CN104684994B - Refuse ink compositions, negative light-sensitive resin combination, cured film, partition wall and optical element - Google Patents

Refuse ink compositions, negative light-sensitive resin combination, cured film, partition wall and optical element Download PDF

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Publication number
CN104684994B
CN104684994B CN201380049711.1A CN201380049711A CN104684994B CN 104684994 B CN104684994 B CN 104684994B CN 201380049711 A CN201380049711 A CN 201380049711A CN 104684994 B CN104684994 B CN 104684994B
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compound
group
sensitive resin
resin combination
negative light
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CN104684994A (en
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高桥秀幸
松浦启吾
川岛正行
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/236—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers using printing techniques, e.g. applying the etch liquid using an ink jet printer

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  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
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  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

The present invention provides and refuses ink and resistance to UV/O thereof3Property good refuse ink compositions, provide upper surface to have good to refuse ink and even across UV/O3Treatment with irradiation its refuse cured film that ink also is able to well keep and partition wall and provide can even spread is black in point optical element.One refuses ink compositions, it comprises the first compound and the second compound, described first compound is the partial hydrolysis condensate of the mixture of the first hydrolysable silanes compound comprising and having fluorine alkylidene and/or fluoroalkyl and hydrolization group, the main chain of described second compound be hydrocarbon chain and comprise there is the side chain of fluorine atom, matter average molecular weight (Mw) is 100～1,000,000.

Description

Refuse ink compositions, negative light-sensitive resin combination, cured film, partition wall and Optical element
Technical field
The present invention relates to refuse ink compositions, negative light-sensitive resin combination and employ this negative-type photosensitive tree The cured film of oil/fat composition, partition wall and optical element.
Background technology
For organic EL (Electro-Luminescence, organic electroluminescent) element, utilize ink-jet (IJ) The method of the organic layers such as method pattern printing luminescent layer.In the process, the profile along point arranges partition wall, to its internal note Enter the ink of the material comprising layer to be formed, it is dried and/or heating etc., thus forms desired pattern film.
In said method, in order to prevent the colour mixture of the ink between consecutive points and be coated with ink equably in point, needs It is that partition wall upper surface has refuses ink, and partition wall side has ink affinity.
Above-mentioned partition wall such as carries out pattern formation by the photoetching process employing photosensitive polymer combination.
Such as, photosensitive polymer combination comprises surface free energy little refuse ink agent time, utilize when making dried coating film Ink agent is refused because of the repulsion that works between itself and other solid constituent to air side (the upper table of film during solvent evaporation Side, face) mobile, it is possible to and ink is refused in the upper surface imparting to gained partition wall.In described method, it is important that refuse the upper table of ink agent Face mobility.In addition, it is important that, do not remain in point after development and refuse ink agent.
For organic EL element, due to the residue of the photosensitive polymer combination in remaining in a little after development, luminous The organic layers such as layer become easily to deteriorate.Thus, for the development residue in removing a little, generally surface to base material before injecting ink Entirety carries out UV (ultraviolet)/O3(ozone) treatment with irradiation.Therefore, for organic EL element, even if UV/O3After treatment with irradiation, the Mo Xingye that refuses of partition wall upper surface is well kept.
In the past, as refusing ink agent, it is known to comprise the propylene of the main chain based on carbon-carbon bond and the side chain with fluorine atom Acids polymers (for example, see [embodiment] item of patent documentation 1～4).
But, comprise the resistance to UV/O refusing ink refusing ink agent of acrylic polymer3Property is low, as organic EL element Partition wall purposes is insufficient.
Patent Document 5 discloses a kind of negative light-sensitive resin combination, its surface free energy is sufficiently small, is formed Partition wall has good ink of refusing at upper surface, and, even across UV/O3Treatment with irradiation its refuse Mo Xingye and well protected Holding, this negative light-sensitive resin combination comprises silicon-type and refuses ink agent, and described silicon-type is refused ink agent and comprised fluorine-containing water-disintegrable The hydrolytic condensate of silane compound.
Prior art literature
Patent documentation
Patent documentation 1: International Publication the 2004/042474th
Patent documentation 2: International Publication the 2007/069703rd
Patent documentation 3: International Publication the 2011/081151st
Patent documentation 4: International Publication the 2010/001976th
Patent documentation 5: International Publication the 2010/013816th
Summary of the invention
The problem that invention is to be solved
For organic EL element, the live width of the partition wall portions being preferably originally not involved in display is the thinnest.In order to Even if the live width of constriction partition wall also can prevent well between consecutive points ink colour mixture, preferably partition wall upper surface refuse ink Higher.
It is an object of the invention to, it is provided that can manufacture and refuse ink and resistance to UV/O thereof3The partition wall that property is good refuse ink Compositions and be difficult to remain the negative-type photosensitive of the characteristic refusing ink compositions in refusing ink compositions containing this and possess a little Resin combination, use this negative light-sensitive resin combination and the cured film that obtains and partition wall.
And then, it is an object of the invention to, it is provided that there is the optical element of partition wall, described partition wall has at upper surface Good refuse ink, point in be difficult to can even spread ink in residual refuses ink agent, point.
For solving the scheme of problem
The present invention provide have following [1]～[17] technical scheme refuse ink compositions, negative photosensitive resin group Compound, cured film, partition wall and optical element.
[1] one refuses ink compositions, it is characterised in that it comprises the first compound and the second compound, and described first Compound is the mixing of the first hydrolysable silanes compound comprising and having fluorine alkylidene and/or fluoroalkyl and hydrolization group The partial hydrolysis condensate of thing,
The main chain of described second compound be hydrocarbon chain and comprise there is the side chain of fluorine atom, matter average molecular weight (Mw) is 100 ～1,000,000.
[2] according to refusing ink compositions described in above-mentioned [1], wherein, aforementioned first hydrolysable silanes compound is following formula (cx-1) compound shown in.
(A-RF11)a-Si(RH11)bX11 (4-a-b)···(cx-1)
(RF11For comprising at least 1 fluorine alkylidene, the divalent organic group of carbon number 1～16 or comprise ethereal oxygen The divalent organic group of the carbon number 2～16 of atom.RH11Alkyl for carbon number 1～6.
X11For hydrolization group.X11When existing multiple, they each other can difference can also be identical.
A is 1 or 2, b is 0 or 1, a+b is 1 or 2.
A is the group shown in fluorine atom or lower formula (I).
-Si(RH12)cX12 (3-c)···(I)
(RH12Alkyl for carbon number 1～6.
C is 0 or 1.
X12For hydrolization group.X12When existing multiple, they each other can difference can also be identical.)
A-RF11When existing multiple, they each other can difference can also be identical.)
[3] according to refusing ink compositions described in above-mentioned [2], wherein, aforementioned mixture also comprises shown in following formula (cx-2) The second hydrolysable silanes compound.
SiX2 4···(cx-2)
(X2Represent hydrolization group, 4 X2Each other can difference can also be identical.)
[4] according to refusing ink compositions, wherein, under aforementioned mixture also comprises according to any one of above-mentioned [1]～[3] The 3rd hydrolysable silanes compound shown in formula (cx-3).
(Y-Q3)g-Si(RH3)hX3 (4-g-h)···(cx-3)
(Y is the group with olefinic double bond.
Q3The divalent organic group without fluorine atom for carbon number 1～6.
RH3Alkyl for carbon number 1～6.
X3For hydrolization group.X3When existing multiple, they each other can difference can also be identical.
G is 1 or 2, h is 0 or 1, g+h is 1 or 2.
Y-Q3When existing multiple, they each other can difference can also be identical.)
[5] according to refusing ink compositions according to any one of above-mentioned [1]～[4], wherein, aforementioned second compound is poly- Compound, described polymer comprises the fluoroalkyl optionally containing etheric oxygen atom and/or has the fluorine optionally containing etheric oxygen atom The side chain of alkyl.
[6] according to refusing ink compositions described in above-mentioned [5], wherein, aforementioned second compound has acidic groups for comprising The polymer of the side chain of group.
[7] according to refusing ink compositions described in above-mentioned [5] or [6], wherein, aforementioned second compound has alkene for comprising Belong to the polymer of the side chain of double bond.
[8] according to refusing ink compositions according to any one of above-mentioned [5]～[7], wherein, aforementioned second compound is bag Polymer containing the side chain with oxyalkylene.
[9] according to refusing ink compositions according to any one of above-mentioned [1]～[8], wherein, aforementioned second compound is relative Mass ratio in aforementioned first compound is 0.01～10.
[10] according to refusing ink compositions according to any one of above-mentioned [1]～[9], wherein, the containing ratio of fluorine atom is 5 ～40 mass %.
[11] a kind of negative light-sensitive resin combination, it comprises refuses ink according to any one of above-mentioned [1]～[10] Compositions and there is alkali soluble resin or base soluble monomer (A), Photoepolymerizationinitiater initiater (B) and the solvent of photo-curable (D)。
[12] according to the negative light-sensitive resin combination described in above-mentioned [11], its be also included in 1 molecule have 2 with Upper olefinic double bond and not there is the cross-linking agent (E) of acidic-group.
[13] according to the negative light-sensitive resin combination described in above-mentioned [11] or [12], wherein, in all solids composition The first compound be 0.05～10 mass % containing ratio, the second compound is 0.01～5 mass % containing ratio.
[14] according to the negative light-sensitive resin combination according to any one of above-mentioned [11]～[13], wherein, all solid What aforementioned in body composition refused ink compositions is 0.06～15 mass % containing ratio.
[15] a kind of cured film, it is characterised in that it is by the negative photosensitive according to any one of above-mentioned [11]～[14] Property resin combination coat substrate surface, remove solvent (D) and expose.
[16] a kind of partition wall, it is characterised in that it comprises the cured film described in above-mentioned [15].
[17] a kind of optical element, it is characterised in that it possesses the partition wall described in multiple point and above-mentioned [16].
The effect of invention
The present invention refuse ink compositions can prepare can form upper surface refuse ink and resistance to UV/O thereof3Property good point The negative light-sensitive resin combination in next door, has the optics of partition wall using this negative light-sensitive resin combination and obtain Element possess the upper surface at partition wall have good refuse ink and point in be difficult to remain the characteristic refusing ink composition, therefore, it is possible to In point, even spread is black, easily form pattern film.
Accompanying drawing explanation
Figure 1A is the process chart of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Figure 1B is the process chart of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 1 C is the process chart of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 1 D is the process chart of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 1 E is the process chart of the manufacture method schematically showing the partition wall formed by cured film of the present invention.
Fig. 2 A is the manufacture method schematically showing the pattern film employing the partition wall formed by cured film of the present invention Process chart.
Fig. 2 B is the manufacture method schematically showing the pattern film employing the partition wall formed by cured film of the present invention Process chart.
Detailed description of the invention
In this specification, " (methyl) acryloyl group " is " methylacryloyl " and the general designation of " acryloyl group ".(methyl) Acrylate, (methyl) acrylamide and (methyl) acrylic resin are also according to this regulation.
In this specification, sometimes the group shown in formula (x) is abbreviated as group (x).
In this specification, sometimes the compound shown in formula (y) is abbreviated as compound (y).
Herein, formula (x), formula (y) represent any formula.
" side chain " in this specification refers to: in repetitive constitutes the polymer of main chain, former with the carbon constituting main chain Group outside the dehydrogenation atom of sub-key conjunction or halogen atom.
" all solids composition of photosensitive polymer combination " in this specification refers to contained by photosensitive polymer combination For forming the composition of aftermentioned cured film among some compositions, by by photosensitive polymer combination with 140 DEG C heating 24 hours and The residue eliminating solvent is obtained.It should be noted that all solids component amount can also be calculated by inventory.
In this specification, the film of photosensitive resin coating compositions is referred to as " film ", dried coating film will be made to obtain To film be referred to as " desciccator diaphragm " and then desciccator diaphragm solidification will be made and the film that obtains is referred to as " cured film ".
Cured film can be pattern film, it is also possible to be the film being unpatterned.
In this specification, " upper surface " of partition wall does not include the side of partition wall.
" black " in this specification includes that the liquid possessing optical function and/or electric function is all.
" black " in this specification includes that the ink used in pattern based on ink-jet (IJ) method printing is all.
For organic EL element, the color filter of liquid crystal cell and organic tft, (Thin Film Transistor, thin film is brilliant Body pipe) for the optical element such as array, it is possible to use IJ method is carried out pattern and is printed various elements." black " bag in this specification Include the ink used in such use.
" refusing ink " in this specification refers to repel the character of above-mentioned ink, including both water repellency and oil repellent.Refuse Ink such as can be evaluated by contact angle during dropping ink.
" resistance to UV/O in this specification3Property " even if referring to carry out UV/O3Keep the most well after treatment with irradiation refusing ink Characteristic.
" point " in this specification represents the Minimum Area of the carried out light modulation in optical element.For organic EL unit For the optical elements such as part, the color filter of liquid crystal cell and organic tft array, 1 point=1 pixel when showing black and white, in display Such as 3 points (R (red), G (green), B (blue) etc.)=1 pixel time colored.
Following description embodiments of the present invention.It should be noted that in this specification, in situation about being not particularly illustrated Under, % represents quality %.
[refusing ink compositions]
The ink compositions of refusing of the present invention (the most otherwise referred to as refuses ink compositions (C).In), as refusing ink chemical combination Thing comprises the first following compound and the second compound.It should be noted that unreacted first compound and the second chemical combination The raw material of thing regards as being included in this and refuses in ink compositions (C).
The ink compositions (C) of refusing of the present invention is the most only made up of the first compound and the second compound.
The present invention refuses ink compositions and can be applied to negative light-sensitive resin combination or normal Photosensitive resin group Contained in compound etc. refuse ink agent.It is particularly preferably applied for negative light-sensitive resin combination.Said composition is suitable as optics The pattern based on IJ method of the various elements of element formed in partition wall formation compositions.
In the forming process of partition wall, refuse ink compositions and move to upper surface and form thin refusing at partition wall upper surface Layer of ink, gives partition wall upper surface and refuses ink.It should be noted that the ink compositions of refusing of the present invention also is able to for other Purposes.
Specify that according to the research of the present inventor: the first compound and the second compound are all individually at partition wall upper surface Ink is refused in performance, but under conditions of fluorine atom containing ratio is identical, when being applied in combination the first compound and the second compound, with point Compare when not being used alone more can improve partition wall upper surface refuse ink.Its reason considers as follows.
Even if being used alone the first compound, cross-linking reaction to a certain degree also can be occurred to be formed at partition wall upper surface Thin refuses layer of ink.But, the molecular weight of the first compound for example, 1000～about 2000, the extension of each molecule is little, therefore Intermolecular easy generation gap.It is believed that fill this gap by the second compound, thus refuse ink and can improve.
Research according to the present inventor, it is believed that some is also applied in combination the first compound and the second compound below Effect.
(1) compared with being used alone the second compound, during alkali development, the removal refusing layer of ink of partition wall upper surface is pressed down Make, refuse ink raising.
(2) compared with being used alone the first compound, the storage-stable of negative light-sensitive resin combination improves.
(3) compared with being used alone the first compound, it is not susceptible to the protuberance of the end of partition wall upper surface.
The reason that can show effect (1) considers as follows.
When being used alone the second compound, if the matter average molecular weight (Mw) of the second compound is more than 100,000, then can be to dividing Next door upper surface gives height and refuses ink, but there is the tendency that the dissolubility in alkaline developer reduces.I.e. it is believed that: alkali development time A part for partition wall upper surface is refused layer of ink and is removed, refuses ink reduction.It is believed that: this tendency will not be produced by being applied in combination The first compound, alkali development time partition wall upper surface the removal refusing layer of ink be suppressed, refuse ink improve.
The reason that can show effect (2) considers as follows.
When being used alone the first compound, due to silanol group reactive height each other, thus exist and comprise the first chemical combination The tendency that the storage-stable of the photosensitive polymer combination of thing is insufficient.It is believed that: reactive low by the by being applied in combination Two compounds, silanol group reaction each other is suppressed, the storage-stable of photosensitive polymer combination improves.
The reason that can show effect (3) considers as follows.
When being used alone the first compound, sometimes the end at partition wall upper surface formed available scanning electron show The tump of the level that micro mirror (SEM) etc. is observed.This protuberance will not cause obstruction especially as partition wall etc., but false If this protuberance comes off because of certain reason, the sidewall of partition wall etc. can be given and refuse ink, thus the most preferred.
It is believed that: the first compound is due to silanol group each other reactive high, even if therefore also can send out in non-exposed portion Give birth to cross-linking reaction to a certain degree and form above-mentioned protuberance.It is believed that: by being applied in combination reactive the second low compound, non- The reaction each other of the silanol group of exposure portion is hindered, suppress the generation of above-mentioned protuberance.
It should be noted that the present inventor confirms: in this protuberance compared with other parts, the content of F and/or Si is relatively Many.
(the first compound)
First compound is mixture (the hereinafter also referred to hydrolysable silanes chemical combination comprising the first hydrolysable silanes compound Thing mixture.) partial hydrolysis condensate.This hydrolysable silanes compound mixture comprises the first hydrolysable silanes compound As essential component, optionally comprise the second hydrolysable silanes compound described later～the 5th hydrolysable silanes compound.All right Comprise the hydrolysable silanes compound in addition to the second hydrolysable silanes compound～the 5th hydrolysable silanes compound.
First compound is the compositions with molecular weight distribution.
<the first hydrolysable silanes compound>
The first hydrolysable silanes compound in the present invention is to have fluorine alkylidene and/or fluoroalkyl and hydrolization group Compound.
As hydrolization group, can list in alkoxyl, halogen atom, acyl group, NCO, amino, amino The group etc. that at least one hydrogen is replaced by alkyl.From being formed hydroxyl (silanol group) by hydrolysis and then dividing There is condensation reaction between son and formed from the viewpoint of the reaction of Si-O-Si key is easily smoothed out, preferably carbon number 1～ The alkoxy or halogen atom of 4, more preferably methoxyl group, ethyoxyl or chlorine atom, particularly preferably methoxy or ethoxy.
First hydrolysable silanes compound can be used singly or in combination of two or more.
Comprised the first hydrolysable silanes compound of fluorine alkylidene and/or fluoroalkyl by use, the first compound has Fluorine alkylidene and/or fluoroalkyl.When using the negative light-sensitive resin combination comprising the first compound, it is possible to partition wall What upper surface imparting was good refuses ink.And then, even across UV/O3Treatment with irradiation also can keep good and refuse ink.
It should be noted that for the effect above showing the first hydrolysable silanes compound further, the first hydrolysis Property silane compound more preferably has fluoroalkyl, perfluorinated alkylidene or perfluoroalkyl, particularly preferably has perfluoroalkyl.It addition, Also preferably comprise the perfluoroalkyl of etheric oxygen atom.That is, the most preferred compound as the first hydrolysable silanes compound It it is the compound with perfluoroalkyl and/or the perfluoroalkyl that comprises etheric oxygen atom.
As the first hydrolysable silanes compound, the preferably compound shown in following formula (cx-1).
(A-RF11)a-Si(RH11)bX11 (4-a-b)···(cx-1)
In formula (cx-1), RF11For comprise at least 1 fluorine alkylidene, the divalent organic group of carbon number 1～16 or Comprise the divalent organic group of the carbon number 2～16 of etheric oxygen atom.
RH11Alkyl for carbon number 1～6.
X11For hydrolization group.X11When existing multiple, they each other can difference can also be identical.
A is 1 or 2, b is 0 or 1, a+b is 1 or 2.
A is the group shown in fluorine atom or lower formula (I).
-Si(RH12)cX12 (3-c)···(I)
In formula (I), RH12Alkyl for carbon number 1～6.
C is 0 or 1.
X12For hydrolization group.X12When existing multiple, they each other can difference can also be identical.
It addition, A-RF11When existing multiple, they each other can difference can also be identical.
Compound (cx-1) is have 1 or 22 functionalities or 3 functionality hydrolyzable silyl group fluorine-containing water-disintegrable Silane compound.
RH11And RH12It is preferably the alkyl of carbon number 1～3, particularly preferably methyl.
In formula (cx-1), it is therefore particularly preferred that a is 1, b is 0 or 1.
X as hydrolization group11And X12Concrete example and optimal way described above.
As the first hydrolysable silanes compound, the particularly preferably compound shown in following formula (cx-1a).
D-RF12-Q11-SiX11 3···(cx-1a)
In formula (cx-1a), RF12The perfluorinated alkylidene optionally comprising etheric oxygen atom for carbon number 2～15.
Q11The divalent organic group without fluorine atom for carbon number 1～10.
X11For hydrolization group.3 X11Each other can difference can also be identical.
D is the group shown in fluorine atom or following formula (Ia).
-Q12-SiX12 3···(Ia)
In formula (Ia), X12For hydrolization group.3 X12Each other can difference can also be identical.
Q12The divalent organic group without fluorine atom for carbon number 1～10.
In formula (cx-1a), when D is fluorine atom, RF12It is preferably perfluorinated alkylidene or the carbon number of carbon number 4～8 The perfluorinated alkylidene comprising etheric oxygen atom of 4～10, the more preferably perfluorinated alkylidene of carbon number 4～8, particularly preferably The perfluorinated alkylidene of carbon number 6.
It addition, in formula (cx-1a), when D is group (Ia), RF12Be preferably carbon number 3～15 perfluorinated alkylidene or The perfluorinated alkylidene comprising etheric oxygen atom of carbon number 3～15, the particularly preferably perfluorinated alkylidene of carbon number 4～6.
RF12During for above-mentioned group, refuse ink compositions by the present invention, it is possible to obtain can form upper surface refuse ink And resistance to UV/O3The negative light-sensitive resin combination of the partition wall that property is good, and the dissolving that compound (cx-1a) is in solvent Property excellent.
As RF12Structure, linear chain structure can be listed, branched structure, ring structure, part have the structure etc. of ring, excellent Elect linear chain structure as.
As RF12Concrete example, following group can be listed.
-(CF2)4-、-(CF2)6-、-(CF2)8-、-CF2CF2OCF2CF2OCF2-、-CF2CF2OCF2CF2OCF2CF2-、- CF2CF2OCF2CF2OCF2CF2OCF2CF2OCF2-、-CF2CF2OCF2CF2OCF2CF2OCF2CF2OCF2CF2-。- CF2CF2CF2OCF2-、-CF2CF2CF2OCF2CF2-、-CF2CF2CF2OCF(CF3)-、-CF2CF2CF2OCF(CF3)CF2-、- CF2CF2CF2OCF(CF3)CF2OCF2CF2-、-CF2CF2CF2OCF(CF3)CF2OCF(CF3)-、-CF2CF2CF2OCF(CF3) CF2OCF(CF3)CF2-、-CF2OCF(CF3)CF2OCF(CF3)-、-CF2CF2OCF(CF3)CF2OCF(CF3)-。
Q11And Q12In, to be bonded Si respectively on the atomic bond on right side and to be bonded R on the atomic bond in left sideF12Form During expression, specifically, it is preferred that-(CH2)i1-(i1 is the integer of 1～5.)、-CH2O(CH2)i2-(i2 be 1～4 whole Number.)、-SO2NR1-(CH2)i3-(R1For hydrogen atom, methyl or ethyl, i3 is the integer of 1～4, R1With (CH2)i3Carbon atom Count adds up to the integer of less than 4.) or-(C=O)-NR1-(CH2)i4-(R1Same as described above, i4 is the integer of 1～4, R1 With (CH2)i4Carbon number add up to less than 4 integer.Group shown in).As Q11And Q12, more preferably i1 be 2～ The integer of 4-(CH2)i1-, particularly preferably-(CH2)2-。
It should be noted that RF12During for perfluorinated alkylidene, as Q11And Q12, it is preferably-(CH2)i1-shown group. I1 be more preferably 2～4 integer, i1 be particularly preferably 2.
RF12During for comprising the perfluorinated alkylidene of etheric oxygen atom, as Q11And Q12, it is preferably-(CH2)i1-、-CH2O (CH2)i2-、-SO2NR1-(CH2)i3-or-(C=O)-NR1-(CH2)i4-shown group.Wherein, more preferably- (CH2)i1-, i1 more preferably 2～4 integer, i1 is particularly preferably 2.
When D is fluorine atom, as the concrete example of compound (cx-1a), following compound can be listed.F(CF2)4CH2CH2Si(OCH3)3、F(CF2)6CH2CH2Si(OCH3)3、F(CF2)6CH2CH2CH2Si(OCH3)3、F(CF2)8CH2CH2Si (OCH3)3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3、F(CF2)2O(CF2)2O(CF2)2CH2CH2Si (OCH3)3。
When D is group (Ia), as the concrete example of compound (cx-1a), following compound can be listed.(CH3O)3SiCH2CH2(CF2)4CH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2(CF2)6CH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2 (CF2)6CH2CH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2(CF2)2OCF2CF(CF3)O(CF2)2OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3。
Wherein, particularly preferably F (CF2)6CH2CH2Si(OCH3)3Or F (CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si (OCH3)3。
In the present invention, as compound (cx-1a), wherein, particularly preferably F (CF2)6CH2CH2Si(OCH3)3, or F (CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3。
Being preferably containing ratio of the first hydrolysable silanes compound in hydrolysable silanes compound mixture is mixed by this Fluorine atom containing ratio in the partial hydrolysis condensate that compound obtains reaches 5～55 mass %, more preferably up to 10～40 matter Amount %, particularly preferably reach the ratio of 15～30 mass %.First hydrolysable silanes compound is above-mentioned scope containing ratio Lower limit more than time, it is possible to the upper surface of cured film is given and good refuses ink, for time below higher limit, with this mixture In the compatibility of other hydrolysable silanes compound become good.
<the second hydrolysable silanes compound>
The second hydrolysable silanes compound in the present invention is the compound shown in following formula (cx-2).
SiX2 4···(cx-2)
In formula (cx-2), X2Represent hydrolization group, 4 X2Each other can difference can also be identical.As X2, can make With with aforementioned X11And X12Identical group.
Compound (cx-2) can be used singly or in combination of two or more.
As the concrete example of compound (cx-2), following compound can be listed.It addition, as compound (cx-2), root According to needs, it is possible to use the partial hydrolysis condensate that multiple this compound partial hydrolysiss in advance condensation is obtained.
As concrete example, for Si (OCH3)4、Si(OCH2CH3)4、Si(OCH3)4Partial hydrolysis condensate (such as COLCOAT CO., Ltd manufacture Methyl Silicate 51 (trade name)), Si (OCH2CH3)4Partial hydrolysis condensate (Ethyl Silicate 40, Ethyl Silicate 48 (being trade name) that such as, COLCOAT CO., Ltd manufacture) Deng.
By making inclusion compound (cx-2) in hydrolysable silanes compound mixture, for the first compound will be comprised For the cured film of negative light-sensitive resin combination solidification, it is possible to increase refuse ink compositions (C) and move to upper surface After film property.I.e. it is believed that: the quantity of the hydrolization group in compound (cx-2) is many, therefore moves to upper surface rear section Hydrolytic condensate is condensed the most well, thin film (film property excellent) can be integrally formed at upper surface.
It addition, by making inclusion compound (cx-2) in hydrolysable silanes compound mixture, the first compound is soluble in Hydrocarbon system solvent.
The second hydrolysable silanes compound in hydrolysable silanes compound mixture containing ratio relative to the first water 1 mole of solution property silane compound is preferably 0.01～5 mole, particularly preferably 0.05～3 mole.It is above-mentioned model containing ratio Time more than the lower limit enclosed, the film property refusing ink compositions (C) is good, for time below higher limit, it is possible to upper to cured film What surface imparting was good refuses ink.
<the 3rd hydrolysable silanes compound>
The 3rd hydrolysable silanes compound in the present invention is the hydrolysable silanes compound shown in following formula (cx-3).
(Y-Q3)g-Si(RH3)hX3 (4-g-h)···(cx-3)
In formula (cx-3), Y is the group with olefinic double bond.
Q3The divalent organic group without fluorine atom for carbon number 1～6.
RH3Alkyl for carbon number 1～6.
X3For hydrolization group.X3When existing multiple, they each other can difference can also be identical.
G is 1 or 2, h is 0 or 1, g+h is 1 or 2.
Y-Q3When existing multiple, they each other can difference can also be identical.
As RH3, it is possible to use with aforementioned RH11And RH12Identical group.
As X3, it is possible to use with aforementioned X11And X12Identical group.
As Y, it is preferably (methyl) acryloxy or ethenylphenyl, particularly preferably (methyl) acryloxy.
As Q3Concrete example, the alkylidene of carbon number 2～6, phenylene etc. can be listed.Wherein, be preferably- (CH2)3-。
Preferably, g be 1, h be 0 or 1.
Compound (cx-3) can be used singly or in combination of two or more.
As the concrete example of compound (cx-3), following compound can be listed.
CH2=C (CH3)COO(CH2)3Si(OCH3)3、
CH2=C (CH3)COO(CH2)3Si(OC2H5)3、
CH2=CHCOO (CH2)3Si(OCH3)3、
CH2=CHCOO (CH2)3Si(OC2H5)3、
[CH2=C (CH3)COO(CH2)3]SiCH3(OCH3)2、
[CH2=C (CH3)COO(CH2)3]SiCH3(OC2H5)2。
By making hydrolysable silanes compound mixture comprises the compound (cx-of the group Y containing band olefinic double bond 3), in the manufacture of the partition wall that negative light-sensitive resin combination is solidified, it is possible to increase refuse ink compositions (C) and exist The fixation performance of partition wall upper surface.
Compound (cx-3) has the group Y of band olefinic double bond, therefore when the exposure of negative light-sensitive resin combination, Refuse ink compound and each other or refuse that ink compound and negative light-sensitive resin combination have other of olefinic double bond Composition can carry out copolymerization via this group.It is believed that: by these action effects, refuse ink compositions (C) chemistry after exposure It is bonded to cured film upper surface, thus fixation performance improves.
The 3rd hydrolysable silanes compound in hydrolysable silanes compound mixture containing ratio relative to the first water 1 mole of solution property silane compound is preferably 0.1～5 mole, particularly preferably 0.5～4 mole.It is above-mentioned scope containing ratio Lower limit more than time, refuse the upper surface mobility of ink compositions (C) and fixation performance be good, it addition, refuse ink compositions Storage-stable is good.For time below higher limit, refuse ink compositions (C) to refuse ink good.
<the 4th hydrolysable silanes compound>
The 4th hydrolysable silanes compound in the present invention is the compound shown in following formula (cx-4).
(RH4)j-SiX4 (4-j)···(cx-4)
In formula (cx-4), RH4Alkyl for carbon number 1～6.RH4When existing multiple, they can difference also may be used each other With identical.
X4For hydrolization group.X4When existing multiple, they each other can difference can also be identical.
J is 2 or 3.
As RH4, it is possible to use with aforementioned RH11And RH12Identical group.
As X4, it is possible to use with aforementioned X11And X12Identical group.
Compound (cx-4) can be used singly or in combination of two or more.
As the concrete example of compound (cx-4), following compound can be listed.
(CH3)3-Si-OCH3、(CH3CH2)3-Si-OCH2CH3、(CH3)3-Si-OCH2CH3、(CH3CH2)3-Si-OCH3、 (CH3)2-Si-(OCH3)2、(CH3)2-Si-(OCH2CH3)2、(CH3CH2)2-Si-(OCH2CH3)2、(CH3CH2)2-Si-(OCH3)2。
When hydrolysable silanes compound mixture uses compound (cx-2), for by negative light-sensitive resin combination For the partition wall of solidification, the end on surface forms protuberance the most thereon.It is available scanning electron microscope Etc. (SEM) tump of the level observed.The present inventor confirms: in this protuberance, compared with other parts, F and/or Si Content more.
Above-mentioned protuberance will not cause obstruction especially as partition wall etc., present inventor have discovered that by by compound (cx-2) a part is replaced into the few compound of hydrolysising group number (cx-4), it is possible to suppress the generation of above-mentioned protuberance.
By the reaction each other of the silanol group that generated by the compound (cx-2) that hydrolysising group number is many, refuse ink combination The film property of thing (C) increases.But it is believed that: produce above-mentioned protuberance because it is reactive high.
On the other hand, it is believed that: by a part for compound (cx-2) is replaced into the chemical combination that hydrolysising group number is few Thing (cx-4), silanol group reaction each other is suppressed, above-mentioned protuberance is suppressed.
The 4th hydrolysable silanes compound in hydrolysable silanes compound mixture containing ratio relative to the first water 1 mole of solution property silane compound is preferably 0.05～5 mole, particularly preferably 0.3～3 mole.It is above-mentioned model containing ratio Time more than the lower limit enclosed, it is possible to the protuberance of the end of suppression partition wall upper surface.For time below higher limit, refuse ink compositions (C) to refuse ink good.
<the 5th hydrolysable silanes compound>
The 5th hydrolysable silanes compound in the present invention does not have fluorine alkylidene for having sulfydryl and hydrolization group Compound with fluoroalkyl.
As hydrolization group, it is possible to use the group identical with the hydrolization group of the first hydrolysable silanes compound.
5th hydrolysable silanes compound can be used singly or in combination of two or more.
Comprised the 5th hydrolysable silanes compound of sulfydryl by use, negative light-sensitive resin combination can be with lower Light exposure be exposed.It is believed that be because: the sulfydryl in the 5th hydrolysable silanes compound has chain tra nsfer, easily The olefinic double bond etc. being had with aftermentioned alkali soluble resin or base soluble monomer (A) links, thus promotes photocuring.
It addition, the pKa comprising the 5th hydrolysable silanes compound of sulfydryl is about 10, the most de-matter in aqueous slkali Sub, the most easily dissociate.
Herein, by pKa=-log10Ka represents, in formula, Ka represents acid ionization constant.It is therefore contemplated that sulfydryl can improve The alkali-soluble during development of negative light-sensitive resin combination.
As the 5th hydrolysable silanes compound, the preferably compound shown in following formula (cx-5).
(HS-Q5)p-Si(RH5)qX5 (4-p-q)···(cx-5)
In formula (cx-5), Q5The divalent organic group without fluorine atom for carbon number 1～10.
RH5Alkyl for carbon number 1～6.
X5For hydrolization group.X5When existing multiple, they each other can difference can also be identical.
P is 1 or 2, q is 0 or 1, p+q is 1 or 2.
HS-Q5When existing multiple, they each other can difference can also be identical.
As X5, it is possible to use with aforementioned X1And X2Identical group.
As Q5, the preferably alkylidene of carbon number 1～10, the more preferably alkylidene of carbon number 1～5, especially It is preferably the alkylidene of carbon number 1～3.
As RH5, it is possible to use with aforementioned RH11And RH12Identical group.
As the concrete example of compound (cx-5), HS-(CH can be listed2)3-Si(OCH3)3、HS-(CH2)3-Si(CH3) (OCH3)2Deng.
The 5th hydrolysable silanes compound in hydrolysable silanes compound mixture containing ratio relative to the first water 1 mole of solution property silane compound is preferably 0.125～18 mole, particularly preferably 0.125～8 mole.It is upper containing ratio When stating more than the lower limit of scope, negative light-sensitive resin combination can be exposed with lower light exposure.For higher limit Time following, refuse ink compositions (C) to refuse ink good.
<other hydrolysable silanes compound>
Hydrolysable silanes compound mixture can comprise one kind or two or more except the first hydrolysable silanes compound ～any hydrolysable silanes compound that the 5th outside hydrolysable silanes compound.
As other hydrolysable silanes compound, can list and there is oxyalkylene and hydrolization group but not have fluorine sub- The hydrolysable silanes compound of alkyl and fluoroalkyl.Specifically, include, for example out CH3O(C2H4O)kSi(OCH3)3(containing poly- The trimethoxy silane of oxygen ethylidene) (herein, k e.g., about 10.) etc..
<combination of preferred hydrolysable silanes compound>
First compound is inclusion compound (cx-1a), any inclusion compound (cx-2)～(cx-5) and compound (cx-1a), during the partial hydrolysis condensate of the mixture that group D is fluorine atom in, its average composition formula is shown in lower formula (II).
[D-RF12-Q11-SiO3/2]n1·[SiO2]n2·[(Y-Q3)g-Si(RH3)hSiO(4-g-h)/2]n3[(RH4)j- SiO(4-j)/2]n4·[(HS-Q5)p-Si(RH5)qO(4-p-q)/2]n5···(II)
In formula (II), n1～n5 is the molar percentage of each construction unit of the integral molar quantity relative to construction unit.n1> 0, n2 >=0, n3 >=0, n4 >=0, n5 >=0, n1+n2+n3+n4+n5=1.Other each symbol is described above.It should be noted that D For fluorine atom.
Owing to reality is to remain the product (partial hydrolysis condensate) of hydrolization group or silanol group, therefore this product It is difficult to represent with chemical formula.Average composition formula shown in formula (II) assumes that the hydrolization group in the first compound or silane Alcohol radical is completely formed chemical formula during siloxane bond.It addition, in formula (II), can speculate be respectively derived from compound (cx-1a) and ～the unit of (cx-5) arranges randomly (cx-2).
In n1:n2:n3:n4:n5 in average composition formula shown in formula (II) and hydrolysable silanes compound mixture Compound (cx-1a) is consistent with the composition that feeds intake of (cx-2)～(cx-5).
The mol ratio of each composition is designed by the balance of the effect of each composition.
N1 is preferably 0.05～0.4.
N2 is preferably 0～0.8, particularly preferably 0.05～0.6.
N3 is preferably 0～0.8, particularly preferably 0.2～0.5.
N4 is preferably 0～0.5, particularly preferably 0.05～0.3.
N5 is preferably 0.05～0.9, particularly preferably 0.05～0.4.
It should be noted that the feelings that D is group (Ia) that the preferred molar ratio of above-mentioned each composition is in compound (cx-1a) Also it is same under condition.
The matter average molecular weight (Mw) of the first compound is preferably more than 500, more preferably more than 1000.Additionally, it is preferred that not Foot 1,000,000, more preferably less than 10000.Particularly preferably less than 6000.
When matter average molecular weight (Mw) is more than lower limit, it is difficult to move to upper surface as the first compound refusing ink agent. During not enough higher limit, first compound dissolubility in solvent becomes good.And then, during not enough higher limit, the first compound Dissolubility in solvent becomes good.
The available manufacturing condition of the matter average molecular weight (Mw) of the first compound regulates.
<manufacture of partial hydrolysis condensate>
First compound known method can be utilized to be hydrolyzed by making said hydrolyzed silane compound mixture and Condensation reaction manufactures.
Preferably by mineral acid or acetic acid, oxalic acid, horses such as normally used hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid in this reaction Carry out the organic acid such as sour and be used as catalyst.It is also preferable to by the organic bases such as inorganic base, Tetramethylammonium hydroxide such as sodium hydroxide, The metal complexs such as dibutyl tin laurate etc. are as catalyst.
Above-mentioned reaction can use known solvent.
(the second compound)
Second compound be main chain be hydrocarbon chain and comprise there is the side chain of fluorine atom, matter average molecular weight (Mw) is 100～100 The compound of ten thousand.Matter average molecular weight (Mw) is preferably more than 3000, more preferably more than 5000.Additionally, it is preferred that be less than 300,000, More preferably less than 200,000.
Second compound preferably comprises the fluoroalkyl optionally containing etheric oxygen atom and/or has optionally containing ethereal oxygen The polymer of the side chain of the fluoroalkyl of atom.
Second compound preferably has the polymer of the polymerized unit containing fluoroalkyl.There is the polymerized unit of fluoroalkyl Preferably by making the polymerizable monomer with fluoroalkyl occur polymerization to import in polymer.
It addition, the various method of modifying reacted by the polymer making suitable compound with there is reactive site, also Fluoroalkyl can be imported in polymer.
Fluoroalkyl can be straight-chain, it is also possible to be branched.
As the concrete example of fluoroalkyl, following structure can be listed.
-CF3、-CF2CF3、-CF2CHF2、-(CF2)2CF3、-(CF2)3CF3、-(CF2)4CF3、-(CF2)5CF3、-(CF2)6CF3、-(CF2)7CF3、-(CF2)8CF3、-(CF2)9CF3、-(CF2)11CF3、-(CF2)15CF3。
Fluoroalkyl optionally comprises etheric oxygen atom.
Comprise concrete example during etheric oxygen atom as fluoroalkyl, following structure can be listed.
-CF(CF3)O(CF2)5CF3、
-CF2O(CF2CF2O)r1CF3、
-CF(CF3)O(CF2CF(CF3)O)r2C6F13、
-CF(CF3)O(CF2CF(CF3)O)r3C3F7。
In above-mentioned formula, integer that integer that r1 is 1～8, r2 are 1～4, r3 are the integer of 1～5.
Fluoroalkyl from refuse ink become good from the viewpoint of be preferably perfluoroalkyl.
The carbon number of fluoroalkyl is preferably 4～15.Refuse ink excellent, during it addition, manufacture the second compound, there is halothane The compatibility of the monomer outside the monomer of base and this monomer aftermentioned becomes good.
As having the monomer of fluoroalkyl, CH can be listed2=CR4COOR5Rf、CH2=CR4COOR6NR4SO2Rf、CH2= CR4COOR6NR4CORf、CH2=CR4COOCH2CH(OH)R5Rf、CH2=CR4CR4=CFRfDeng.
In above-mentioned formula, it is respectively as follows: RfFor fluoroalkyl, R4For hydrogen atom or methyl, R5Divalent for singly-bound or carbon number 1～6 has Machine group, R6Divalent organic group for carbon number 1～6.
As R5And R6Concrete example ,-CH can be listed2-、-CH2CH2-、-CH(CH3)-、-CH2CH2CH2-、-C (CH3)2-、-CH(CH2CH3)-、-CH2CH2CH2CH2-、-CH(CH2CH2CH3)-、-CH2(CH2)3CH2-and-CH (CH2CH (CH3)2)-。
Above-mentioned polymerizable monomer may be used singly or in combination of two or more.
Second compound, from the viewpoint of the alkali-soluble of the second compound becomes well, preferably comprises and has acidity The polymer of the side chain of group.
It should be noted that the side chain with fluoroalkyl optionally comprises acidic-group.Alternatively, it is also possible to exist and there is fluorine The side chain of alkyl different, there is acidic-group but not there is the side chain of fluoroalkyl.
As acidic-group, at least one being preferably selected from the group being made up of carboxyl, phenolic hydroxyl group and sulfonic group is acid Group or its salt.
From have photocrosslinking reaction, solidify on upper strata partition wall forming process, refuse viewpoint lasting for Mo Xinghui come Seeing, the second compound preferably comprises the polymer of the side chain with olefinic double bond.
In 1 side chain, particularly preferably comprise the polymer of more than 2 olefinic double bonds.
It should be noted that the side chain with fluoroalkyl optionally comprises olefinic double bond.
Furthermore it is also possible to exist different from the side chain with fluoroalkyl, there is olefinic double bond and not there is fluoroalkyl Side chain.
Second compound can be the polymer comprising the side chain with oxyalkylene.Oxyalkylene can be sub-with multiple oxygen The form of the polyoxy alkylidene chain (POA chain) that alkyl links and comprised.As oxyalkylene, oxygen Asia second can be listed Base, oxygen propylidene, preferably oxygen ethylidene.
Oxyalkylene self does not have a photocrosslinking reaction, but has the second compound of oxyalkylene and have olefinic double bond Situation is identical, solidifies on upper strata, refuses Mo Xinghui persistently in partition wall forming process.Oxyalkylene has hydrophilic, because of This also has the effect improving the wettability for developer solution.
It should be noted that the side chain with fluoroalkyl optionally comprises oxyalkylene.Alternatively, it is also possible to exist and there is fluorine The side chain of alkyl different, there is oxyalkylene and not there is the side chain of fluoroalkyl.
Second compound can comprise and has the side chain of acidic-group, has the side chain of olefinic double bond and to have oxygen sub- More than a kind side chain among the side chain of alkyl.Acidic-group, olefinic double bond and oxygen alkylene can also be comprised in 1 side chain Two or more among base.
Second compound can comprise the side chain except having acidic-group, the side chain with olefinic double bond and have The side chain with any group outside the side chain of oxyalkylene.
As there is acidic-group and not there is the introduction method of side chain of fluoroalkyl, preferably make the list with fluoroalkyl Body with there is acidic-group and not there is the method that the monomer of fluoroalkyl is copolymerized.It addition, by making suitable compound and tool Respond the various method of modifying that the polymer at position reacts, it is also possible to imported in polymer by acidic-group.
As having the monomer of carboxyl, (methyl) acrylic acid, vinylacetic acid .beta.-methylacrylic acid, itaconic acid, Malaysia can be listed Acid, fumaric acid, cinnamic acid and their salt.They may be used singly or in combination of two or more.
As having the monomer of phenolic hydroxyl group, o-hydroxystyrene, a hydroxy styrenes, 4-Vinyl phenol can be listed Deng.It addition, more than can list on their phenyl ring 1 hydrogen atom is by alkyl, methoxyl group, second such as methyl, ethyl, normal-butyls Haloalkyl that the alkoxyl such as epoxide, n-butoxy, halogen atom, more than 1 hydrogen atom of alkyl are substituted with halogen atoms, nitre The compound that base, cyano group or amide groups replace.
As having sulfonic monomer, can list vinyl sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid, 2-hydroxyl-3-(methyl) allyloxy propane sulfonic acid, (methyl) acrylic acid-2-Sulfoethyl esters, (methyl) acrylic acid-2-sulfo group third Ester, 2-hydroxyl-3-(methyl) acryloxy propane sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic and they Salt.
The various method of modifying that react as the polymer by making suitable compound with there is reactive site and incite somebody to action Carboxyl imports to the method in polymer, include, for example out (1) and makes the monomer with hydroxyl be copolymerized in advance, then makes it The method reacted with anhydride；(2) make the anhydride with olefinic double bond be copolymerized in advance, then make it and there is hydroxyl The method that compound reacts.
As the concrete example of the monomer with hydroxyl, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) propylene can be listed Acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 5-hydroxyl Pentyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 4-hydroxycyclohexyl, neopentyl glycol single (methyl) acrylic acid Ester, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, glycerol list (methyl) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxyl Base butyl vinyl ether, cyclohexanediol mono vinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (methyl) acryloyl Amine, N, double (hydroxymethyl) (methyl) acrylamides of N-etc..They may be used singly or in combination of two or more.
The monomer with hydroxyl can be the monomer with the polyoxy alkylidene chain (POA chain) that end is hydroxyl.
Include, for example out CH2=CHOCH2C6H10CH2O(C2H4O)k1H、CH2=CHOC4H8O(C2H4O)k1H、CH2= CHCOOC2H4O(C2H4O)k1H、CH2=C (CH3)COOC2H4O(C2H4O)k1H、CH2=CHCOOC2H4O(C2H4O)k2(C3H6O)k3H、CH2=C (CH3)COOC2H4O(C2H4O)k2(C3H6O)k3H etc..They may be used alone, can also be used in combination 2 kinds with On.
In above-mentioned formula, integer that integer that k1 is 1～100, k2 are 0～100, k3 be 1～100 integer, k2+k3 be 1 ～100.
As anhydride, the anhydride of the compound in 1 molecule with more than 2 carboxyls can be listed.Pivalic acid can be listed Acid anhydride and trimellitic anhydride.It addition, maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methyl neighbour can be listed Phthalate anhydride, methyl-5-norborene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, cis-1,2,3, 6-tetrabydrophthalic anhydride, 2-butylene-1-base succinic anhydrides etc. have the anhydride of olefinic double bond.They can be used alone, Can also be applied in combination two or more.
As having the compound of hydroxyl, as long as have the compound of more than 1 hydroxyl, aforementioned institute can be listed Alcohols, the 2-methoxyl group second such as the concrete example of the monomer with hydroxyl that shows, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, ethylene glycol Cellosolve class, 2-(2-methoxy ethoxy) ethanol, 2-(the 2-ethoxy ethoxy such as alcohol, cellosolvo, butoxy ethanol Base) the carbitol class such as ethanol, 2-(2-Butoxyethoxy) ethanol.Wherein, preferably intramolecular has the chemical combination of 1 hydroxyl Thing.They may be used singly or in combination of two or more.
According to said method, it is possible to import comprise acidic-group side chain, comprise acidic-group and the side chain of olefinic double bond, Or comprise the side chain of acidic-group and oxyalkylene.
Can also use not hydroxyl and acidic-group but there is the monomer of polyoxy alkylidene chain (POA chain), such as following formula (POA-1), the monomer shown in (POA-2).
CH2=CR71-COO-W-(R72-O)k4-R73···(POA-1)、
CH2=CR71-O-W-(R72-O)k4-R73···(POA-2)
(R71For hydrogen atom, chlorine atom, bromine atoms, atomic iodine, cyano group, the alkyl of carbon number 1～20, carbon number 7～20 fragrant The substituted alkyl of base, the aryl of carbon number 6～20 or the cycloalkyl of carbon number 3～20.
R72Alkylidene for carbon number 1～5.
R73Alkyl for carbon number 1～4.
W is the divalent organic group without fluorine atom of singly-bound or carbon number 1～10.
K4 is the integer of 6～30.)
It addition, suitably select known monomer and reaction by composition desirably, it is possible to obtain and comprise there is acid The side chain of property group, there is the side chain of olefinic double bond and there is the one kind or two or more side chain among the side chain of oxyalkylene The second compound.
Refuse the mass ratio (matter of the second compound relative to the first compound of the second compound in ink compositions (C) The quality of amount the/the first compound) it is preferably 0.01～10, more preferably 0.02～5, particularly preferably 0.05～2.
It addition, the containing ratio of the fluorine atom refused in ink compositions (C) be preferably 5～40 mass %, more preferably 10～ 35 mass %, more preferably 13～32 mass %.During for this scope, that refuses ink compositions (C) refuses ink and with negative The characteristics such as the compatibility of other composition in type photosensitive polymer combination become good.
[negative light-sensitive resin combination]
The negative light-sensitive resin combination of the present invention contains alkali soluble resin or the alkali-soluble with photo-curable Monomer (A), Photoepolymerizationinitiater initiater (B), above-mentioned refuse ink compositions (C) and solvent (D).Can also contain crosslinking as required Agent (E), coloring agent (F) etc..
(alkali soluble resin or base soluble monomer (A))
Alkali soluble resin is given symbol (AP), gives symbol (AM) to base soluble monomer, illustrate respectively.
As alkali soluble resin (AP), preferably 1 molecule has the photoresist of acidic-group and olefinic double bond. By having olefinic double bond in the molecule of alkali soluble resin (AP), the exposure portion of negative light-sensitive resin combination is because producing There is polymerization from the free radical of Photoepolymerizationinitiater initiater (B) thus solidify.The exposure portion solidified in this wise will not be by alkali Developer solution is removed.
It addition, there is acidic-group in the molecule by alkali soluble resin (AP) such that it is able to select with alkaline developer Property ground remove the non-exposed portion of uncured negative light-sensitive resin combination.It is as a result, it is possible to form the solidification of desired pattern Film, i.e. partition wall.
As acidic-group, can list carboxyl, phenolic hydroxyl group, sulfo group, phosphate etc., they can be used alone a kind, Can also be applied in combination two or more.
As olefinic double bond, (methyl) acryloyl group, pi-allyl, vinyl, vinyl epoxide, vinyl oxygen can be listed Base alkyl etc. has the double bond of polyaddition.They can be used singly or in combination of two or more.
It should be noted that had one of hydrogen atom of olefinic double bond or all optionally replaced by alkyl such as methyl.
As alkali soluble resin (AP), can list containing there is the side chain of acidic-group and there is the side of olefinic double bond The resin (A-1) of chain, in epoxy resin, it is imported with the resin (A-2) etc. of acidic-group and olefinic double bond.They can be independent It is used singly, or in combination of two or more kinds.
Resin (A-1) such as can utilize the method for following (i) or (ii) to synthesize.
(i) make side chain have acidic-group outside reactive group, such as hydroxyl, the list of epoxy radicals isoreactivity group Body and side chain have the monomer of acidic-group and are copolymerized, thus obtain containing having the side chain of reactive group and having acidity The copolymer of the side chain of group.Then, make this copolymer and there is the functional group and alkene that can be bonded to above-mentioned reactive group The compound belonging to double bond reacts.Or, after making side chain have the monomer copolymerization of the acidic-groups such as carboxyl, making to have can key The amount that can remain with acidic-group after the reaction together in the functional group of acidic-group and the compound of olefinic double bond reacts.
(ii) make side chain have with above-mentioned (i) identical acidic-group outside the monomer of reactive group with have can The functional group being bonded to this reactive group reacts with the compound of the olefinic double bond being protected.Then, this monomer is made After there is the monomer copolymerization of acidic-group with side chain, the protection of removal olefinic double bond.Or, make side chain have the list of acidic-group After body and side chain have the monomer copolymerization of the olefinic double bond being protected, the protection of removal olefinic double bond.
It should be noted that (i) and (ii) implements the most in a solvent.
Among said method, the method that (i) is preferably used.Hereinafter, the method for (i) is specifically described.
About having the hydroxyl monomer as reactive group, (methyl) acrylic acid 2-hydroxy methacrylate, (first can be listed Base) acrylic acid 2-hydroxy propyl ester, neopentyl glycol single (methyl) acrylate, glycerol list (methyl) acrylate, 2-hydroxyethyl Vinyl ethers, 2-hydroxyethyl allyl ether, N-hydroxymethyl (methyl) acrylamide, double (hydroxymethyl) (methyl) third of N, N- Acrylamide etc..
Use when there is hydroxyl as the monomer of reactive group, the monomer with acidic-group of copolymerization except aftermentioned Have outside the monomer of carboxyl, as having the monomer of phosphate, also can list 2-(methyl) acryloyl-oxyethyl phosphoric acid Ester etc..Having hydroxyl can be according to existing known as the monomer of reactive group and the copolymerization of the monomer with acidic-group Method is carried out.
As the change that to react with gained copolymer, there is functional group and the olefinic double bond that can be bonded to hydroxyl Compound, can list have olefinic double bond anhydride, have NCO and the compound of olefinic double bond, have acid chloride group and The compound etc. of olefinic double bond.
As having the anhydride of olefinic double bond, maleic acid acid can be listed, ice drops in itaconic anhydride, citraconic anhydride, methyl-5- Sheet alkene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, cis-1,2,3,6-tetrabydrophthalic anhydride, 2-fourth Alkene-1-base succinic anhydrides etc..
As having the compound of NCO and olefinic double bond, 2-(methyl) acryloyl-oxyethyl can be listed different Double ((methyl) acryloyloxymethyl) ethyl isocyanates of cyanate, 1,1-etc..
As having the compound of acid chloride group and olefinic double bond, (methyl) acryloyl chloride etc. can be listed.
About having the epoxy radicals monomer as reactive group, can list (methyl) glycidyl acrylate, third Olefin(e) acid 3,4-epoxycyclohexanecarboxylate etc..
As will with there is the monomer with acidic-group of the epoxy radicals monomer copolymerization as reactive group, can make With with above-mentioned have hydroxyl as the monomer of reactive group in the identical monomer of monomer of explanation, make for having epoxy radicals Copolymerization for monomer and the monomer with acidic-group of reactive group, it is also possible to carry out according to existing known method.
As that to react with gained copolymer, have and can be bonded to the functional group of epoxy radicals and olefinic double bond Compound, can list the compound etc. with carboxyl and olefinic double bond.As the concrete example of described compound, third can be listed Olefin(e) acid, methacrylic acid, vinylacetic acid .beta.-methylacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt, two Its monoesters etc. can be listed in the case of unit's acid.It should be noted that make the dehydrating condensation portion of hydroxyl and the carboxylic acid generated herein The anhydride of a part for fractal structure circlewise reacts, it is also possible to import carboxyl in resin (A-1).
About having the carboxyl monomer as reactive group, acrylic acid, methacrylic acid, vinyl vinegar can be listed Acid .beta.-methylacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt, can list it single in the case of binary acid Ester etc..It should be noted that these monomers are also used as the above-mentioned monomer with acidic-group.
Use when there is carboxyl as the monomer of reactive group, as it has been described above, make this monomer be polymerized.As will be with That resulting polymers reacts, there is the compound of functional group and the olefinic double bond that can be bonded to carboxyl, can enumerate and provide There is the compound of epoxy radicals and olefinic double bond.As described compound, (methyl) glycidyl acrylate, propylene can be listed Acid 3,4-epoxycyclohexanecarboxylate etc..It should be noted that now, that will react with the polymer with carboxyl, have The amount of the functional group of carboxyl and the compound of olefinic double bond of can being bonded to be set to after reaction in the polymer carboxyl with acidic groups The form of group residues in the amount of side chain.
Resin (A-2) can react with the compound with carboxyl and olefinic double bond described later by making epoxy resin After, react synthesize with polybasic carboxylic acid or its acid anhydride.
Specifically, by making epoxy resin and there is carboxyl and the compound of olefinic double bond reacts, thus to ring Epoxy resins imports olefinic double bond.Then, the epoxy resin by making polybasic carboxylic acid or its acid anhydride and be imported with olefinic double bond occurs Reaction, it is possible to import carboxyl.
As epoxy resin, it is not particularly limited, bisphenol A type epoxy resin, bisphenol f type epoxy resin, benzene can be listed Phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, tris-phenol type epoxy resin, there is naphthalene skeleton The fluorenes shown in the epoxy resin of biphenyl backbone, following formula (A-2b) that has shown in epoxy resin, following formula (A-2a) replaces bisphenol A-type The epoxy resin etc. with biphenyl backbone shown in epoxy resin, following formula (A-2c).
(v is the integer of 1～50, the integer of preferably 2～10.It addition, the hydrogen atom of phenyl ring is the most optionally by carbon The phenyl that the alkyl of atomic number 1～12, halogen atom or a part of hydrogen atom are optionally substituted with a substituent is replaced.)
(R31、R32、R33And R34Be each independently hydrogen atom, chlorine atom or the alkyl of carbon number 1～5, w be 0 or 1～ The integer of 10.)
(hydrogen atom of phenyl ring is the most optionally by alkyl, halogen atom or the part of carbon number 1～12 The phenyl that hydrogen atom is optionally substituted with a substituent is replaced.Z is 0 or the integer of 1～10.)
It should be noted that make the epoxy resin shown in formula (A-2a)～(A-2c) and the change with carboxyl and olefinic double bond Compound react after again with polybasic carboxylic acid anhydride reactant time, as polybasic acid anhydride, dicarboxylic anhydride and tetrabasic carboxylic acid two are preferably used The mixture of acid anhydride.
As having the compound of carboxyl and olefinic double bond, can list acrylic acid, methacrylic acid, vinylacetic acid, .beta.-methylacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt.This compound is preferably single in the case of binary acid Ester, particularly preferably (methyl) acrylic acid.
As alkali soluble resin (AP), the stripping of the cured film when development is suppressed, is obtained in that high-resolution The viewpoint of pattern, the good viewpoint of rectilinearity of line chart case, be readily available smooth cured film surface from the viewpoint of, preferably Use resin (A-2).
As resin (A-2), in bisphenol A type epoxy resin, acidic-group and olefinic double bond are particularly preferably imported Resin, in bisphenol f type epoxy resin, acidic-group and the resin of olefinic double bond are imported, to phenol novolak-type epoxy tree Fat has imported acidic-group and the resin of olefinic double bond, imported in cresol novolak type epoxy resin acidic-group and The resin of olefinic double bond, imported in tris-phenol type epoxy resin acidic-group and the resin of olefinic double bond or to Epoxy resin shown in formula (A-2a)～(A-2c) has imported the resin of acidic-group and olefinic double bond.
As base soluble monomer (AM), such as, it is preferably used and comprises the side chain with acidic-group and there is olefinic double bond The monomer (A-3) of side chain.Acidic groups is identical with alkali soluble resin (AP) with olefinic double bond.
As monomer (A-3), 2,2,2-tri-acryloyloxymethyl ethyl phthalic acids etc. can be listed.
The alkali soluble resin (AP) or the base soluble monomer (AM) that comprise in negative light-sensitive resin combination can be single Solely it is used singly, or in combination of two or more kinds.
The alkali soluble resin in all solids composition in negative light-sensitive resin combination or base soluble monomer (A) Be preferably 5～80 mass %, particularly preferably 10～60 mass % containing ratio.When being above-mentioned scope containing ratio, minus Photo-curable and the developability of photosensitive polymer combination are good.
(Photoepolymerizationinitiater initiater (B))
Photoepolymerizationinitiater initiater (B) in the present invention is as long as have the compound of the function as Photoepolymerizationinitiater initiater, just It is not particularly limited, preferably utilizes light to produce the compound of free radical.
As Photoepolymerizationinitiater initiater (B), can list methyl phenyl glyoxylate ester, 9, the α-diones such as 10-phenanthrenequione；Benzene is even The acyloin classes such as relation by marriage；The acyloin ethers such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether；Thiaxanthone, CTX, 2- The thioxanthene ketones such as methyl thiaxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone；Benzophenone, 4,4 '-bis-(dimethylaminos) The benzophenones such as benzophenone, 4,4 '-bis-(lignocaine) benzophenone；1-Phenylethanone., 2-(4-tosyloxy)-2-benzene Benzoylformaldoxime, to dimethylamino 1-Phenylethanone., 2,2 '-dimethoxy-2-phenyl acetophenone, acetanisole, 2-methyl- [4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone Deng acetophenones；The quinones such as anthraquinone, 2-ethyl-anthraquinone, camphorquinone, 1,4-naphthoquinone；2-dimethyl ethyl aminobenzoate, 4-diformazan The aminobenzoic acids such as amino benzoic Acid (n-butoxy) ethyl ester；Phenacyl chloride (phenacyl chloride), three halos The halogen compounds such as methyl phenyl sulfone；Acylphosphine oxide class；The peroxide such as di-tert-butyl peroxide；{ 1-[4-(benzene sulfur Base)-2-(O-benzoyl oxime)] the oxime esters such as 1,2-acetyl caproyl, acetyl oxime；Triethanolamine, methyl diethanolamine, three isopropanols The aliphatic amines such as amine, n-butylamine, N methyldiethanol amine, diethylaminoethyl methacrylate；2-mercaptobenzimidazole, 2- Mercaptobenzooxazole, 2-mercaptobenzothiazole, 1,4-butanol double (3-mercaptobutylate), three (2-mercaptopropionyl epoxide ethyls) are different The mercaptan compounds etc. such as cyanurate, tetramethylolmethane four (3-mercaptobutylate).
Among Photoepolymerizationinitiater initiater (B), benzophenone, aminobenzoic acids, aliphatic amine, mercaptan compound etc. with When other radical initiator is used in conjunction with, show sensitization effect sometimes, be preferred.
As Photoepolymerizationinitiater initiater (B), preferably 2-methyl-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone, 2- Benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1, 2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone or 2,4- Diethyl thioxanthone.And then, particularly preferably they with benzophenone, such as 4,4 '-bis-(lignocaine) benzophenone Combination.
Photoepolymerizationinitiater initiater (B) can be used singly or in combination of two or more.
Photoepolymerizationinitiater initiater (B) in all solids composition in negative light-sensitive resin combination preferred containing ratio It is 0.1～50 mass %, more preferably 0.5～30 mass %, particularly preferably 5～15 mass %.It is above-mentioned model containing ratio When enclosing, photo-curable and the developability of negative light-sensitive resin combination are good.
(refusing ink compositions (C))
Being preferably containing ratio of the first compound in all solids composition in negative light-sensitive resin combination 0.05～10 mass %, more preferably 0.1～3 mass %, particularly preferably 0.2～1 mass %.
Being preferably containing ratio of the second compound in all solids composition in negative light-sensitive resin combination 0.01～5 mass %, more preferably 0.03～2 mass %, particularly preferably 0.05～0.5 mass %.
All solids composition in negative light-sensitive resin combination refuses the preferred containing ratio of ink compositions (C) It is 0.06～15 mass %, more preferably 0.13～5 mass %, particularly preferably 0.25～1.5 mass %.
In negative light-sensitive resin combination, the second compound is relative to mass ratio (second compound of the first compound The quality of quality/the first compound) be preferably 0.01～10, more preferably 0.02～5, particularly preferably 0.05～2.For front When stating the scope of mass ratio, the storage-stable of negative light-sensitive resin combination, refuse ink, its resistance to UV/O3Property, photo-curable Good with developability.
(solvent (D))
Negative light-sensitive resin combination in the present invention is by containing solvent (D), viscosity is minimized, negative photosensitive Property resin combination coating on substrate surface becomes easy.It is as a result, it is possible to form the negative-type photosensitive tree of homogeneous film thickness The film of oil/fat composition.
As solvent (D), it is possible to use known solvent.
Solvent (D) in negative light-sensitive resin combination be preferably 50～99 mass %, more preferably containing ratio 60～95 mass %, particularly preferably 65～90 mass %.
(cross-linking agent (E))
As the cross-linking agent (E) in the present invention, preferably 1 molecule has more than 2 olefinic double bonds but not there is acidity The compound of group.Cross-linking agent (E) is contained by negative light-sensitive resin combination, thus negative photosensitive resin when exposing The curable of compositions improves, also is able to form partition wall even with low light exposure.
As cross-linking agent (E), diethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) third can be listed Olefin(e) acid ester, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, double trimethylolpropane four (first Base) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, ethoxylation be different Double [4-(the 2-propylene of cyanuric acid triacrylate, 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester, 9,9- Oyloxyethoxy) phenyl] fluorenes, urethane acrylate etc..
From the viewpoint of photoreactivity, preferably there is multiple olefinic double bond.For example, it is preferable to be tetramethylolmethane four (methyl) Acrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol Five (methyl) acrylate, ethoxylation isocyanuric acid triacrylate, urethane acrylate etc..
Cross-linking agent (E) can be used singly or in combination of two or more.
Cross-linking agent (E) in all solids composition in negative light-sensitive resin combination containing ratio be preferably 10～ 60 mass %, particularly preferably 20～55 mass %.
(coloring agent (F))
As the coloring agent (F) in the present invention, white carbon black, nigrosine, anthraquinone system black pigment can be listed, be black face Material, specifically C.I. pigment black 1,6,7,12,20,31 etc..Red pigment, blue pigment and viridine green etc. can also be used Organic pigment and/or the mixture of inorganic pigment.
Coloring agent (F) in all solids composition in the negative light-sensitive resin combination of the present invention excellent containing ratio Elect 15～65 mass %, particularly preferably 20～50 mass % as.During for above-mentioned scope, gained negative light-sensitive resin combination Sensitivity good, it addition, the light-proofness of the partition wall formed is excellent.
(other composition)
The negative light-sensitive resin combination of the present invention can also contain as required thermal cross-linking agent, macromolecule dispersing agent, Dispersing aid, silane coupler, microgranule, phosphate cpd, curing accelerator, thickening agent, plasticizer, defoamer, levelling agent, anti- One kind or two or more in other additive such as contracting agent, UV absorbent.
[partition wall]
The partition wall of the present invention is the coating of above-mentioned negative light-sensitive resin combination on substrate surface and to be exposed The figuratum cured film of tool with development.
Hereinafter, use Figure 1A～Fig. 1 E illustrates an example of the manufacture method of partition wall, but the manufacture method of partition wall is not It is defined in following description.
As shown in Figure 1A, film 21 is formed to the surface entirety coating negative light-sensitive resin combination of base material 10.This Time, in film 21, have and refuse the first compound of ink and the second compound integrally dissolves and is uniformly dispersed.Need Bright, in figure, refuse ink compositions (C) and schematically show, the most do not exist with this grain shape.
Then, as shown in Figure 1B, film 21 is made to be dried and make desciccator diaphragm 22.As drying means, heating can be listed Be dried, drying under reduced pressure and heating under reduced pressure are dried.
Although also depending on the kind of solvent (D), but heating-up temperature being preferably 50～120 in the case of heat drying DEG C, more preferably 70～120 DEG C, more preferably 80～120 DEG C.
In this dry run, refuse the ink compositions (C) upper surface to desciccator diaphragm and move about.
Then, as shown in Figure 1 C, across the photomask 30 of the peristome 31 with predetermined pattern, desciccator diaphragm 22 is irradiated light L is exposed.Film after being exposed desciccator diaphragm 22 is referred to as exposed film 23.In exposed film 23,23A is exposure portion, 23B For non-exposed portion.In this operation, exposure portion 23A carries out photocuring.
As the light L irradiated, visible ray can be listed；Ultraviolet；Far ultraviolet rays；KrF excimer laser, ArF quasi-molecule Laser, F2Excimer laser, Kr2Excimer laser, KrAr excimer laser, Ar2The excimer laser such as excimer laser；X penetrates Line；Electron beam etc..
As irradiate light L, the preferably light of wavelength 100～600nm, more preferably 300～the light of 500nm, the most excellent Elect as and comprise i ray (365nm), h ray (405nm) or the light of g ray (436nm).
As Exposure mode, can list whole face expose in the lump, scan exposure etc..Same position can also be entered several times Row exposure.Now, the condition of multiexposure, multiple exposure is identical or different.
Light exposure in above-mentioned any Exposure mode, the most both preferably 5～1000mJ/cm2, more preferably 5～ 500mJ/cm2, more preferably 5～300mJ/cm2, particularly preferably 5～200mJ/cm2, most preferably 5～50mJ/cm2。 It should be noted that light exposure is according to the wavelength of light irradiated, the composition of negative light-sensitive resin combination, the thickness etc. of film Suitably optimize.
The time of exposure of per unit area is not particularly limited, by the exposure power of the exposure device used and necessary exposure Light quantities etc. design.It should be noted that during scan exposure, the scanning speed of light obtain time of exposure.
The time of exposure of per unit area is usually about 1～60 second.
Then, as shown in figure ip, use alkaline developer to develop, form the cured film 24 with desired pattern.Solidification In film 24, the exposure portion 23A in previous exposure becomes protuberance 24A, non-exposed portion 23B becomes pattern openings portion 24B.
It should be noted that in this operation, the ink compositions (C) of refusing of non-exposed portion 23B is dissolved in alkali development well Liquid, will not residue in pattern openings portion 24B.
Have figuratum cured film 24 can heat further as referring to figure 1e.Heating-up temperature be preferably 130～250 DEG C, More preferably 180～250 DEG C, more preferably 200～230 DEG C.By heating, refuse ink compositions (C) and be firmly bonded In cured film, form thin layer on distance surface closer to place.
After above-mentioned heating, for the partition wall of the organic layers such as the luminescent layer for utilizing IJ method pattern printing organic EL element For purposes, generally for removing the development residue of the negative light-sensitive resin combination of residual in pattern openings portion 24B, And base material 10 is carried out UV/O3Treatment with irradiation.
Negative light-sensitive resin combination according to the present invention, it is possible to the partition wall that formation has the property that: upper surface Have and good refuse ink and even across UV/O3Treatment with irradiation its refuse Mo Xingye and well kept, will not remain and refuse in point Ink agent.
The partition wall of the present invention, when utilizing IJ method to carry out pattern printing, can be used as delimiting the partition wall of ink injection zone.
The upper surface of the partition wall of the present invention has good refuses ink, when carrying out pattern printing hence with IJ method, and energy Enough in the region surrounded by partition wall, it is coated with ink equably.Note in undesirably region it addition, can suppress to cross partition wall Enter ink, can be with desired pattern printer's ink well.
As shown in Figure 2 A, after forming cured film 24, (Fig. 1 E) is dripped ink 51 by ink gun 40, to the pattern of cured film 24 Peristome 24B injects ink 51.Then, be dried and/or heating etc. and remove solvent, as shown in Figure 2 B, it is possible to obtain expectation Pattern film 52.
[optical element]
The optical element of the present invention possesses multiple point and the partition wall of the invention described above.
As optical element, organic EL element, the color filter of liquid crystal cell, organic tft array element etc. can be listed.
Organic tft array element refers to following element: multiple points are configured to overlook rectangular, are provided with pixel in each point Electrode and the TFT as the switch element for driving it, use organic semiconductor layer partly leading as the channel layer comprising TFT Body layer.
Organic tft array element is equipped with as tft array substrate in organic EL element or liquid crystal cell etc..
Organic EL element such as can operate as follows and manufacture.
By optically transparent electrodes such as film forming tin-doped indium oxide (ITO) such as sputtering methods on the light-transmitting substrates such as glass.Should Optically transparent electrode patterns as required.
Then, the negative light-sensitive resin combination of the present invention is used, by including coating, exposed and developed photoetching process Partition wall is formed as overlooking clathrate by the profile along each point.
Then, utilize the known method point to being surrounded by partition wall to implement ink-receptiveization as required to process.
Then, point in utilize IJ method be respectively coated hole injection layer, hole transmission layer, luminescent layer, hole blocking layer and The material of electron injecting layer is also dried, and stacks gradually these layers.Kind and the quantity of the organic layer formed in point can suitably set Meter.
Finally, vapour deposition method etc. is utilized to form the reflecting electrodes such as aluminum.
Embodiment
Based on embodiment, the present invention will be described, and the present invention is not by their limited explanation.Example 1～10, example 14 and Example 15 is embodiment, and example 11～13 is comparative example.
Each mensuration utilizes following methods to carry out.
[number-average molecular weight (Mn) and matter average molecular weight (Mw)]
Utilize gel permeation chromatography, using polystyrene as standard substance, measure number-average molecular weight (Mn) and matter is divided equally Son amount (Mw).As chromatograph of gel permeation, use HPLC-8220GPC (TOSOH Co., Ltd's system).As post, use 3 The post that shodex LF-604 is formed by connecting.As detector, use RI (Refractive Index, refractive index) detector.Make For standard substance, use EasiCal PS1 (Polymer Laboratories company system).And then, measuring number-average molecular weight During with matter average molecular weight, post is kept with 37 DEG C, as eluent, use oxolane, flow velocity is set to 0.2mL/ and divides Clock, injects the 0.5 mass % tetrahydrofuran solution 40 μ L measuring sample.
[fluorine atom containing ratio]
The containing ratio (quality %) of the fluorine atom in the first compound and the second compound is made with 1,4-dual-trifluoromethyl benzene For standard substance, utilize19F NMR measures and calculates.It addition, refuse the fluorine atom containing ratio of ink compositions (C) by the first chemical combination The fluorine atom containing ratio of thing and the content of the second compound and the first compound and the second compound calculates.
[content of olefinic double bond (C=C)]
The content of the olefinic double bond (C=C) in the first compound and the second compound is come theoretical by the compounding ratio of raw material Calculate to property.
[acid number]
Acid number in second compound is calculated by the compounding ratio of raw material with carrying out theoretical property.
The abbreviation of the compound used in each example described below.
(raw material of the first compound)
Be equivalent to the compound (cx-11) of compound (cx-1): CF3(CF2)5CH2CH2Si(OC H3)3(Asahi Glass strain formula Commercial firm's system), compound (cx-12): CF3(CF2)5CH2CH2Si(C H3)(OCH3)2、
Be equivalent to the compound (cx-21) of compound (cx-2): Si (OC2H5)4(COLCOAT CO., Ltd system), compound (cx-22): Si (OC2H5)4Partial hydrolysis condensate (COLC OAT CO., Ltd system, trade name: Ethyl Silicate 48)、
Be equivalent to the compound (cx-31) of compound (cx-3): CH2=CHCOO (CH2)3Si(O CH3)3(Tokyo chemical conversion work Industry Co., Ltd. system),
Be equivalent to the compound (cx-41) of compound (cx-4): (CH3)3SiOCH3(Tokyo HuaCheng Industry Co., Ltd System),
Be equivalent to the compound (cx-51) of compound (cx-5): SH (CH2)3Si(OCH3)3(SHIN-ETSU HANTOTAI's chemical industry strain formula meeting Society's system, trade name: KBM-803),
Other hydrolysable silanes compound (cx-61): CH3O(C2H4O)kSi(OCH3)3(the trimethoxy containing polyoxyethylene Base silane, in formula, k is about 10.).
DBTDL: dibutyl tin laurate
(raw material of the second compound)
C6FMA:CH2=C (CH3)COOCH2CH2(CF2)6F。
MAA: methacrylic acid.
2-HEMA: 2-hydroxyethyl methacrylate.
PME-400:CH2=C (CH3)COO(CH2CH2O)kCH3(Alpha-Methyl-ω-methacryloxy poly-(oxygen ethylene), K in formula represents intermolecular meansigma methods, and k is about 9.NOF Corp's system, trade name: BLEMMER PME-400).
IBMA: isobornyl methacrylate.
V-65:2,2 '-azo double (2,4-methyl pentane nitrile) (with Guang Chun medicine Co., Ltd. system).
N-DM: n-dodecyl mercaptan.
BEI:1,1-(double acryloyloxymethyl) ethyl isocyanate (Showa Denko K. K's system, trade name: Karenz BEI)。
AOI:2-acryloyloxyethyl isocyanate (Showa Denko K. K's system, trade name: Karenz AOI).
DBTDL: dibutyl tin laurate.
TBQ: tert-butyl group 1,4-benzoquinone.
MEK:2-butanone.
(alkali soluble resin (AP))
A-11: make cresol novolak type epoxy resin react with acrylic acid, then with 1,2,3,6-tetrahydrochysene O-phthalics Anhydride reaction imports acryloyl group and carboxyl, thereafter, the resin purified with hexane, solid constituent 70 mass %, acid number 60mgKOH/g。
A-12: import carboxyl and the resin (Nippon Kayaku K. K of olefinic double bond in bisphenol A type epoxy resin System, trade name: KAYARAD ZAR-2002H, solid constituent 70 mass %, acid number 60mgKOH/g).
Having in the epoxy resin of biphenyl backbone shown in A-13: upper quadrant (A-2a) imports olefinic double bond and acidic-group Resin (Nippon Kayaku K. K's system, trade name: ZCR-1642H, matter average molecular weight (Mw): 5800, acid number: 100mgKOH/g, solid constituent: 70 mass %).
A-14: import olefinic double bond and acidic-group to having in the epoxy resin of biphenyl backbone shown in formula (A-2b) and Resin (the solid constituent: 70 mass %, PGMEA:30 mass % become.Acid number 70mgKOH/g.).
(Photoepolymerizationinitiater initiater (B))
IR907:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropane-1-ketone (BASF AG's system, trade name: IRGACURE907)。
(BASF is public for OXE02:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) Department's system, trade name: OXE02 ETHANON).
OXE01:{1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1,2-acetyl caproyl (BASF AG's system, trade name: OXE01)。
(sensitizer)
EAB:4,4 '-bis-(lignocaine) benzophenone (Tokyo HuaCheng Industry Co., Ltd's system).
NR1: three (2-mercaptopropionyl epoxide ethyl) isocyanuric acid ester (Showa Denko K. K's system, trade name: Karenz MT NR1)。
PE1: tetramethylolmethane four (3-mercaptobutylate) (Showa Denko K. K's system, trade name: Karenz MT PE1)。
BTT:2-mercaptobenzothiazoler
(solvent (D))
PGMEA: propylene glycol methyl ether acetate.
PGME: propylene glycol monomethyl ether.
EDM: diethylene glycol ethylmethyl ether.
EDGAC: diethylene glycol monoethyl ether acetas.
(cross-linking agent (E))
Melange (the Xin Zhong village chemistry of A9550W: dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate Industrial Co., Ltd's system, trade name: NK ESTER A-9550W).
UX5002D: polyfunctional carbamate acrylate oligomer (Nippon Kayaku K. K's system, trade name: KAYARAD UX-5002D-P20)。
ADPH: dipentaerythritol acrylate (chemical industry Co., Ltd. of Xin Zhong village system, trade name: NK ESTER A- DPH)。
Double [4-(2-acryloyloxyethoxy) phenyl] fluorenes of ABPEF:9,9-(chemical industry Co., Ltd. of Xin Zhong village system, Trade name: NK ESTER A-BPEF).
(coloring agent (F))
Mixing organic pigment: C.I. pigment blue 15: 6, C.I. paratonere 254, C.I. pigment yellow 13 9 and macromolecule dispersing agent The mixture (solid constituent: 25 mass %, PGMEA:75 mass % of 10:5:5:5.).
(other)
BHT: polymerization inhibitor (DBPC 2,6 ditertiary butyl p cresol).
XD1000: polyfunctional epoxy resin (Nippon Kayaku K. K's system, trade name: XD1000).
[synthesis example 1: the synthesis of compound (CX-1)]
Possessing the 1000cm of blender3There-necked flask in put into compound (cx-11) 14.5g, compound (cx-21) 32.9g, compound (cx-31) 21.9g, compound (cx-41) 21.9g and compound (cx-51) 8.8g, obtain water-disintegrable Silane compound mixture.Then, in this mixture, put into PGMEA 320.2g, make material solution.
1 mass % aqueous solution of nitric acid 98.7g is dripped in gained material solution.After completion of dropwise addition, little with 40 DEG C of stirrings 5 Time, obtain the solution (compound concentration: 10 mass %, hereinafter also referred to (CX-1) solution of compound (CX-1).).
It should be noted that after reaction terminates, use gas chromatograph that reactant liquor is measured, it is thus identified that as raw material Each compound below detection limit.
By raw material composition and evaluation result (number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio and The content of olefinic double bond) it is shown in table 1.
[synthesis example 2～6: compound (CX-2)～(CX-6)]
In addition to raw material composition is set to shown in table 1, operate as synthesis example 1, obtain compound (CX-2)～ (CX-6) solution (is compound concentration: 10 mass %, the most each solution is referred to as (CX-2)～(CX-6) liquid.).
By evaluation result (containing of number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio and olefinic double bond Amount) it is shown in table 1.
[table 1]
[synthesis example 7: the synthesis of compound (CY-1)]
Possessing the internal volume 1000cm of blender3Autoclave in put into MEK 420.0g, C6FMA 81.0g, MAA 18.0g, 2-HEMA 81.0g, polymerization initiator V-65 5.0g and n-DM 4.7g, limit stirs in a nitrogen atmosphere, while with 50 DEG C are polymerized 24 hours.And then, make polymerization initiator inactivate with 70 DEG C of heating 5 hours, obtain the solution of copolymer 1.Copolymerization The number-average molecular weight (Mn) of thing 1 is 5540, matter average molecular weight (Mw) is 13200.
Then, to the internal volume 300cm possessing blender3Autoclave in put into above-mentioned copolymer 1 solution 130.0g, BEI 30.5g, DBTDL 0.12g and TBQ 1.5g, react 24 hours with 40 DEG C while stirring, synthesizes crude polymer.To institute Obtain interpolation hexane in the solution of crude polymer and carry out reprecipitation after purification, be vacuum dried, obtain 65.6g compound (CY- 1)。
Raw material is formed, the evaluation result of yield and gained compound (number-average molecular weight (Mn), matter average molecular weight (Mw), Fluorine atom containing ratio, the content of olefinic double bond and acid number) it is shown in table 2.
[synthesis example 8: the synthesis of compound (CY-2)]
In addition to using the solution of above-mentioned copolymer 1, AOI, DBTDL and TBQ with composition shown in table 2, same with synthesis example 7 Sample operates, and obtains compound (CY-2).
[synthesis example 9: the synthesis of compound (CY-3)]
Possessing the internal volume 1000cm of blender3Autoclave in shown in table 2 composition put into MEK, C6FMA, MAA, 2-HEMA, PME-400 and polymerization initiator V-65, limit is stirred in a nitrogen atmosphere, while be polymerized 24 hours with 50 DEG C. And then, heat 5 hours with 70 DEG C, make polymerization initiator inactivate, obtain the solution of compound (CY-3).With Rotary Evaporators with 50 DEG C temperature distillation remove solvent, thereafter, be vacuum dried, obtain compound (CY-3).
[synthesis example 10～11: compound (CY-4)～the synthesis of (CY-5)]
In addition to raw material composition is set to shown in table 2, operate as synthesis example 9, obtain compound (CY-4)～ (CY-4)。
[synthesis example 12: compound (CY-6)]
As compound (CY-6), prepare the trade name that Liao great Japanese ink Co., Ltd. manufactures: Megafac RS102。
This compound is the polymer with following repetitive.It should be noted that m2/m1=3～4.
[synthesis example 13: the synthesis of compound (CY-7)]
Except form with the raw material shown in table 2 use MEK, C6FMA, MAA, 2-HEMA and polymerization initiator V-65 it Outward, the method identical with the copolymer 1 of synthesis example 7 is utilized to obtain the solution of copolymer 2.The number-average molecular weight (Mn) of copolymer 2 Be 32400, matter average molecular weight (Mw) be 69320.
In addition to forming with the raw material shown in table 2 and using the solution of above-mentioned copolymer 2, AOI, DBTDL and TBQ, profit Compound (CY-7) is obtained by the method as example 5.
The raw material of compound (CY-2)～compound (CY-7) is formed, yield and evaluation result (number-average molecular weight (Mn), Matter average molecular weight (Mw), fluorine atom containing ratio, the content of olefinic double bond and acid number) it is shown in table 2.
[table 2]
[example 1: negative light-sensitive resin combination and the manufacture of partition wall]
(manufacture of negative light-sensitive resin combination)
Compound (CX-1) 1.5g (compound (CX-containing 0.15g with solid component meter that will obtain in synthesis example 1 1), remaining as solvent PGMEA), (solid constituent is for compound (CY-1) 0.015g, A-11 16.07g of obtaining in synthesis example 7 11.25g, remaining as solvent PGMEA), IR907 1.21g, EAB 1.125g, A9550W 11.25g, PGMEA 55.0g and EDM 20.0g puts into 200cm3Stirring container in, stir and manufacture negative light-sensitive resin combination in 5 hours.By former Material composition is shown in table 3.
In table, solid constituent total amount refers to that all solids composition in addition to solvent (D) is relative to negative photosensitive resin The amount (quality %) of total composition.
Solid constituent composition represents relative to the amount (quality %) of all solids component amount with each solid material.
Solvent (D) composition represents relative to the amount (quality %) of total composition with each solvent (D).
Table 3 illustrates the quality of quality/the first compound of the second compound the most in the lump.
(manufacture of partition wall)
Glass substrate EtOH Sonicate ripple square for 10cm is cleaned 30 seconds, then, carries out the UV/O of 5 minutes3Process. UV/O3Process and use PL2001N-58 (SenEngineering Co., Ltd. system) as UV/O3Generating means.254nm converts Luminous power be 10mW/cm2.It should be noted that following all UV/O3Process all uses this device.
Use and be coated with above-mentioned negative light-sensitive resin combination, so on spinner glass baseplate surface after above-mentioned cleaning After with 100 DEG C on hot plate be dried 2 minutes, formed thickness 2.4 μm desciccator diaphragm.
Across having the photomask of patterns of openings (2.5cm × 5cm), with 100mJ/cm in the way of whole face exposes in the lump2 Light exposure to gained desciccator diaphragm irradiate 365nm conversion exposure power be 25mW/cm2The UV light of ultrahigh pressure mercury lamp.Exposure Time, clip the light of below 330nm.It addition, the spacing distance between desciccator diaphragm and photomask is set to 50 μm.
Then, the glass substrate after above-mentioned exposure-processed is impregnated in 2.38 mass % tetramethylammonium hydroxide aqueous solutions Within 40 seconds, develop, rinse non-exposed portion with water and make it be dried.Then, it is heated 60 minutes with 230 DEG C on hot plate, thus Obtain the partition wall (cured film) with pattern corresponding with the patterns of openings of photomask.
For gained partition wall, implement following evaluation.Evaluation result is shown in table 3.
<compatibility of negative light-sensitive resin combination>
Use the negative light-sensitive resin combination after just manufacturing, be dried under the formation condition of above-mentioned desciccator diaphragm Film.Detect by an unaided eye gained desciccator diaphragm, is evaluated according to following benchmark.
Zero (well): film is clear, colorless.△ (can): film generation white opacity, but can't see foreign body.× (bad): Film generation white opacity, visible foreign matters in film.
<storage-stable of negative light-sensitive resin combination>
Use and save the negative light-sensitive resin combination of 30 days with 60 DEG C, under the formation condition of above-mentioned desciccator diaphragm To desciccator diaphragm.Detect by an unaided eye gained desciccator diaphragm, is evaluated according to following benchmark.
If there is big foreign body in negative light-sensitive resin combination, then during spin coating, foreign body is drawn to periphery, gained film The radial striped of upper generation.
Zero (well): foreign and radial-like streak.△ (can): visible foreign matters but without radial-like streak.× (bad): There is radial-like streak.
<thickness of cured film>
Laser microscope (Keyemce company system, device name: VK-8500) is used to be measured.
< partition wall upper surface refuse ink and resistance to UV/O thereof3Property >
Following method is utilized to measure the PGMEA contact angle of gained cured film upper surface.
Utilize sessile drop method, according to JIS R3257 " base plate glass wettability of the surface test method ", at cured film upper surface 3 at load PGMEA drop, be measured for each PGMEA drop.Drop is that 2 μ L/ drip, and measures and carries out at 20 DEG C.Contact Angle is obtained by the meansigma methods of 3 measured values.It should be noted that PGMEA is the abbreviation of propylene glycol methyl ether acetate.
The whole surface of the glass substrate being formed with cured film carries out 3 minutes, and (light quantity is calculated as with 254nm conversion 1800mJ/cm2) UV/O3After treatment with irradiation, measure the PGMEA contact angle of cured film upper surface again with said method.
<SEM of partition wall upper surface observes>
Carry out gained partition wall upper surface SEM observe (5000 times, Keyemce company system, the actual surface of device name: 3D see Examine microscope VE-9800), the end of observation partition wall upper surface, with or without protuberance, is evaluated according to following benchmark.
Zero (well): the end of partition wall upper surface does not observes protuberance.
△ (can): protuberance is observed in the end of partition wall upper surface.
[example 2～15]
In addition to negative light-sensitive resin combination is changed in example 1 composition shown in table 3, utilize same method Manufacture negative light-sensitive resin combination and partition wall and be evaluated.Evaluation result is shown in table 3.
[table 3]
In table 3, " % " is " quality % ".
(summary of result)
It is applied in combination the first compound and the second compound, i.e. use refuse the example 1～10 of ink compositions (C), example 14 and In example 15, partition wall upper surface have excellence refuse ink, even if it refuses ink at UV/O3Also it is able to well maintained after process.
At UV/O3In evaluation before treatment with irradiation, the partition wall upper surface of example 1～10, example 14 and example 15 refuse Mo Xingyu The partition wall upper surface of the example 13 that only used the matter average molecular weight (Mw) the second compound more than 100,000 is equal.
At UV/O3In evaluation before treatment with irradiation, the partition wall upper surface of example 1～10, example 14 and example 15 refuse Mo Xinggao In only used the example 11 of the first compound and only used the second compound that matter average molecular weight (Mw) is less than 50,000 Example 12.
The storage of the negative light-sensitive resin combination being applied in combination the example 1～10 of the first compound and the second compound is steady Qualitative the best.Relative to the visible raising of example 11 that only used the first compound.
The end of the partition wall upper surface being applied in combination the example 1～10 of the first compound and the second compound is not observed grand Rise, it is possible to form the partition wall of neat shape.Relative to the visible raising of example 11 that only used the first compound.
Only used the example 12 of the second compound and the negative light-sensitive resin combination of example 13 at UV/O3Dividing after process The ink of refusing of next door upper surface significantly reduces.
Industrial applicability
The present invention refuses ink compositions at optics such as organic EL element, the color filter of liquid crystal cell and organic tft arrays Photosensitive polymer combination that partition wall when can be suitably used as utilizing ink-jet method to carry out pattern printing in element is formed or What person was contained therein refuses ink agent etc..
It addition, the partition wall formed by the photosensitive polymer combination refusing ink compositions containing the present invention can be used as For utilizing the partition wall (protruding) of the organic layers such as IJ method pattern printing luminescent layer in organic EL element, or can be used as at liquid crystal In element, for utilizing the partition wall of IJ method pattern printing color filter, (this partition wall can double as black matrix" (BM).), Jin Erke It is used as in organic tft array for utilizing IJ method pattern printed conductor pattern or the partition wall of semiconductor pattern, additionally can use Act on and utilize IJ method pattern printing to become the organic semiconductor layer of channel layer of TFT, gate electrode, source electrode, drain electrode, grid cloth The partition wall of line and source wiring etc..
It should be noted that by the description of Japanese patent application 2012-209084 filed in JIUYUE in 2012 24 days, The full content of claims, accompanying drawing and summary is quoted so far, as the present invention description disclosure and group enters.
Description of reference numerals
10: base material, 21: film, 22: desciccator diaphragm, 23: exposed film, 23A: exposure portion, 23B: non-exposed portion, 24: solidification Film, 24A: protuberance, 24B: pattern openings portion, 30: photomask, 40: ink gun, 51: ink, 52: pattern film, L: light.

Claims (15)

1. a negative light-sensitive resin combination, it is characterised in that it is refused ink compositions for comprising and have photocuring The alkali soluble resin of property or base soluble monomer (A), Photoepolymerizationinitiater initiater (B) and the negative photosensitive resin group of solvent (D) Compound,
Described ink compositions of refusing comprises the first compound and the second compound, and described first compound has fluorine alkylene for comprising The partial hydrolysis condensate of the mixture of the first hydrolysable silanes compound of base and/or fluoroalkyl and hydrolization group, institute State the main chain of the second compound be hydrocarbon chain and comprise there is the side chain of fluorine atom, matter average molecular weight (Mw) is 100～1,000,000,
Described second compound is the polymer comprising the side chain with acidic-group.
Negative light-sensitive resin combination the most according to claim 1, wherein, described first hydrolysable silanes compound is Compound shown in following formula (cx-1),
(A-RF11)a-Si(RH11)bX11 (4-a-b)···(cx-1)
RF11For comprising at least 1 fluorine alkylidene, the divalent organic group of carbon number 1～16 or comprise etheric oxygen atom The divalent organic group of carbon number 2～16, RH11For the alkyl of carbon number 1～6,
X11For hydrolization group, X11When existing multiple, they each other can difference can also be identical；
A is 1 or 2, b is 0 or 1, a+b is 1 or 2,
A is the group shown in fluorine atom or lower formula (I),
-Si(RH12)cX12 (3-c)···(I)
RH12For the alkyl of carbon number 1～6,
C is 0 or 1,
X12For hydrolization group, X12When existing multiple, they each other can difference can also be identical,
A-RF11When existing multiple, they each other can difference can also be identical.
Negative light-sensitive resin combination the most according to claim 2, wherein, described mixture also comprises following formula (cx-2) The second shown hydrolysable silanes compound,
SiX2 4···(cx-2)
X2Represent hydrolization group, 4 X2Each other can difference can also be identical.
4. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, described mixture also wraps Containing the 3rd hydrolysable silanes compound shown in following formula (cx-3),
(Y-Q3)g-Si(RH3)hX3 (4-g-h)···(cx-3)
Y is the group with olefinic double bond,
Q3For the divalent organic group without fluorine atom of carbon number 1～6,
RH3For the alkyl of carbon number 1～6,
X3For hydrolization group, X3When existing multiple, they each other can difference can also be identical,
G is 1 or 2, h is 0 or 1, g+h is 1 or 2,
Y-Q3When existing multiple, they each other can difference can also be identical.
5. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, described second compound For polymer, described polymer comprises the fluoroalkyl optionally containing etheric oxygen atom and/or has optionally containing etheric oxygen atom The side chain of fluoroalkyl.
Negative light-sensitive resin combination the most according to claim 5, wherein, described second compound has alkene for comprising Belong to the polymer of the side chain of double bond.
Negative light-sensitive resin combination the most according to claim 5, wherein, described second compound has oxygen for comprising The polymer of the side chain of alkylidene.
8. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, described second compound It is 0.01～10 relative to the mass ratio of described first compound.
9. described according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, refuse ink combination The containing ratio of the fluorine atom of thing is 5～40 mass %.
10., according to the negative light-sensitive resin combination according to any one of claims 1 to 3, it is also included in 1 molecule tool There are more than 2 olefinic double bonds and not there is the cross-linking agent (E) of acidic-group.
11. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, in all solids composition The first compound be 0.05～10 mass % containing ratio, the second compound is 0.01～5 mass % containing ratio.
12. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, in all solids composition Described in refuse ink compositions is 0.06～15 mass % containing ratio.
13. 1 kinds of cured film, it is characterised in that it is by the negative photosensitive resin according to any one of claim 1～12 Compositions coats substrate surface, removal solvent (D) exposure.
14. 1 kinds of partition walls, it is characterised in that it comprises the cured film described in claim 13.
15. 1 kinds of optical elements, it is characterised in that it possesses the partition wall described in multiple point and claim 14.
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