436nm).As acid producing agent (C), preferably
Select the big acid producing agent (C) of absorbance at the wavelength for exposing used light.It is preferred that have in 350～450nm absorbing
Acid producing agent, particularly to the light comprising at least a kind in i rays (365nm), h rays (405nm) and g rays (436nm)
Line has the acid producing agent for absorbing, because curability is high it is preferred that.
As acid producing agent (C), specifically, can enumerate:Salt system acid producing agent, nonionic system acid producing agent.Make
ForSalt system acid producing agent, for example, can enumerate:The compound with list～triphenylsulfonium skeleton shown in following formula (C0)
Salt, iodineSalt based compound etc..
In formula (C0), Ra1And Ra2Represent the alkyl or phenyl of the carbon number 1～20 can with substituent, Ra3Represent 1
The organic group of valency.W is 0～5 integer.X-Anion is represented, specifically, can be enumerated:SbF6 -, the anion of phosphorus system
Such as PF6 -、(Rf1)nPF6-n -(Rf1For fluoroalkyl, n is 1～3), the anion such as R of sulfonate systemaSO3 -(RaFor a part
Or the alkyl or the aryl of carbon number 6～18 of the carbon number 1～12 that all can be replaced by fluorine atoms) etc..As RaSO3 -
Ra, for example, can enumerate:- CF3,-C4F9,-C8F17Deng perfluoroalkyl ,-C6F5Deng perfiuoroaryl ,-Ph-CH3(its
In, Ph represents phenyl) etc. aryl etc..
As compound (C0), preferred Ra1And Ra2It is the compound of phenyl (can be substituted).Specifically, preferably
The compound with triphenylsulfonium skeleton shown in following formula (C1) or following formula (C2)Salt.Should illustrate, compound (C1) and
In compound (C2), the compound that the hydrogen atom of the phenyl of triphenylsulfonium skeleton is substituted can also make as acid producing agent (C)
With.
In formula (C1) and formula (C2), Xa-And Xb-Represent anion, specifically, can enumerate with above-mentioned formula (C0)
X-Same anion.As Xa-And Xb-, the anion of preferred phosphorus system, the anion of sulfonate system.
Should illustrate, theseIn salt, cation portion absorbs the light of irradiation, and anion portion becomes the generating source of acid.
As compound (C0), can enumerate shown in following formula (C0-1)Salt is used as the change with single phenyl sulfonium skeleton
CompoundSalt.
In addition, as the compound with triphenylsulfonium skeletonIn the compound (C1) and compound (C2) of salt,
, for the compound being exposed with i rays (365nm), can enumerate as example:Triphenyl shown in following formula (C1-1)
The triaryl matte PF that the fluorine butane sulfonate of sulfonium nine, following formula (C2-1) and following formula (C2-2) are respectively shown in6Salt and three fragrant
The special phosphorus system salt of base sulfonium.Absorbance at wavelength 365nm it is big in terms of, be readily available from the aspect of, preferably these changes
Compound.
In formula (C2-2), Rf1For fluoroalkyl, n is 1～3.
As iodineSalt based compound, can enumerate:Diaryl iodoniumSalt, triarylsulfonium salt.
As Diaryl iodoniumThe concrete example of the cationic moiety of salt, can enumerate:Diphenyl iodine4- anisyls
Phenyl-iodideDouble (4- tert-butyl-phenyls) iodineDeng.As Diaryl iodoniumThe concrete example of the anionicsite of salt, can be with
Enumerate:Trifluoro-methanyl sulfonate, nine fluorine butane sulfonate, tosilate, phenyl-pentafluoride sulfonate, hexafluorophosphate, tetrafluoro
Borate, hexafluoro antimonate etc..
Diaryl iodoniumSalt is made up of above-mentioned cationic moiety and anionicsite, by the concrete example of above-mentioned cationic moiety
1 kind and a kind of concrete example of anionicsite of combination constitute.For example, double (4- tert-butyl benzenes) iodineFluoroform sulphur
Hydrochlorate is an example.
As the concrete example of the cationic moiety of triarylsulfonium salt, can enumerate:Triphenylsulfonium, diphenyl -4- methyl
Phenyl sulfonium, diphenyl -2,4,6- trimethylphenyl sulfoniums etc..As the concrete example of the anionicsite of triarylsulfonium salt, can be with
Enumerate:Above-mentioned Diaryl iodoniumThe concrete example of the anionicsite of salt.
Triarylsulfonium salt is made up of above-mentioned cationic moiety and anionicsite, by the concrete example of above-mentioned cationic moiety
1 kind of combination with a kind of the concrete example of anionicsite is constituted.For example, triphenylsulfonium triflate alkyl sulfonate is an example.
As the acid producing agent of nonionic system, for example, can enumerate the compound with following structure:With the formyl of naphthalene two
Imines skeleton, nitro benzene skeleton, diazomethane skeleton, phenyl acetophenone skeleton, 9- thioxanthone skeletons, triazine skeleton and bonding
There are chlorine atom, alkanesulfonic acid, aryl sulfonic acid etc..
As such compound, specifically, can enumerate:Following formula (C3), following formula (C4), following formula (C5), following formula
(C6) what, following formula (C7) was respectively shown in possess with naphthalimide skeleton, nitro benzene skeleton (when wherein, nitro is 1,
Its position be 2 or 4, nitro be 2 when, its position be 2,5), diazomethane skeleton, phenyl acetophenone skeleton, thioxanthene
Ketone skeleton and be bonded with alkanesulfonic acid, aryl sulfonic acid etc. structure compound.Furthermore it is possible to enumerate:Shown in following formula (C8)
Compound with triazine skeleton and chlorine atom.Further, can enumerate:The sulfonyl of the dialkyl group glyoxime shown in following formula (C9)
(sulfonyloxyimino) thiophene -3 shown in sulfonyloxyimino cyanide compound, (C11) shown in compound, (C10)
(2H)-subunit -2- (2- aminomethyl phenyls) cyanide compound etc..
Should illustrate, in compound (C3), (C4), (C6), (C7), (C11), form the phenyl ring of each compound scaffold
The substituted compound of hydrogen atom can also play a role as acid producing agent.
R in formula (C3)～(C7), (C9), (C10), (C11)b1～Rb5、Rb7、Rb9And Rb11It is independently of one another a part
Or straight-chain, branched or the ring-type that all can be replaced by fluorine atoms is (wherein, also comprising thing of the part with circulus
Matter) carbon number 1～12 alkyl or the aryl of carbon number 6～18.R in formula (C8), (C9), (C10)b6、Rb8With
Rb10Can be independently of one another with substituent, unsaturated bond, can be containing heterocycle carbon number 1～18 organic group.
As shown in above-mentioned formula (C4) with nitro benzene skeleton (wherein, nitro be 1 when, its position be 2 or 4,
Nitro be 2 when, its position then be 2,5) compound, specifically, 2- nitrobenzyl p-methyl benzenesulfonic acid esters can be enumerated
Deng.
As the double sulfonyidiazomethanes compounds shown in above-mentioned formula (C5), specifically, can enumerate:It is double (to first
Benzenesulfonyl) it is diazomethane, double (2,4- 3,5-dimethylphenyl sulfonyls) diazomethanes, double (phenyl sulfonyl) diazomethanes, double
It is (tert. butylsulfonyl) diazomethane, double (normal-butyl sulfonyl) diazomethanes, double (iso-butylsulfonyl) diazomethanes, double
It is (isopropelsulfonyl) diazomethane, double (n-propyl sulfonyl) diazomethanes, double (cyclohexylsulfonyl) diazomethanes, double
(isopropelsulfonyl) diazomethane etc..
As the concrete example with triazine skeleton and the compound of chlorine atom shown in above-mentioned formula (C8), can enumerate:2-
2- (4- methoxyphenyls) shown in double (the trichloromethyl) -1,3,5- triazines of methyl -4,6-, following formula (C8-1) -
4,6- double (trichloromethyl) -1,3,5- triazines, 2- (2- furyls) vinyl-bis- (trichloromethyl) -1,3,5- three
Double (trichloromethyl) -1,3 of 2- (5- methyl -2- furyls) vinyl -4,6- shown in piperazine, following formula (C8-2),
Double (trichloromethyl) -1,3 of 2- (4- methoxyphenyls) vinyl -4,6- shown in 5- triazines, following formula (C8-3),
Double (trichloromethyl) -1,3,5- triazines of 5- triazines, 2- (3,4- Dimethoxyphenyls) vinyl -4,6- etc..
As the concrete example of the sulfonyloxyimino cyanide compound shown in above-mentioned formula (C10), can enumerate:α-(first
Base sulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino) -4- methoxyphenylacetonitriles, α-(three
Methyl fluoride sulfonyloxyimino)-phenylacetonitrile, α-(trimethyl fluoride sulfonyl epoxide imino group) -4- methoxyphenyl second
Nitrile, α-(ethylsulfonyloxy imino group) -4- methoxyphenylacetonitriles, α-(sulfonyl propyl epoxide imino group) -4- first
Base phenylacetonitrile, α-(methylsulfonyloxyimino) -4- Bromophenylacetonitriles etc..
As (sulfonyloxyimino) thiophene -3 (2H) shown in above-mentioned formula (C11)-subunit -2- (2- methylbenzenes
Base) cyanide compound, specifically, can enumerate:Rb11For 2- [2- (n-propyl sulfonyloxyimino) thiophenes of n-propyl
Fen -3 (2H)-subunit] -2- (2- aminomethyl phenyls) acetonitrile), Rb11For 2- [2- (the n-octyl sulfonyloxy Asias of n-octyl
Amino) thiophene -3 (2H)-subunit] -2- (2- aminomethyl phenyls) acetonitrile, Rb11For 2- [2- (the 4- first of 4- aminomethyl phenyls
Base phenylsulfonyloxy group imino group) thiophene -3 (2H)-subunit] -2- (2- aminomethyl phenyls) acetonitrile etc..
Should illustrate, in the acid producing agent of these nonionic systems, be bonded with chlorine atom, alkanesulfonic acid, aryl sulfonic acid etc.
Part becomes the generating source of acid.
As the acid producing agent of nonionic system, such as the compound for being exposed with i rays (365nm), from
The big aspect of absorbance at wavelength 365nm, be readily available from the aspect of, the N- fluoroforms shown in preferred following formula (C3-1)
2- phenyl -2- (tolysulfonyl epoxide) acetophenone shown in alkyl sulfonic acid -1,8- naphthalimides, following formula (C6-1)
With double (the trichloromethyl) -1,3,5- triazines of 2- (4- anisyls) vinyl -4,6- shown in above-mentioned formula (C8-3)
Deng.
As the acid producing agent of nonionic system, such as with comprising i rays (365nm), h rays (405nm) and g rays
(436nm) compound that the light of at least a kind in is exposed, can enumerate:Shown in above-mentioned formula (C8) with triazine bone
(sulfonyloxyimino) thiophene -3 (2H)-subunit -2- shown in the compound of frame and chlorine atom, above-mentioned formula (C-11)
(2- aminomethyl phenyls) cyanide compound etc..Absorbance particularly at wavelength 405nm and/or 436nm it is big in terms of, easily
From the aspect of obtaining, preferred 2- (2- furyls) vinyl-bis- (trichloromethyl) -1,3,5-triazines, formula (C8-2)
Shown 2- (5- methyl -2- furyls) vinyl -4,6- double (trichloromethyl) -1,3,5- triazines, formulas (C8-3)
Shown 2- (4- methoxyphenyls) vinyl -4,6- double (trichloromethyl) -1,3,5- triazines, 2- (3,4- diformazans
Phenyl) R in vinyl -4,6- double (trichloromethyl) -1,3,5- triazines, formula (C-11)b11For n-propyl, n-octyl
Or the compound of 4- aminomethyl phenyls etc..
In addition, by these in the presence of lightThe acid that salt system acid producing agent and nonionic system acid producing agent are produced is salt
Acid, alkanesulfonic acid, aryl sulfonic acid, the aryl sulfonic acid being partially or completely fluorinated, alkanesulfonic acid etc..
Acid producing agent (C) can be constituted by the 1 of above-claimed cpd kind, it is also possible to be made up of two or more.Negative-type photosensitive tree
Content preferably 0.01～10 mass % of the acid producing agent (C) in the total solid content of oil/fat composition, more preferably 0.1～5 matter
Amount %, particularly preferred 0.3～3 mass %.By make acid producing agent (C) content be above range, obtain upper surface have fill
Divide the next door refused ink and fine and high precision pattern can be formed.
Should illustrate, by being used in combination with following sensitizers, sensitivity uprise and it is preferred that.As relative to the quick of acid producing agent
Agent, can enumerate:Double (the 2- of 9,10- diethoxy anthracenes, 9,10- dipropoxy anthracenes, 9,10- dibutoxy anthracenes, 9,10-
Ethyl hexyl oxy) anthracene, double (octanoyloxy) anthracenes of 9,10- etc..
(acid as curing agent (D))
Acid as curing agent (D) as long as the compound for reacting with the acidic-group such as carboxylic acid, phenolic hydroxyl group in presence of an acid
Just it is not particularly limited.
As acid as curing agent (D), be preferably selected from amino resins, epoxide,In isoxazoline compound at least 1
Kind.These compounds can be used alone, it is also possible to and use two or more.
As amino resins, can enumerate:The one of the amino of melamine compound, guanamines compound, carbamide compound etc.
Partly or entirely by the compound of HM or by the hydroxyl of the compound of the HM, part or all uses first
It is melamine based compound shown in the following formula (D1) of the etherificates such as alcohol, ethanol, n-butanol, 2- methyl isophthalic acids-propyl alcohol, following
The urea based compound shown in guanamines based compound, following formula (D3), (D4) or (D5) or its resin shown in formula (D2) etc..
R in formula (D1)～(D5)11～R32It is each independently hydrogen atom, hydroxymethyl or alkoxy methyl.R11～R16In
At least one is alkoxy methyl, R17～R20Middle at least one be alkoxy methyl, R21～R24Middle at least one is alkoxy methyl,
R27～R30Middle at least one be alkoxy methyl, R31And R32Middle at least one is alkoxy methyl.R33～R36It is each independently
Hydrogen atom, hydroxyl, alkyl or alkoxyl, Xc is singly-bound, methylene or oxygen atom.
R11～R32For alkoxy methyl when alkoxyl carbon number preferably 1～6, more preferably 1～3.R33～R36For alkane
During epoxide, its carbon number preferably 1～6, more preferably 1～3.As the alcohol for becoming alkoxyl, for example, can enumerate:Methyl alcohol, second
Alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, 2- methyl isophthalic acids-propyl alcohol etc..
In compound (D1)～(D4), from from the aspect of the easiness of manufacture, the substituent whole preferably each having
For identical alkoxy methyl.
As the urea based compound shown in above-mentioned formula (D5), for example, can enumerate following compound.
2,4,6- tri- [double (methoxyl groups when acid as curing agent (D) is amino resins, shown in preferably following formula (D1-1)
Methyl) amino] -1,3,5- triazines or (methoxy) glycolurils of 1,3,4,6- tetra- shown in its resin, formula (D3-1) or
Its resin etc..
As epoxy based compound, can enumerate:Bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolac are clear
Paint shaped epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, trisphenol
The glycidol ethers such as methane type epoxy resin, brominated epoxy resin, 3,4- epoxycyclohexyl-methyl -3,4- epoxy hexamethylenes
The alicyclic epoxy resins such as alkane carboxylate, double (2,3- epoxycyclopentyl) ethers, hexahydrophthalic acid 2-glycidyl ester, four
The glycidol esters such as hydrogen o-phthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, four glycidyl group two
The glycidol amines such as aminodiphenylmethane, triglycidyl group para-aminophenol, triglycidyl isocyanurate etc. are miscellaneous
Ring type epoxy resin etc..
It is dicyclopentadiene-type epoxy resin shown in preferably for example following formula (De1), following as epoxy based compound
Formula (De2) shown in naphthalene type epoxy resin.
(in formula (De1), n is 0～30 integer)
AsIsoxazoline compound, can enumerate:2- vinyl -2-Oxazoline, 2- vinyl -4- methyl -
2-Oxazoline, 2- vinyl -5- methyl -2-Oxazoline, 2- isopropenyl -2-Oxazoline, 2- isopropyl alkene
Base -4- methyl -2-The copolymer of the polymerizable monomers such as oxazoline.
As acid as curing agent (D), wherein, preferred melamine based compound, urea based compound, epoxy based compound.Should
Explanation, acid as curing agent (D) is given to be constituted by the 1 of above-claimed cpd kind, it is also possible to be made up of two or more.Relative to above-mentioned alkali
100 mass parts of soluble resin (A), acid as curing agent (D) content preferably 0.1～100 in negative light-sensitive resin combination
Mass parts, more preferably 1～50 mass parts, particularly preferred 5～20 mass parts.It is above-mentioned model by making the content of acid as curing agent (D)
Enclose, obtain upper surface and there is the next door fully refused ink and can form fine and high precision pattern.If in addition, particularly
The above-mentioned content of acid as curing agent (D) is the scope of 5～20 mass parts, then the storage stability of negative light-sensitive resin combination becomes
Well, and the excellent next door of linearity that pattern is obtained by said composition.
(refusing ink agent (E))
The ink agent (E) of refusing of the present invention has fluorine atom in intramolecular.Thus, refuse ink agent (E) to have using containing
Its negative light-sensitive resin combination migrate during forming cured film to the property of upper surface (upper surface animal migration) and
Refuse ink.By using ink agent (E) is refused, the upper layer part comprising upper surface of the cured film for obtaining becomes refuses ink agent (E)
The layer (below, being also sometimes referred to as " refusing ink layer ") of intensive presence, gives to cured film upper surface and refuses ink.
Refuse fluorine atom containing ratio preferably 1～40 mass % in ink agent (E), more preferably 5～35 mass %, particularly preferably
10～32 mass %.If the fluorine atom containing ratio for refusing ink agent (E) is more than the lower limit of above range, can be to cured film
Upper surface give it is good refuse ink, if below higher limit, then with negative light-sensitive resin combination in other compositions
Intermiscibility become good.
In ink layer is refused, refuse ink agent (E) itself for it is non-reacted when, to imbed solidified resin in form deposit
The light such as alkali soluble resin (A), the acid as curing agent (D) in, the solidified resin is by negative light-sensitive resin combination are consolidated
Chemical conversion point polymerization, cross-linking reaction and obtain.Generally, when ethylenic double bond carries out radical polymerization, cured film, next door
The easier response inhabitation by caused by oxygen in face connected with air.Connect with air due to refusing ink layer, therefore, refusing ink
There is radical polymerization during photocuring for alkali soluble resin (A) in layer segment, easily by response inhabitation.However, this
The alkali soluble resin (A) of bright negative light-sensitive resin combination is hardly subject to oxygen institute with the reaction of acid as curing agent (D)
The response inhabitation of cause, even if being also sufficiently carried out ink layer segment is refused.Thus, substantially ensure that that refuses ink layer refuses ink agent
(E) stationarity.
That is, in order to improve the stationarity for refusing ink agent (E) for refusing ink layer, it is important that make above-mentioned alkali soluble resin
(A) it is sufficiently carried out with the curing reaction of acid as curing agent (D).For this purpose, during solidification particularly under low light exposure, using compared with
The active ray of long wavelength (350～450nm) produces the high acid producing agent (C) of curability of acid can be with as acid producing agent (C)
Say it is favourable.
In addition, refusing ink agent (E) from raising, to from the viewpoint of the stationarity for refusing ink layer, refusing, ink agent (E) is preferred to be had
There is the compound of ethylenic double bond.By refusing ink agent (E) with ethylenic double bond, so as to Free Radical is in migrating to upper table
The ethylenic double bond for refusing ink agent (E) in face, can make to refuse ink agent (E) each other or refuse ink agent (E) and negative-type photosensitive tree
Other compositions with ethylenic double bond contained by oil/fat composition are crosslinked by (co) polymerization.Should illustrate, the reaction
Can be promoted by the mercaptan compound (G) (aftermentioned) for arbitrarily containing.
Thus, in the manufacture of the cured film for solidifying negative light-sensitive resin combination, it is possible to increase refuse ink
Agent (E) cured film upper layer part, refuse the stationarity of ink layer.In the negative light-sensitive resin combination of the present invention particularly
During containing mercaptan compound (G), even if in the case that light exposure during exposure is low, it is also possible to make to refuse ink agent (E) fully solid
Due to refusing ink layer.
As described above, generally, when ethylenic double bond carries out radical polymerization, cured film, next door connect with air
The easier response inhabitation by caused by oxygen in face, but using mercaptan compound (G) radical reaction hardly be subject to oxygen
Caused suppression, therefore, the fixation for refusing ink agent (E) being particularly conducive under low light exposure.Further, in next door manufacture,
When being developed, can be adequately suppressed refuse ink agent (E) from refuse ink layer depart from or refuse ink layer upper surface peel off.
As ink agent (E) is refused, for example, can enumerate the partial hydrolysis condensate of hydrolysable silanes compound.Water-disintegrable silicon
Hydride compounds can be used alone or two or more kinds may be used.Contract as the partial hydrolysis by hydrolysable silanes compound
Compound is constituted and refuses ink agent (E) with fluorine atom, specifically, can be enumerated and following be refused ink agent (E1).As tool
Have fluorine atom refuses ink agent (E), it is also possible to using being refusing of constituting of the hydrocarbon chain and side chain compound that contains fluorine atom by main chain
Ink agent (E2).
Refuse ink agent (E1) and refuse ink agent (E2) to be used alone or in combination.In the negative photosensitive resin of the present invention
In composition, from UV resistant/ozon it is excellent from the aspect of, particularly preferably using refusing ink agent (E1).
<Refuse ink agent (E1)>
Refuse the part water that ink agent (E1) is homogeney of hydrolysable silanes compound mixture (hereinafter also referred to as " mixture (M) ")
Solution condensation product.The mixture (M) contains with fluorine alkylidene and/or fluoroalkyl and is bonded with hydrolization group on the silicon atoms
Group hydrolysable silanes compound (hereinafter also referred to as " hydrolysable silanes compound (s1) ") as required composition,
And arbitrarily containing the hydrolysable silanes compound beyond hydrolysable silanes compound (s1).Arbitrarily contain as mixture (M)
Some hydrolysable silanes compounds, can enumerate following hydrolysable silanes compound (s2), (s3).Appoint as mixture (M)
The hydrolysable silanes compound that meaning ground contains, particularly preferred hydrolysable silanes compound (s2).
Hydrolysable silanes compound (s2):The hydrolysable silanes compound of 4 hydrolization groups is bonded with the silicon atoms.
Hydrolysable silanes compound (s3):It is bonded with comprising the group with ethylenic double bond and on the silicon atoms water-disintegrable
The group of group and the hydrolysable silanes compound without fluorine atom.
Mixture (M) can arbitrarily containing beyond one kind or two or more hydrolysable silanes compound (s1)～(s3)
Hydrolysable silanes compound.
As other hydrolysable silanes compounds, can enumerate:Only there is alkyl and hydrolization group as being bonded to
The hydrolysable silanes compound (s4) of the group of silicon atom, the water-disintegrable silicon with sulfydryl and hydrolization group and without fluorine atom
Hydride compounds (s5), the hydrolysable silanes compound (s6) with epoxy radicals and hydrolization group and without fluorine atom, with oxygen
Alkylidene and hydrolyzable silyl group and the hydrolysable silanes compound (s7) without fluorine atom etc..
As hydrolysable silanes compound (s1)～(s3) and other hydrolysable silanes compounds, can enumerate:WO2014/
It is described in 046209 such as [0034th]～[0072] section, such as [0096th]～[0136] section of WO2014/069478
Compound etc..
As an example for refusing ink agent (E1), the compound containing n1 (s1), the compound containing n2 can be enumerated
(s2), the partial hydrolysis condensate of the mixture (M) of (s3) containing n3.
Here, n1～n3 represents molar fraction of each Component units relative to total mole of Component units.n1>0、n2
>=0, n3 >=0 and n1+n2+n3=1.
n1:n2:N3 is consistent with the composition that feeds intake of the compound (s1) of mixture (M), (s2), (s3).
The mol ratio of each composition can be designed according to the balance of the effect of each composition.
N1 becomes preferably 0.02～0.4 in the amount of above-mentioned preferred scope in the fluorine atom containing ratio for refusing ink agent (E1).
N2 preferably 0～0.98, particularly preferred 0.05～0.6.
N3 preferably 0～0.8, particularly preferred 0.2～0.5.
Refuse the matter average molecular weight (Mw) preferably more than 500, preferably smaller than 1000000, particularly preferred 5000 of ink agent (E1)
Below.
If matter average molecular weight (Mw) is more than lower limit, using negative light-sensitive resin combination cured film is being formed
When, refuse ink agent (E1) and easily migrate to upper surface.If be less than higher limit, opening portion residue tail off and it is preferred that.
Refusing the matter average molecular weight (Mw) of ink agent (E1) can be adjusted according to manufacturing condition.
Refuse ink agent (E1) and by known method above-mentioned mixture (M) can be made to be hydrolyzed make with condensation reaction
Make.
Inorganic acid or acetic acid, oxalic acid and the horses such as the hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid that are usually used are preferably used in the reaction
Carry out the organic acid such as sour as catalyst.Alternatively, it is also possible to use NaOH, tetramethyl ammonium hydroxide (TMAH) etc. as needed
Base catalyst.
Above-mentioned reaction can use known solvent.
What is obtained in above-mentioned reaction refuses ink agent (E1) and together can be matched with negative photosensitive with the proterties of solution with solvent
Property resin combination.
<Refuse ink agent (E2)>
It is main chain for hydrocarbon chain and comprising the compound of the side chain with fluorine atom to refuse ink agent (E2).Refuse ink agent (E2)
Matter average molecular weight (Mw) preferably 100～1000000, particularly preferred 5000～100000.If matter average molecular weight (Mw) is lower limit
More than, then when forming cured film using negative light-sensitive resin combination, refuse ink agent (E2) and easily migrate to upper surface.If
Below higher limit, then opening portion residue tail off and it is preferred that.
As ink agent (E2) is refused, specifically, can enumerate:Such as [0079]～[0102] of WO2014/046209,
It is for example in [0144]～[0171] of WO2014/069478 described to refuse ink agent etc..
The content ratio preferably 0.01～15 for refusing ink agent (E) in the total solid content of negative light-sensitive resin combination
Quality %, more preferably 0.01～5 mass %, particularly preferred 0.03～1.5 mass %.If content ratio is the lower limit of above range
More than value, then the upper surface of the cured film for being formed by negative light-sensitive resin combination has excellent refuses ink.If on
State below the higher limit of scope, then cured film becomes good with the adaptation of base material.
(crosslinking agent (F))
The crosslinking agent (F) that arbitrarily contains of negative light-sensitive resin combination of the present invention be have in 1 molecule 2 with
On unsaturated double-bond, i.e. ethylenic double bond and with any one of acidic-group and fluorine atom compound.By negative
Type photosensitive polymer combination contains crosslinking agent (F), and the curability of negative light-sensitive resin combination during exposure is improved, even if
Cured film can be also formed for low light exposure.
As crosslinking agent (F), specifically, can enumerate:Such as [0137], [0138] of WO2014/046209,
Such as in [0194], [0195] of WO2014/069478 described crosslinking agent etc..
Crosslinking agent (F) can be used alone or two or more kinds may be used.
Content ratio preferably 10～60 matter of the crosslinking agent (F) in the total solid content of negative light-sensitive resin combination
Amount %, particularly preferred 20～55 mass %.
(mercaptan compound (G))
The mercaptan compound (G) that the negative light-sensitive resin combination of the present invention arbitrarily contains is that have 2 in 1 molecule
The compound of the sulfydryl more than individual.If the negative light-sensitive resin combination of the present invention contains mercaptan compound (G), there is institute
Meaning alkene-thiol reactant, i.e., generate mercaptan compound (G) by the free radical generated by Photoepolymerizationinitiater initiater (B) in exposure
Free radical and act on the ethylenic double bond of alkali soluble resin (A).Alkene-the thiol reactant and common ethylenic double bond
The radical polymerization for carrying out is different, the response inhabitation that will not be subject to caused by oxygen, therefore, have the advantage that:Turn with high chain
Shifting property, and then crosslinking is also carried out while polymerization, therefore, shrinkage factor when becoming solidfied material is also low, is readily obtained uniform
Network structure etc..
When the negative light-sensitive resin combination of the present invention contains mercaptan compound (G), even if being as mentioned above low exposure
Amount also can be cured sufficiently, particularly comprising easily by oxygen caused by response inhabitation next door upper surface upper layer part
Photocuring can be sufficiently carried out, be given therefore, it is possible to counter septum upper surface and good is refused ink.
Sulfydryl in mercaptan compound (G) preferably in 1 molecule contain 2～10, more preferably 3～8, further preferably
3～5.
The molecular weight of mercaptan compound (G) is not particularly limited.From the viewpoint of curability under low light exposure, mercaptan
Mercapto equivalents (hereinafter also referred to as " SH equivalents ") preferably 40～1000 shown in [molecular weight/sulfydryl number] of compound (G), more
It is preferred that 40～500, particularly preferred 40～250.
As mercaptan compound (G), specifically, can enumerate:Three (2- mercaptopropionyl epoxide ethyls) isocyanuric acids
Ester, pentaerythrite four (3- mercaptobutylates), trimethylolpropane tris mercaptoacetate, pentaerythrite tri-thiol acetic acid esters, season
The mercaptoacetate of penta tetrol four, the mercaptoacetate of dipentaerythritol six, trimethylolpropane tris (3-thiopropionate), season penta
Tetrol four (3-thiopropionate), three-[(3- mercaptopropionyl epoxides)-ethyl]-isocyanuric acid esters, dipentaerythritol six
(3-thiopropionate), trimethylol propane three (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), two seasons penta
Tetrol six (3- mercaptobutylates), trimethylol propane three (2- mercaptoisobutanoic acid esters), (the 3- sulfydryl butyryl acyloxies of 1,3,5- tri-
Ethyl) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, tris-phenol three (3-thiopropionate), trisphenol
Methane three (3- mercaptobutylates), trimethylolethane trimethacrylate (3- mercaptobutylates), 2,4,6- tri-thiols-s-triazine, 1,
Double (3- sulfydryl butyryl acyloxies) butane of 4- etc..
Mercaptan compound (G) can be used alone or two or more kinds may be used.
When negative light-sensitive resin combination contains mercaptan compound (G), its content ratio is preferably with respect to negative photosensitive
1 mole of sulfydryl of the ethylenic double bond that the total solid content in property resin combination has becomes 0.0001～1 mole of amount,
More preferably 0.0005～0.5 mole, particularly preferred 0.001～0.5 mole.If content ratio is above range, even if being low
Light exposure, the photo-curable and developability of negative light-sensitive resin combination is also good.
Should illustrate, the use of mercaptan compound (G) under the low light exposure for refusing ink layer for refusing consolidating for ink agent (E)
It is fixed highly effective, but the acid producing agent (C) with the fixed effect for refusing ink agent (E) under low light exposure in the same manner as and acid are solid
The use of agent (D) is compared, exist the carboxylic acid from (A) not easily pass through reaction and be consumed, for the raising of patternability
The few tendency of effect.Therefore, though in the case where negative light-sensitive resin combination contains mercaptan compound (G), for acid
Producing agent (C) and acid as curing agent (D), it is also preferred that containing above-mentioned ormal weight.
(phosphate cpd (H))
In order to improve adaptation of the cured film for obtaining to the transparent electrode materials such as base material, ITO etc., the minus sense of the present invention
Photosensitive resin composition can arbitrarily contain phosphate cpd (H).
As such phosphate cpd (H), as long as cured film can be improved to the close of base material, transparent electrode material etc.
Conjunction property is just not particularly limited, the phosphate cpd preferably in the molecule with ethylenic unsaturated double-bond.
As the phosphate cpd in the molecule with ethylenic unsaturated double-bond, preferably phosphoric acid (methyl) acroleic acid esterification
Compound, i.e. intramolecular at least have from the O=P structures of phosphoric acid and as the ethylene linkage from (methyl) acrylic compounds
The compound, phosphoric acid vinyl compound of (methyl) acryloyl group of formula unsaturated double-bond.
As phosphoric acid (methyl) acrylate compounds used in the present invention, can enumerate:Single (2- (methyl) propylene
Trimethylammonium) phosphate ester acid, two (2- (methyl) acryloyl-oxyethyl) phosphate ester acids, two (2- acryloxies
Ethyl) phosphate ester acid, three ((methyl) acryloyl-oxyethyl) phosphate ester acids, list (2- methacryloxyethyls)
Capronate phosphate ester acid etc..
For the negative light-sensitive resin combination of the present invention, as phosphate cpd (H), can individually containing classified
In a kind of this compound, it is also possible to contain two or more.
When negative light-sensitive resin combination contains phosphate cpd (H), relative in negative light-sensitive resin combination
Total solid content, its content ratio preferably 0.01～10 mass %, particularly preferred 0.1～5 mass %.If content ratio is upper
Scope is stated, then the cured film for obtaining is good with the adaptation of base material etc..
(polymerization inhibitor (I))
The present invention polymerization inhibitor (I) as long as the compound with the function as polymerization inhibitor is just not particularly limited, it is excellent
Choosing produces the compound of the free radical for suppressing alkali soluble resin (A) reaction.In the negative light-sensitive resin combination of the present invention
In, polymerization is controlled by the light quantity irradiated during polymerization inhibitor (I) adjustment exposure, the solidification that can make said composition is smoothly entered
OK.Thus, the carrying out of the solidification of non-exposed portion is inhibited, and contributes to the reduction of the development residue of opening portion.Further, can obtain
To the pattern of high-resolution point, and contribute to the linear raising of pattern.
As polymerization inhibitor (I), specifically, it is possible to use diphenyl picryl hydrazides, three p-nitrophenyl ylmethyls, to benzene
Quinone, p-tert-Butylcatechol, picric acid, copper chloride, methylnaphthohydroquinone, 4- metoxyphenols, tertiary butylated hydroquinone, the tertiary fourths of 2-
The polymerization inhibitor of the common reactions such as base -1,4- benzoquinones, 2,6- di-t-butyl-paracresol.Wherein, preferred 2- methyl hydrogens
Quinone, 2,6- di-t-butyl paracresol, 4- metoxyphenols etc..Further, from from the aspect of storage stability, preferred quinhydrones
System, quinone system polymerization inhibitor, particularly preferably use 2- methylnaphthohydroquinones, the 2- tert-butyl groups-Isosorbide-5-Nitrae-benzoquinones.
The content ratio preferably 0.001～20 of the polymerization inhibitor (I) in the total solid content of negative light-sensitive resin combination
Quality %, more preferably 0.005～10 mass %, particularly preferred 0.01～5 mass %.If content ratio is above range, bear
The development residue of type photosensitive polymer combination is reduced, and the linearity of pattern is good.
(solvent (J))
The negative light-sensitive resin combination of the present invention is by the way that containing solvent (J), viscosity is reduced, easily by negative-type photosensitive
Resin combination coats substrate surface.As a result, the film of the negative light-sensitive resin combination of homogeneous film thickness can be formed.
As solvent (J), using known solvent.Solvent (J) can be used alone or two or more kinds may be used.
As solvent (J), can enumerate:Aklylene glycol alkyl ether, aklylene glycol alkylether acetates class, alcohol
Class, solvent naphtha class etc..Wherein, be preferably selected from aklylene glycol alkyl ether, aklylene glycol alkylether acetates class and
At least a kind solvent in alcohols, further preferably selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethyl two
At least a kind solvent in alcohol ethyl-methyl ether, TC acetic acid esters and 2- propyl alcohol.
Relative to total composition, content ratio preferably 50～99 matter of the solvent (J) of negative light-sensitive resin combination
Amount %, more preferably 60～95 mass %, particularly preferred 65～90 mass %.
(colouring agent (K))
The negative light-sensitive resin combination of the present invention is needing to give shading to cured film, particularly next door according to purposes
During property, containing colouring agent (K).As the colouring agent (K) of the present invention, carbon black, nigrosine, anthraquinone system black pigment He perylene can be enumerated
It is black pigment, specifically, C.I. pigment blacks 1,6,7,12,20,31 etc. can be enumerated.Red pigment, indigo plant can also be used
The mixture of the organic pigment such as color pigment and viridine green and/or inorganic pigment.
Colouring agent (K) can be used alone or two or more kinds may be used.The negative photosensitive resin combination of the present invention
When thing contains colouring agent (K), content ratio preferably 5～65 mass % of the colouring agent (K) in total solid content, particularly preferred 10
～50 mass %.If above range, then the sensitivity of the negative light-sensitive resin combination for obtaining is good, in addition, formed
The light-proofness in next door is excellent.
(other compositions)
The negative light-sensitive resin combination of the present invention can further as needed containing one kind or two or more heat friendship
Connection agent, macromolecule dispersing agent, dispersing aid, silane coupler, particulate, curing accelerator, thickener, plasticizer, defoamer, stream
Other additives such as flat agent and anti-shrinking medium.
The negative light-sensitive resin combination of the present invention can mix the ormal weight of above-mentioned each composition and obtain.The present invention's
Negative light-sensitive resin combination can be used in Production Example such as organic EL element, quantum dot displays, tft array, the film sun
The optical elements such as energy battery, colour filter.Specifically, by for organic EL element, quantum dot displays, tft array, film
The formation of cured film, next door used in the optical elements such as solar cell and can especially play effect.If using this
Bright negative light-sensitive resin combination, then can manufacture upper surface have the good cured film for refusing ink, particularly every
Wall.Ink layer is refused in addition, refusing ink agent (E) and being essentially fully fixed on, in the next door than refusing ink layer part more on the lower
With low concentration exist refuse ink agent (E) also due to the abundant photocuring in next door and refuse in development ink agent (E) be difficult to migrate to
In the opening portion surrounded by next door, therefore, obtain the opening portion that ink can equably be coated with.
[resin cured film and next door]
The resin cured film of embodiments of the present invention shape using the negative light-sensitive resin combination of the invention described above
Into.The resin cured film of embodiments of the present invention for example can be obtained by following operation:In the coating of the substrate surfaces such as substrate
The negative light-sensitive resin combination of the present invention, is dried as needed and removes solvent etc., is then exposed and obtains.
The resin cured film of embodiments of the present invention is for optical element, particularly organic EL element, quantum dot displays, TFT
Especially significant effect is played when array, thin-film solar cells.
The next door of the present invention is by being formed as substrate surface being divided into the above-mentioned of a shape of the multiple subregions for being formed
The next door that the cured film of the present invention is constituted.Next door for example can be obtained by following operation:In the manufacture of above-mentioned resin cured film
In, before exposure the part to becoming the subregion of a formation implements to shelter, and is developed after exposure and is obtained.By aobvious
Shadow, because sheltering and the part of non-exposed is removed, with next door opening portion corresponding with the subregion of point formation is together formed.This
The next door of bright embodiment is being used for optical element, particularly organic EL element, quantum dot displays, tft array, film too
It is positive to play especially significant effect during battery.
The next door of embodiments of the present invention is for example as follows, and high-temperature process is not necessarily required in the fabrication process, therefore,
Also the flexible application of the plastic bases such as polyethylene terephthalate (PET), Merlon can be suitable for use with.
Hereinafter, using Figure 1A～1D illustrate embodiments of the present invention next door manufacture method an example, but every
The manufacture method of wall is not limited to following.Should illustrate, manufacture method below is contained with negative light-sensitive resin combination
The situation of solvent (J) is illustrated.
As shown in Figure 1A, the interarea in a side of substrate 1 is integrally coated with negative light-sensitive resin combination and forms film
21.Now, in film 21, refuse ink agent (E) and integrally dissolve and be uniformly dispersed.Should illustrate, Tu1AZhong schematically shows
Go out to refuse ink agent (E), not actually with the presence of such shape of particle.
Then, as shown in Figure 1B, film 21 is made to be dried and make desciccator diaphragm 22.As drying means, can enumerate:Heating
Dry, drying under reduced pressure and heating under reduced pressure are dried etc..Although also depending on the species of solvent (J), in the case of heat drying,
Preferably 50～120 DEG C of heating-up temperature.
In the dry run, refuse ink agent (E) and migrate to the upper layer part of desciccator diaphragm.Should illustrate, even if in minus sense
Photosensitive resin composition moves to upper table without in the case of solvent (J), similarly realizing refusing ink agent (E) moving to the interior in film
Face.
Then, as shown in Figure 1 C, the irradiation light of desciccator diaphragm 22 is exposed via photomask 30, the photomask 30 has
The shelter 31 of the shape of the opening portion surrounded equivalent to next door.Film after being exposed to desciccator diaphragm 22 is referred to as into exposed film
23.In exposed film 23, there is photocuring in exposure portion 23A, non-exposed portion 23B is the state same with desciccator diaphragm 22.
As the light of irradiation, can enumerate:Visible ray；Ultraviolet；Far ultraviolet；KrF PRKs, ArF quasi-molecules
Laser, F2PRK, Kr2PRK, KrAr PRKs and Ar2The PRKs such as PRK；X is penetrated
Line；Electron beam etc..
Used as the light of irradiation, the light of the light of 100～600nm of optimal wavelength, more preferably 300～500nm particularly preferably contains
The light of i rays (365nm), h rays (405nm) or g rays (436nm).Alternatively, it is also possible to end below 330nm as needed
Light.
Should illustrate, as the light irradiated in exposure, need for the light contained by negative light-sensitive resin combination
Polymerization initiator (B) and acid producing agent (C) select the light of the wavelength for making them activate respectively.
As Exposure mode, can enumerate:Whole face single exposure, scan exposure etc..Can also be to same position fraction
It is exposed.Now, multiple conditions of exposure can be with identical, it is also possible to different.
Light exposure preferably such as 5～1000mJ/cm in any of the above-described Exposure mode2, more preferably 5～500mJ/cm2,
Further preferred 5～300mJ/cm2, particularly preferred 5～200mJ/cm2, most preferably 5～50mJ/cm2.Should illustrate, light exposure
The appropriate optimization such as the wavelength of light, the composition of negative light-sensitive resin combination and coating thickness of irradiation can be passed through.
The time for exposure of per unit area is not particularly limited, can be according to the exposure power of the exposure device for using and need
Light exposure wanted etc. is designed.Should illustrate, in the case of scan exposure, exposure can be obtained according to the sweep speed of light
Time.
The time for exposure of per unit area is usually 1～60 second or so.
Using the negative light-sensitive resin combination of the present invention, in above-mentioned exposure portion, in exposure alkali-soluble tree is carried out
The radical polymerization of fat (A), while acid producing agent (C) produces acid, in the presence of the acid, acid as curing agent (D) and alkali by exposure
The acidic-groups such as the carboxylic acid of soluble resin (A) are reacted.Thus, using the negative light-sensitive resin combination of the present invention,
Be obtained cured film, particularly the upper surface of cured film alkali soluble resin (A) curability and refuse consolidating for ink agent (E)
The qualitative cured film being improved.Even if in addition, obtaining that also there is curability, the spy equal with conventional cured film for low light exposure
It is not the cured film of the curability of upper surface.
Then, as shown in figure ip, carry out using the development of alkaline developer, formed only by the exposure portion 23A with exposed film 23
The next door 4 that corresponding position is constituted.The opening portion 5 surrounded by next door 4 is the portion that non-exposed portion 23B is present in exposed film 23
Position, Fig. 1 D to be illustrated and remove the state after non-exposed portion 23B by development.As described above, non-exposed portion 23B is refusing oil
Black agent (E) migrates to upper layer part and there's almost no than its layer on the lower and refuses to utilize alkaline developer quilt in the state of ink agent (E)
Dissolving, removal, therefore, refuse ink agent (E) and hardly residue in opening portion 5.
Should illustrate, in the next door 4 shown in Fig. 1 D, the superiors comprising its upper surface are to refuse ink layer 4A.Refuse ink
When agent (E) is not comprising the side chain with ethylenic double bond, refuses ink agent (E) in exposure and be present in high concentration with maintaining the original state
The superiors and become and refuse ink layer.In exposure, it is present in and refuses the alkali soluble resin (A) of ink agent (E) periphery and particularly exist
Photocuring is carried out securely with acid as curing agent (D) in the presence of the acid that acid producing agent (C) is produced, and refuses ink agent (E) and be fixed on to refuse
Ink layer.Further, when negative light-sensitive resin combination arbitrarily contains mercaptan compound (G), promote to be based on ethylenic double bond
Reaction, more firmly carry out refusing the solidification of ink layer.
Even if in the case where ink agent (E) is refused comprising the side chain with ethylenic double bond, alkali soluble resin (A) also exists
Photocuring is carried out securely with acid as curing agent (D) in the presence of the acid that acid producing agent (C) is produced, while refusing ink agent (E) each other
And/or with alkali soluble resin (A) and the mercaptan compound (G) for arbitrarily containing, other photocuring compositions together photocuring,
What formation refused that ink agent (E) is securely joined with refuses ink layer 4A.
In either case, refusing to form mainly alkali soluble resin (A), acid as curing agent on the downside of ink layer 4A
(D) mercaptan compound (G) and the photocuring composition beyond it for and arbitrarily containing is produced by using Photoepolymerizationinitiater initiater (B)
Cationic polymerization in the presence of the acid that the radical polymerization of raw free radical and acid producing agent (C) are produced carries out photocuring and several
Without the layer 4B for refusing ink agent (E).
By operating as above, refuse ink agent (E) and be fully fixed on comprising the next door for refusing ink layer 4A and its underpart layer 4B,
Therefore, hardly migrate to opening portion in development.
Thus, in the negative light-sensitive resin combination of the present invention, by combining the radical polymerization carried out using light
Reaction and the curing reaction in the presence of the acid produced by light, are sufficiently carried out the surface of cured film and the solidification of inside.Cause
This, as exposure portion cured portion for development when alkaline developer caused by erosion, peel off have patience.Therefore, expose
Portion is not easy to be affected in prolonged development, therefore, be conducive to removing of the residue of opening portion etc..
After development, further can be heated counter septum 4.Preferably 80～250 DEG C of heating-up temperature.By heating, next door 4
Solidification become more firm.Refuse in ink layer 4A in addition, refusing ink agent (E) and being more firmly fixed on.Even if the composition of the present invention
In the case of low-temperature setting, it is also possible to manifest high liquid-repellant, and then after it impregnated in the chemical reagent such as acid, organic solvent,
There can be high liquid-repellant.Particularly in plastic basis material as using PET film, Merlon, need lower to set
Heating-up temperature.Now, less than 150 DEG C of heating-up temperature, the particularly preferably heating-up temperature of less than 120 DEG C of setting are preferably set.This
When the composition of invention is heated in a low temperature of as mentioned above, liquid-repellant is also maintained, and chemical reagent resistance is excellent.
Even if by operating as above the resin cured film of the invention that obtains and next door 4 is exposed under low light exposure
In the case of, also refuse ink with good in upper surface.In addition, for next door 4, after development, hardly depositing in opening portion 5
Ink agent (E) is being refused, the uniform coating of the ink of opening portion 5 can be fully being guaranteed.
Should illustrate, for the purpose of the ink-receptive for more reliably obtaining opening portion 5, after above-mentioned heating, in order to remove
Development residue of negative light-sensitive resin combination for going to there may be present in opening portion 5 etc., it is also possible to the substrate with next door 4
1 implements ultraviolet/ozone process.
The next door preferably such as width formed by the negative light-sensitive resin combination of the present invention is less than 100 μm, especially
Preferably less than 20 μm.In addition, the distance (width of pattern) between adjacent next door is preferably less than 300 μm, particularly preferably
Less than 100 μm.The highly preferred of next door is 0.05～50 μm, particularly preferably 0.2～10 μm.
By the next door that formed of negative light-sensitive resin combination of the present invention when above-mentioned width is formed as, in marginal portion
It is concavo-convex less and linearity is excellent.Should illustrate, the high linear of next door is apparent in using resin (A-2) as alkali-soluble
Particularly significant during resin, the resin (A-2) is the tree for being imported with acidic-group and ethylenic double bond in the epoxy
Fat.Even the pattern also high thereby, it is possible to form fine pattern accuracy.If the pattern shape of such high precision can be carried out
Into then particularly useful as the next door of organic EL element, quantum dot displays, tft array, thin-film solar cells.
When pattern printing is carried out by IJ methods, the next door of the present invention can act as using its opening portion as ink injection region
Next door.When carrying out pattern printing by IJ methods, if forming this in its opening portion mode consistent with desired ink injection region
The next door of invention utilizing, then due to next door upper surface have it is good refuse ink, it is possible to suppressing ink to exceed next door
And it is injected into undesirable opening portion i.e. ink injection region.In addition, by the opening portion of next door encirclement due to ink moistening autgmentability
Well, therefore, it is possible to do not produce show money or valuables one carries unintentionally etc. in the case of ink is equably printed in desired region.
If using the next door of the present invention, can fine carry out as mentioned above using the pattern printing of IJ methods.Therefore, originally
The next door of invention is used as in the light in substrate surface with multiple points and the next door positioned between consecutive points that point is formed by IJ methods
Learn element, particularly organic EL element, quantum dot displays, tft array, thin-film solar cells next door it is useful.
[optical element]
The optical element of the present invention, particularly organic EL element, quantum dot displays, tft array or thin film solar electricity
Pond is the optical element in the next door for having multiple points and the invention described above positioned between consecutive points in substrate surface.For the present invention
Optical element, particularly organic EL element, quantum dot displays, tft array or thin-film solar cells, preferably by IJ methods
Form point.
So-called organic EL element be with anode and negative electrode clamping organic film luminescent layer structure, the present invention next door energy
It is enough in the next door purposes for dividing organic luminous layer, the next door purposes for dividing organic tft layer, divides application type oxide semiconductor
Next door purposes etc..
In addition, organic tft array element is following element:Multiple points are configured to overlook rectangular, and in each point picture is arranged
Plain electrode and as driving the TFT of its switch element, using organic semiconductor layer as half of the channel layer comprising TFT
Conductor layer.Organic tft array element for example can be arranged at organic EL element or liquid crystal cell etc. as tft array substrate.
For optical element, such as organic EL element of embodiments of the present invention, below to using it is obtained above every
Wall is illustrated in opening portion by the example that IJ methods form point.Should illustrate, the optical element such as organic EL element of the present invention
Point forming method be not limited to it is following.
Fig. 2A and Fig. 2 B are to schematically show using the next door 4 being formed on substrate 1 shown in above-mentioned Fig. 1 D to manufacture
The figure of the method for organic EL element.Here, the next door 4 on substrate 1 is with the figure of opening portion 5 and the point of the organic EL element to be manufactured
The consistent mode of case is formed.
As shown in Figure 2 A, the opening portion 5 for being surrounded from the counter septum 4 of ink gun 9 is added dropwise ink 10, and the injection of opening portion 5 is advised
Quantitative ink 10.As ink, can suitably select to use the known oil as organic EL element according to the function of point
Ink.
Then, according to the species of the ink 10 for using, such as the removing, solidification for solvent is implemented to be dried and/or is heated
Deng processing, as shown in Figure 2 B, the organic EL element 12 that the shape to adjoin with next door 4 is formed with desired point 11 is obtained.
The optical element of embodiments of the present invention, particularly organic EL element, quantum dot displays, tft array or thin
Film solar cell is following optical element, particularly organic EL element, quantum dot displays, tft array or the film sun
Can battery:By using the next door of the present invention, in the fabrication process ink can it is uneven and equably moisten spread over by
The opening portion that next door divides, the point for thus being formed well with precision.
Should illustrate, organic EL element for example can be manufactured as follows, but be not limited to this.
By sputtering method etc. by optically transparent electrode film forming such as tin-doped indium oxides (ITO) in the translucency of the plastics such as glass, PET
Substrate.The optically transparent electrode is patterned as needed.
Then, using the negative light-sensitive resin combination of the present invention, by comprising coating, exposed and developed photoetching process
Next door is formed along the profile of each point to overlook clathrate.
Then hole injection layer, hole transporting layer, luminescent layer, hole blocking layer and electricity are respectively coated by IJ methods in point
The material of sub- implanted layer is simultaneously dried, and these layers are stacked gradually.The type and quantity of the organic layer being formed in a little can be appropriate
Design.
Finally, the reflecting electrodes such as aluminium are formed by vapour deposition method etc..
In addition, quantum dot displays for example can be manufactured as follows, but it is not limited to this.
By sputtering method etc. by optically transparent electrode film forming such as tin-doped indium oxides (ITO) in the translucency of the plastics such as glass, PET
Substrate.The optically transparent electrode can be patterned as needed.
Then, using the negative light-sensitive resin combination of the present invention, by comprising coating, exposed and developed photoetching process
Next door is formed along the profile of each point to overlook clathrate.
Then, hole injection layer, hole transporting layer, quantum dot layer, hole blocking layer are respectively coated by IJ methods in point
It is with the material of electron injecting layer and dry, these layers are stacked gradually.The type and quantity of the organic layer being formed in a little can be with
Suitable design.
Finally, the optically transparent electrodes such as reflecting electrode or ITO such as aluminium are formed by vapour deposition method etc..
Further, the optical element of embodiments of the present invention can also apply to the blue light conversion hysteria amount of for example following manufacture
Son point display.
In the light-transmitting substrate of the plastics such as glass, PET, using the negative light-sensitive resin combination of the present invention along each point
Profile with overlook clathrate formed next door.
Then, point in by IJ methods coating convert blue light into green glow nano-particle solution, convert blue light into it is red
The nano-particle solution of light and blue colored ink as needed and dry, making module.The use of colour developing is blue light
Source is as backlight and uses above-mentioned module as the substitute of colour filter, thus obtains the excellent liquid crystal display of colorrendering quality
Device.
Tft array for example can be manufactured as follows, but be not limited to this.
By sputtering method etc. by gate electrode film forming such as aluminium, its alloys in the light-transmitting substrate of the plastics such as glass, PET.The grid
Electrode can be patterned as needed.
Then, the gate insulating films such as silicon nitride are formed by plasma CVD method etc..Can also on gate insulating film shape
Into source electrode, drain electrode.Source electrode and drain electrode for example can pass through vacuum evaporation, sputtering formed aluminium, gold, silver, copper, they
The metallic film of alloy etc. is making.Method as source electrode and drain electrode are patterned, there is following method:Forming gold
After category film, application resist is exposed, develops, and resist is remained in the part that form electrode, then with phosphoric acid, king
Water etc. removes the metal for exposing, and finally removes resist.In addition, when the metallic film of gold etc. is formed, also following method:
The resist of application in advance, is exposed, develops, and in the part that should not form electrode resist is remained, and is then forming metal foil
After film, resist is together removed with metallic film.Alternatively, it is also possible to pass through spray using metal nano colloid of silver, copper etc. etc.
The methods such as ink form source electrode and drain electrode.
Next, using the negative light-sensitive resin combination of the present invention, by comprising coating, exposed and developed photoetching
Method forms next door along the profile of each point to overlook clathrate.
Then, IJ method coating semiconductor solution is passed through in point and solution is dried, semiconductor layer is consequently formed.As this
Semiconductor solution, it is possible to use solutions of organic semiconductors, inorganic application type oxide semiconductor solution.Source electrode, drain electrode
Can be formed using methods such as ink-jets after the semiconductor layer is formed.
Finally, the optically transparent electrode film forming such as ITO, by the diaphragm film forming such as silicon nitride, is consequently formed by sputtering method etc..
Embodiment
Hereinafter, based on embodiment, the present invention will be described, but the present invention is not limited to these embodiments.Example 1～10
For embodiment, example 11～13 is comparative example.
Each measure is carried out by following method.
[number-average molecular weight (Mn), matter average molecular weight (Mw)]
By gel permeation chromatography, number-average molecular weight (Mn) and the equal molecule of matter are determined as standard substance using polystyrene
Amount (Mw).As gel permeation chromatograph, using HPLC-8220GPC (eastern Cao's company system).As chromatographic column, using being connected with
The post of 3 shodex LF-604.As detector, using RI detectors.As standard substance, using EasiCal PS1
(Polymer Laboratories company systems).Further, when number-average molecular weight and matter average molecular weight is determined, chromatographic column is kept
At 37 DEG C, as eluent, using tetrahydrofuran, flow velocity is made for 0.2mL/ minutes, 0.5% tetrahydrofuran of injection measure sample
The μ L of solution 40.
[fluorine atom containing ratio]
Fluorine atom containing ratio, as standard substance, is passed through using Isosorbide-5-Nitrae-two (trifluoromethyl) benzene19F NMR are determined and calculated.
[acid number]
Acid number is calculated according to the mixing ratio theoretical property of raw material.
The abbreviation of the compound used in following each example is shown in following.
(alkali soluble resin (A))
Alkali soluble resin (A1) composition:Cresol novolak type epoxy resin and propylene acid reaction are made, then with 1,
2,3,6- tetrabydrophthalic anhydrides react and import acryloyl group and carboxyl, and the resin hexane for obtaining is purified
The composition (mass % of solid constituent 70, PGMEA30 mass %) of resin (alkali soluble resin (A1), acid number 60mgKOH/g)
Alkali soluble resin (A2) composition:The resin of carboxyl and ethylenic double bond has been imported to bisphenol A type epoxy resin
The composition (mass % of solid constituent 70, mass % of PGMEA 30) of (alkali soluble resin (A2), acid number 100mgKOH/g).
Alkali soluble resin (A3) composition:To the epoxy resin derivative with biphenyl backbone shown in following formula (A-2a)
Entered the resin (alkali soluble resin (A3), acid number 70mgKOH/g) of ethylenic double bond and acidic-group composition (solid into
Divide 70 mass %, PGMEA30 mass %).
(in formula (A-2a), v is 1～50 integer, preferably 2～10 integer.In addition, the hydrogen atom of phenyl ring can be respective
Independent to be replaced by the alkyl of carbon number 1～12, halogen atom or phenyl, a part of hydrogen atom of the phenyl can be substituted base and take
Generation.)
Alkali soluble resin (A-R-1):In the reactive tank of the internal volume 1L for possessing mixer load acetone (555g),
AA (acrylic acid) (36.0g), 2-HEMA (108.0g), IBMA (72.0g), chain-transferring agent DSH (9.7g) and polymerization initiator
V-70 (5.1g), stirs while make it be polymerized 18 hours at 40 DEG C under nitrogen environment, obtains alkali soluble resin (A-
R-1 solution).Adding water in the acetone soln of the alkali soluble resin (A-R-1) for obtaining carries out reprecipitation purifying, then,
Reprecipitation is carried out with petroleum ether to purify, be vacuum dried, obtain alkali soluble resin (A-R-1) 235g.Alkali-soluble tree
The number-average molecular weight (Mn) of fat (A-R-1) is 5000, and the acid number of alkali soluble resin (A-R-1) is 119mgKOH/g.
(Photoepolymerizationinitiater initiater (B))
IR907:2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinopropane -1- ketone (BASF AG's system,
Trade name IRGACURE907).
OXE02:Ethyl ketone 1- [9- ethyl -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -1-
(O- acetyl group oximes) (BASF AG's system, trade name:OXE02).
EAB:Double (diethylamino) benzophenone (Tokyo chemical conversion industry company system) of 4,4'-.
(acid producing agent (C))
PAG-A:Double (the trichloromethyl) -1,3,5- triazines of 2- (5- methyl -2- furyls) vinyl -4,6-
(compound shown in above-mentioned formula (C8-2))
PAG-B:2- [2- (n-propyl sulfonyloxyimino) thiophene -3 (2H)-subunit] -2- (2- methylbenzenes
Base) acetonitrile (R in the compound shown in above-mentioned formula (C11)b11For the compound of n-propyl)
WPAG199:Double (p-toluenesulfonyl) diazomethanes
SI-150L:Aromatic matte SbF shown in above-mentioned formula (C0-1)6 -Salt (three new chemical industrial company's systems, commodity
Name:San-aid SI-150L)
(acid as curing agent (D))
Epoxy A:The epoxide containing bicyclopentane ring shown in above-mentioned formula (De1)
Epoxy B:Naphthalene-ring containing epoxide shown in above-mentioned formula (De2)
Melamine A:2,4,6- tri- [double (methoxy) amino] -1,3,5- triazines (above-mentioned formula (D1-1) institute
The compound for showing)
Melamine B:1,3,4,6- tetra- (methoxy) glycoluril (compound shown in above-mentioned formula (D3-1))
(refusing the raw material of ink agent (E1))
Compound (s1-1) equivalent to compound (s1):F(CF2)6CH2CH2Si(OCH3)3(by known method system
Make).
Compound (s2-1) equivalent to compound (s2):Si(OC2H5)4(colcoat company systems).
Compound (s3-1) equivalent to compound (s3):CH2=CHCOO (CH2)3Si(OCH3)3(Tokyo chemical conversion industry
Company system).
Compound (s5-1) equivalent to compound (s5):
Compound (s6-1) equivalent to compound (s6):
(refusing the raw material of ink agent (E2))
C6FMA:CH2=C (CH3)COOCH2CH2(CF2)6F
X-174DX:Methacrylate (chemical industrial company of SHIN-ETSU HANTOTAI system, trade name X- containing dimethyl silscone chain
22-174DX)
X-8201:Methacrylate (chemical industrial company of SHIN-ETSU HANTOTAI system, trade name X-24- containing dimethyl silscone chain
8201)
C4 α-Cl acrylate:CH2=C (Cl) COOCH2CH2(CF2)4F
C8FA:CH2=CHCOOCH2CH2(CF2)8F
CHMA:Cyclohexyl methacrylate
MAA:Methacrylic acid
2-HEMA:2-hydroxyethyl methacrylate
MMA:Methyl methacrylate
GMA:GMA
IBMA:Isobornyl methacrylate
V-65:(2,2 '-azo is double (2,4- methyl pentane nitriles))
V-70:2,2 '-azo is double (4- methoxyl group -2,4- methyl pentane nitriles)
DSH:N-dodecyl mercaptan
BEI:1,1- (double acryloyloxymethyls) ethyl isocyanate)
AOI:2- acryloyloxyethyl isocyanates)
DBTDL:Dibutyl tin laurate
TBQ:Tert-butyl group 1,4-benzoquinone
MEK:2- butanone
(crosslinking agent (F))
DPHA:Dipentaerythritol acrylate
(other)
KBM403:3- glycidoxypropyltrime,hoxysilanes
Mercaptan compound:Pentaerythrite four (3- mercaptobutylates)
MHQ:2- methylnaphthohydroquinones
(solvent (J))
PGME:Propylene glycol monomethyl ether
EDM:Diethylene glycol ethyl methyl ether
IPA:2- propyl alcohol
DEGDM:Diethylene glycol dimethyl ether
PGMEA:Propylene glycol monomethyl ether
[refusing the synthesis of ink agent (E)]
Following synthesis prepares to refuse ink agent (E).
(synthesis example 1:Refuse the synthesis of ink agent (E-1))
In the internal volume 1000cm for possessing mixer3Autoclave in load MEK 420.0g, C6FMA99.0g,
MAA9.0g, 2-HEMA18.0g, MMA45.0g, IBMA9.0g, polymerization initiator V-65 3.0g and DSH 5.0g, in azo-cycle
Stir under border while make it be polymerized 24 hours at 50 DEG C, then heat 5 hours at 70 DEG C, be passivated polymerization initiator and
Obtain the solution (solid component concentration of copolymer (refusing ink agent (E-1))；30 mass %).The solution is used for described later negative
The manufacture of type photosensitive polymer combination.Should illustrate, in the following synthesis for refusing ink agent, for containing refusing ink agent
The state of solution obtain refusing the situation of ink agent, after solid component concentration is determined or adjusted, be used for the state of the solution
The manufacture of negative light-sensitive resin combination.
The number-average molecular weight for refusing ink agent (E-1) is 14200, and matter average molecular weight is 21500, and fluorine atom containing ratio is
31.4 mass %, acid number is 32.6 (mgKOH/g).
(synthesis example 2:Refuse the synthesis of ink agent (E-2))
In the internal volume 1000cm for possessing mixer3Autoclave in load MEK 415.1g, C6FMA81.0g, MAA
18.0g, 2-HEMA 81.0g, polymerization initiator V-65 5.0g and DSH 4.7g, stir while making it under nitrogen environment
It is polymerized 24 hours at 50 DEG C, then heats 5 hours at 70 DEG C, polymerization initiator is passivated and is obtained the solution of copolymer.Altogether
The number-average molecular weight of polymers is 5540, and matter average molecular weight is 13200.
Then, in the internal volume 300cm for possessing mixer3Autoclave in load above-mentioned copolymer solution 130.0g,
BEI 33.5g, DBTDL 0.13g, TBQ 1.5g, stir while making it react 24 hours at 40 DEG C, synthesis is thick to be polymerized
Thing.Add hexane to carry out reprecipitation after purification in the crude polymer solution for obtaining, be vacuum dried and obtained refusing ink agent
(E-2).The number-average molecular weight for refusing ink agent (E-2) is 7540, and matter average molecular weight is 16200, and fluorine atom containing ratio is 14.8
Quality %, acid number is 35.1 (mgKOH/g).
(synthesis example 3:Refuse the synthesis of ink agent (E-3))
In the internal volume 1000cm for possessing mixer3Autoclave in load MEK 420.0g, C6FMA 99.0g, MAA
9.0g, 2-HEMA 18.0g, GMA 18.0g, MMA 36.0g, polymerization initiator V-65 3.0g and DSH 5.0g, in azo-cycle
Stir under border while make it be polymerized 24 hours at 50 DEG C, then heat 5 hours at 70 DEG C, be passivated polymerization initiator and
Obtain the solution (solid component concentration of copolymer (refusing ink agent (E-3))；30 mass %).
The number-average molecular weight for refusing ink agent (E-3) is 14850, and matter average molecular weight is 22700, and fluorine atom containing ratio is
31.4 mass %, acid number is 32.6 (mgKOH/g).
(refusing the preparation of ink agent (E-4))
As ink agent (E-4) is refused, prepare Megafac RS102 (trade name, DIC company systems:With following formula (E2F)
The polymer of shown repetitive, n/m=3～4).The number-average molecular weight for refusing ink agent (E-4) is 5700, matter average molecular weight
For 8800, fluorine atom containing ratio is 19.0 mass %.
(synthesis example 5:Refuse the synthesis of ink agent (E-5))
In the internal volume 2000cm for possessing mixer3Autoclave in be put into C4 α-Cl acrylate 317.5g, MAA
79.4g, IBMA 47.7g, 2-HEMA 52.9g, DSH 4.6g, polymerization initiator V-70 2.0g, MEK 1160g, in azo-cycle
Stir under border while make it be polymerized 24 hours at 50 DEG C, then heat 5 hours at 70 DEG C, be passivated polymerization initiator and
Obtain the solution of copolymer.The number-average molecular weight of copolymer is 5060, and matter average molecular weight is 8720.If it is dense to determine solid constituent
Degree, then be 30 mass %.
Then, in the internal volume 300cm for possessing mixer3Autoclave in load above-mentioned copolymer solution 130.0g,
AOI 3.6g (being 0.8 equivalent relative to the hydroxyl of copolymer), DBTDL0.014g, TBQ 0.18g, stir while making it
React 24 hours at 40 DEG C, synthesize crude polymer.Hexane is added to carry out reprecipitation purifying in the crude polymer solution for obtaining
Afterwards, it is vacuum dried and is obtained refusing ink agent (E-5).The number-average molecular weight for refusing ink agent (E-5) is 8000, the equal molecule of matter
Measure as 10600, fluorine atom containing ratio is 28.0 mass %, acid number is 93.3 (mgKOH/g).
(synthesis example 6:Refuse the synthesis of ink agent (E-6))
Load acetone 555.0g, C6FMA60.0g, X-174DX in the autoclave of the internal volume 1L for possessing mixer
120.0g, MAA24.0g, CHMA36.0g, chain-transferring agent DSH 5.4g and polymerization initiator V-70 2.0g, it is next in nitrogen environment
Stir while making it be polymerized 18 hours at 40 DEG C and obtain refusing the solution of ink agent (E-6) on side.
Add water to carry out reprecipitation purifying in the acetone soln for refusing ink agent (E-6) for obtaining, then entered with petroleum ether
Row reprecipitation is purified, and is vacuum dried and is obtained refusing ink agent (E-6).The number-average molecular weight for refusing ink agent (E-6) is
9000, matter average molecular weight is 11700, and fluorine atom containing ratio is 14.7 mass %, and acid number is 65mgKOH/g.
(synthesis example 7:Refuse the synthesis of ink agent (E-7))
Load acetone 555.0g, C8FA48.0g, X-8201 in the autoclave of the internal volume 1L for possessing mixer
120.0g, MAA12.0g, IBMA 60.0g, chain-transferring agent DSH 10.8g and polymerization initiator V-70 3.0g, under nitrogen environment
Stir while making it be polymerized 18 hours at 40 DEG C and obtain refusing the solution of ink agent (E-7).
Add water to carry out reprecipitation purifying in the acetone soln for refusing ink agent (E-7) for obtaining, then entered with petroleum ether
Row reprecipitation is purified, and is vacuum dried and is obtained refusing ink agent (E-7).The number-average molecular weight for refusing ink agent (E-7) is
4500, matter average molecular weight is 5590, and fluorine atom containing ratio is 12.5 mass %, and acid number is 33mgKOH/g.
The above-mentioned raw material composition for refusing ink agent (E-1)～(E-7) for obtaining or preparing and characteristic are collected and is shown in table 1.
[table 1]
(synthesis example 8:Refuse the synthesis of ink agent (E-8))
Possessing the 1000cm of mixer3Compound (s1-1) 15.0g, compound (s2-1) are put in there-necked flask
20.0g, compound (s3-1) 27.0g, obtain homogeney of hydrolysable silanes compound mixture.Then, IPA is put in the mixture
284.3g, make material solution.
1% aqueous hydrochloric acid solution 30.0g is added dropwise in the material solution for obtaining.Stir 5 hours at 40 DEG C after completion of dropwise addition,
The IPA solution for obtaining refusing ink agent (E-8) (refuses ink agent (E-8) concentration:10 mass %).
Should illustrate, after reaction terminates, using the composition of gas chromatograph for determination reactant liquor, confirm eachization as raw material
Compound is below test limit.
(synthesis example 9,10:Refuse ink agent (E-9), the synthesis of (E-10))
The hydrolysable silanes compound of the monomer component in synthesis example 8 and its amount are changed as table 2, except this with
Outward, the IPA solution for obtaining refusing ink agent (E-9) in the same manner as synthesis example 8 (refuses ink agent (E-9) concentration:10 mass %), refuse
The IPA solution of ink agent (E-10) (refuses ink agent (E-10) concentration:10 mass %).
By the throwing for refusing the raw material hydrolysable silanes compound used in ink agent ((E-8)～(E-10)) manufacture for obtaining
Doses etc. is shown in table 2.In table 2, silane compound represents hydrolysable silanes compound.In addition, refusing ink agent ((E- by what is obtained
8)～(E-10)) number-average molecular weight (Mn), matter average molecular weight (Mw), the measurement result of fluorine atom containing ratio (quality %) show
In table 2.
[table 2]
[example 1:The manufacture of negative light-sensitive resin combination and cured film, the manufacture of next door (pattern film)]
(manufacture of negative light-sensitive resin combination)
By solid constituent (resin (A1)) be alkali soluble resin (A1) composition of amount of 10.0g, IR907 0.30g,
OXE02 0.10g, EAB 0.20g, PAG-A 0.30g, epoxy A1.60g, refuse ink agent (E-3) 0.05g, DPHA5.0g,
EDM 30.0g are put into 200cm3Stirring container and PGME is added in the way of total amount is as 100g, stirring 3 hours and manufacture negative
Type photosensitive polymer combination 1.
(manufacture of cured film)
The glass substrate of 10cm square is carried out into 30 seconds ultrasonic waves with ethanol to clean, the UV/O of 5 minutes is then carried out3Place
Reason.UV/O3Process uses PL2001N-58 (Sen Engineering company systems) as UV/O3Generation device.254nm converts
Luminous power (light output) be 10mW/cm2。
Glass baseplate surface after above-mentioned cleaning is coated with negative photosensitive resin combination obtained above using circulator
After thing 1, it is dried 2 minutes on hot plate at 100 DEG C and form the desciccator diaphragm of 2.4 μm of thickness (only example 3 is 1.2 μm).It is right
The exposure power (exposure output) of the whole face once irradiating 365nm conversions of desciccator diaphragm for obtaining is 300mW/cm2Super-pressure mercury
The UV light of lamp.With it, with light exposure as 30mJ/cm2Or 50mJ/cm2Mode to adjust irradiation time solid to manufacture 2 kinds
Change film.Should illustrate, in either case, the light of below 330nm has been turned off in exposure.
Then, the glass substrate after above-mentioned exposure-processed is carried out 10 seconds in 2.38% tetramethylammonium hydroxide aqueous solution
Impregnation process, after being rinsed using water so as to be dried.Then, it is heated 60 minutes on hot plate at 230 DEG C and is not had
The cured film of opening portion.
(manufacture of pattern film 1)
The glass substrate of 10cm square is carried out into 30 seconds ultrasonic washers with ethanol, then, the UV/O of 5 minutes is carried out3Place
Reason.UV/O3Process uses PL2001N-58 (Sen Engineering company systems) as UV/O3Generation device.254nm converts
Luminous power (light output) be 10mW/cm2。
Glass baseplate surface after above-mentioned cleaning is coated with negative photosensitive resin combination obtained above using circulator
After thing 1, it is dried 2 minutes on hot plate at 100 DEG C and form the desciccator diaphragm of 2.4 μm of thickness (only example 3 is 1.2 μm).It is situated between
The exposure by shelter (non-exposed portion) the whole face once irradiating 365nm of desciccator diaphragm for obtaining converted for the photomask of 2.5cm × 5cm
Luminous power (exposure output) is 300mW/cm2The UV light of extra-high-pressure mercury vapour lamp (light exposure is 30mJ/cm2Or 50mJ/cm2).Expose
Light time, the light of below 330nm is ended.In addition, desciccator diaphragm is 50 μm with the spacing distance of photomask.Photomask using line/
Away from for 20 μm/50 μm, 10 μm/50 μm, 8 μm/50 μm, 6 μm/50 μm, the photomask of 4 μm/50 μm of design.
Then, the glass substrate after above-mentioned exposure-processed is impregnated 40 seconds in 2.38% tetramethylammonium hydroxide aqueous solution
Developed, after non-exposed portion is rinsed using water so as to be dried.Then, it is heated 60 minutes on hot plate at 230 DEG C
And pattern film 1 is obtained as the cured film with opening portion corresponding with the shelter of photomask.
(manufacture of pattern film 2)
The glass substrate of 10cm square is carried out into 30 seconds ultrasonic waves with ethanol to clean, then, the UV/O of 5 minutes is carried out3Place
Reason.UV/O3Process uses PL2001N-58 (Sen Engineering company systems) as UV/O3Generation device.254nm converts
Luminous power (light output) be 10mW/cm2。
Glass baseplate surface after above-mentioned cleaning is coated with negative photosensitive resin combination obtained above using circulator
After thing 1, it is dried 2 minutes on hot plate at 100 DEG C and form the desciccator diaphragm of 2.4 μm of thickness (only example 3 is 1.2 μm).It is situated between
The exposure by shelter (non-exposed portion) the whole face once irradiating 365nm of desciccator diaphragm for obtaining converted for the photomask of 2.5cm × 5cm
Luminous power (exposure output) is 300mW/cm2The UV light of extra-high-pressure mercury vapour lamp (light exposure is 30mJ/cm2Or 50mJ/cm2).Expose
Light time, the light of below 330nm is ended.In addition, desciccator diaphragm is 50 μm with the spacing distance of photomask.Photomask using line/
Away from for 20 μm/50 μm, 10 μm/50 μm, 8 μm/50 μm, 6 μm/50 μm, the photomask of 4 μm/50 μm of design.
Then, the glass substrate after above-mentioned exposure-processed is impregnated into 200 in 2.38% tetramethylammonium hydroxide aqueous solution
Second developed, by high pressure water washing 10 second of the non-exposed portion with 1.5MPa after so as to be dried.Then, by its on hot plate
Heat 60 minutes at 230 DEG C and obtain pattern film 2 as the cured film with opening portion corresponding with the shelter of photomask.
(manufacture of pattern film 3)
Using the ito substrate on the glass substrate with ITO layer, above-mentioned minus is coated with using circulator in the ITO layer
After photosensitive polymer combination 1, it is dried at 100 DEG C 2 minutes and form 2.4 μm of thickness (only example 3 is 1.2 μ
M) desciccator diaphragm.Via the photomask (clathrate that light shielding part is 200 μm of 100 μ m, transmittance section is 20 μm with patterns of openings
Pattern) exposure power (exposure output) of the whole face once irradiating 365nm conversions of desciccator diaphragm to obtaining is 300mW/cm2Superelevation
The UV light of medium pressure mercury lamp.During exposure, the light of below 330nm is ended.In addition, desciccator diaphragm is 50 μ with the spacing distance of photomask
m.In each example, conditions of exposure was the time for exposure for 4 seconds, and light exposure is 100mJ/cm2。
Then, the glass substrate after above-mentioned exposure-processed is impregnated in 2.38 mass % tetramethylammonium hydroxide aqueous solutions
Developed within 40 seconds, after non-exposed portion is rinsed using water so as to be dried.Then, heat 60 minutes at 230 DEG C on hot plate
And pattern film 3 is obtained as the cured film with pattern corresponding with the patterns of openings of photomask.
Negative light-sensitive resin combination 1 and cured film, pattern film 1～3 to obtaining implements following evaluation.To evaluate
As a result together it is shown in table 3 with the composition of negative light-sensitive resin combination 1.
(evaluation)
<The thickness of cured film>
Using laser microscope (Keyence company systems, device name:VK-8500) it is measured.
<Refuse ink>
The PGMEA contact angles of cured film upper surface obtained above are determined by following method, as refusing ink
Evaluate.
By sessile drop method, according to JIS R3257 " the wettability test method on base plate glass surface " in cured film upper surface 3
Place's mounting PGMEA drops, are measured to each PGMEA drops.Drop is 2 μ L/ drops, and measure is carried out at 20 DEG C.Contact angle is determined by 3
The mean value of value is obtained.
The PGMEA contact angles of cured film upper surface obtained above are determined by above-mentioned method.
◎:Contact angle is more than 45 degree
○:Contact angle is 40 degree less than 45 degree
△:Contact angle is 35 degree less than 40 degree
×:Contact angle is less than 35 degree
<Patternability>
With regard to pattern film 1, by following benchmark evaluation patternabilities.Determine the line portion that line/spacing is for 20 μm/50 μm
The live width divided.
◎:It is the live width within ± 3 μm relative to mask size.
○:It is more than ± 3 μm and for the live width within 5 μm relative to mask size.
×:Relative to mask size live width is more than ± 5 μm or is peeling.
<(200 seconds) residual resolution ratio of developing time>
With regard to pattern film 2, by peel resistance of following benchmark evaluations to long-time development.
◎:Remain the line of at least 10 μm of live width.
○:Remain the line of at least 20 μm of live width.
×:In whole line/spacing samples, line is partially stripped.
<Opening portion residue>
Under the following conditions by X-ray photoelectron spectroscopy (XPS) to the opening portion of the ito substrate with pattern film 3
Middle body carries out surface parsing.By the F/In value (F1s/In3d5 on the opening portion surface measured by XPS；Phosphide atom concentration phase
For the ratio of carbon atom concn) less than 1.0 in the case of be set to " ◎ ", 1.0～2.0 situation is set to "○", more than 2.0 feelings
Condition is set to "×".
[condition of XPS]
Device:ULVAC-PHI company systems Quantera-SXM
X-ray source:Al Kα
The beam sizes of X-ray:About 20 μm of φ
Mensuration region:About 20 μm of φ
Detection angle:From 45 ° of sample face
Determine peak:F1s
Minute (in terms of Acquired Time):Within 5 minutes
Analysis software:MultiPak
[example 2～13]
Negative light-sensitive resin combination in example 1 is changed to into the composition shown in table 3, table 4 or table 5, in addition, is led to
Cross same method and manufacture negative light-sensitive resin combination and next door, cured film, carry out the evaluation same with example 1.By each example
Evaluation result be together shown in table 3, table 4 and table 5 with the composition of negative light-sensitive resin combination respectively.
[table 3]
[table 4]
[table 5]
There is unsaturation due to containing equivalent to the example 1～10 of the embodiment of the negative light-sensitive resin combination of the present invention
The alkali soluble resin or base soluble monomer (A) of double bond, Photoepolymerizationinitiater initiater (B), acid producing agent (C) and acid as curing agent (D),
Therefore, even if light exposure such as 30mJ/cm2It is like that low light exposure, also obtains high liquid-repellant.Even if in addition, light exposure is 50mJ/
cm2, live width is not easy to thicker, and patternability is good.
On the other hand, equivalent to comparative example example 11,12 due to without in Photoepolymerizationinitiater initiater (B), acid producing agent (C)
Any one, therefore, in light exposure such as 30mJ/cm2Like that in the case of low light exposure, liquid-repellant is insufficient.So, cured film
Upper surface to refuse ink insufficient.Equivalent to comparative example example 13 due to increase Photoepolymerizationinitiater initiater (B) amount, therefore, refuse
Fluidity is abundant, but due to not containing acid producing agent (C), therefore, even if in light exposure such as 30mJ/cm2It is like that the feelings of low light exposure
Under condition, live width is also easily thicker, and patternability is not enough.
Symbol description
1 ... substrate, 21 ... films, 22 ... desciccator diaphragms, 23 ... exposed films, 23A ... exposure portions, 23B ... non-exposed portions, 4 ...
Next door, 4A ... refuse ink layer, 5 ... opening portions, 31 ... shelters, 30 ... photomasks, 9 ink guns, 10 ... ink, 11 ... points,
12 ... optical elements.
Claims (9)
1. a kind of negative light-sensitive resin combination, it is characterised in that containing the alkali soluble resin with photo-curable or alkali
Soluble and monomeric (A), optical free radical polymerization initiator (B), light acid producing agent (C), acid as curing agent (D) and refusing with fluorine atom
Ink agent (E).
2. negative light-sensitive resin combination according to claim 1, it is characterised in that further containing compound (F),
The compound (F) has the unsaturated double-bond of more than 2 and does not have any one of acidic-group and fluorine atom in intramolecular.
3. negative light-sensitive resin combination according to claim 1 and 2, wherein, the acid as curing agent (D) is selected from three
At least a kind in paracyanogen amine compound, urea based compound and epoxy based compound.
4. the negative light-sensitive resin combination according to any one of claims 1 to 3, for manufacture organic EL element,
Quantum dot displays, tft array or thin-film solar cells.
5. a kind of resin cured film, it is characterised in that be negative-type photosensitive tree that usage right requires any one of 1～4
Oil/fat composition and formed.
6. a kind of next door, it is characterised in that the shape of the multiple subregions for being created as substrate surface is divided into a formation
Next door, the next door is made up of the resin cured film described in claim 5.
7. a kind of optical element, it is characterised in that be the light that there is multiple points and the next door positioned between consecutive points in substrate surface
Element is learned, the next door is formed by the next door described in claim 6.
8. optical element according to claim 7, wherein, the optical element be organic EL element, quantum dot displays,
Tft array or thin-film solar cells.
9. the optical element according to claim 7 or 8, wherein, the point is formed by ink-jet method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014148345 | 2014-07-18 | ||
| JP2014-148345 | 2014-07-18 | ||
| PCT/JP2015/070289 WO2016010077A1 (en) | 2014-07-18 | 2015-07-15 | Negative-type photosensitive resin composition, and resin cured film, partition and optical element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106662815A true CN106662815A (en) | 2017-05-10 |
| CN106662815B CN106662815B (en) | 2020-06-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580038938.5A Active CN106662815B (en) | 2014-07-18 | 2015-07-15 | Negative photosensitive resin composition, resin cured film, partition wall, and optical element |
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| Country | Link |
|---|---|
| JP (1) | JP6536578B2 (en) |
| KR (1) | KR102411740B1 (en) |
| CN (1) | CN106662815B (en) |
| TW (1) | TWI660239B (en) |
| WO (1) | WO2016010077A1 (en) |
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| CN109254443A (en) * | 2017-07-14 | 2019-01-22 | 三星显示有限公司 | Show equipment and its manufacturing method |
| CN110412829A (en) * | 2018-04-26 | 2019-11-05 | 东友精细化工有限公司 | Negative light-sensitive resin combination, photocuring pattern and image display device |
| CN111752097A (en) * | 2019-03-29 | 2020-10-09 | 常州强力电子新材料股份有限公司 | Self-luminous photosensitive resin composition, color filter and image display device |
| WO2023103058A1 (en) * | 2021-12-10 | 2023-06-15 | Tcl华星光电技术有限公司 | Display panel and method for manufacturing same |
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| KR102622857B1 (en) * | 2017-02-09 | 2024-01-10 | 동우 화인켐 주식회사 | Black photo sensitive resin composition for a forming pixel defined layer of oled and qled |
| JPWO2018155016A1 (en) * | 2017-02-21 | 2019-12-12 | 日本ゼオン株式会社 | Negative photosensitive resin composition |
| KR102146095B1 (en) | 2017-09-15 | 2020-08-19 | 주식회사 엘지화학 | Photoacid generator and photoresist composition for thick layer comprising the same |
| KR102311491B1 (en) * | 2019-02-13 | 2021-10-08 | 삼성에스디아이 주식회사 | Composition for double layer partition wall, double layer partition wall using the same and display device including the double layer partition wall |
| KR20200135682A (en) | 2019-05-24 | 2020-12-03 | 삼성디스플레이 주식회사 | Display apparatus and manufacturing the same |
| JPWO2021177253A1 (en) * | 2020-03-04 | 2021-09-10 | ||
| KR20210121917A (en) * | 2020-03-31 | 2021-10-08 | 동우 화인켐 주식회사 | Light Conversion Ink Composition, Color Filter and Display Device |
| CN116438218A (en) | 2020-10-28 | 2023-07-14 | 中央硝子株式会社 | Fluorine-containing resin, liquid repellent, photosensitive resin composition, cured product, and display |
| WO2022210797A1 (en) * | 2021-03-29 | 2022-10-06 | 株式会社カネカ | Negative photosensitive composition, optical semiconductor device, solid-state imaging device and electronic device |
| KR20240002709A (en) | 2022-06-29 | 2024-01-05 | 샌트랄 글래스 컴퍼니 리미티드 | Photosensitive resin composition, resin film, cured product, dividing wall, organic electroluminescent element, wavelength conversion layer, display, method for producing cured product and method for producing dividing wall |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2016010077A1 (en) | 2016-01-21 |
| KR102411740B1 (en) | 2022-06-21 |
| KR20170032318A (en) | 2017-03-22 |
| JP6536578B2 (en) | 2019-07-03 |
| TWI660239B (en) | 2019-05-21 |
| TW201619694A (en) | 2016-06-01 |
| JPWO2016010077A1 (en) | 2017-04-27 |
| CN106662815B (en) | 2020-06-16 |
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