CN104541202B - Resin combination, cured film, object and its preparation method and display device with pattern - Google Patents

Resin combination, cured film, object and its preparation method and display device with pattern Download PDF

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Publication number
CN104541202B
CN104541202B CN201380042751.3A CN201380042751A CN104541202B CN 104541202 B CN104541202 B CN 104541202B CN 201380042751 A CN201380042751 A CN 201380042751A CN 104541202 B CN104541202 B CN 104541202B
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ingredient
group
mentioned
photosensitive polymer
base
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CN104541202A (en
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中村秀之
铃木成
铃木成一
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The hardening thing that the purpose of the present invention is to provide a kind of available mist degrees is small, refractive index is high, and the photosensitive polymer combination that analyticity is excellent.Polymer, (ingredient B) heterocyclic compound, (ingredient C) photoacid generator, (ingredient D) metal oxide particle and (ingredient E) solvent with 2 or more nitrogen-atoms of photosensitive polymer combination of the invention the is characterized in that Component units with the base protected containing acidic group by sour decomposability base that include: (ingredient A).In addition, ingredient B preferably has on 1,3 at least compound of the heterocycle structure containing nitrogen-atoms.

Description

Resin combination, cured film, object and its preparation method and display device with pattern
Technical field
The present invention relates to a kind of photosensitive polymer combination (hereinafter sometimes referred to simply as " composition of the invention ").In addition, The present invention relates to one kind to make hardening thing and its manufacturing method made of above-mentioned photosensitive polymer combination hardening, using above-mentioned photosensitive Property resin combination resin pattern manufacturing method, harden above-mentioned photosensitive polymer combination made of cured film and make With the various image display devices of above-mentioned cured film.
More specifically, the present invention relates to one kind to be suitable for forming liquid crystal display device, organic electroluminescent (Electroluminescence, EL) display device, touch panel display device, integrated circuit component, solid photographic element etc. The system of the planarization film of electronic component, the photosensitive polymer combination of protective film or interlayer dielectric and the cured film using it Make method.
Background technique
According to the development of solid photographic element or liquid crystal display device, and start to carry out utilizing organic material (tree extensively Rouge) make the optical components such as lenticule, optical waveguide, anti-reflective film.
In order to get higher the refractive index of these optical components, and studying the particles such as addition zirconium oxide.
In addition, as existing composition, it is known to documented composition in patent document 1 and patent document 2.
Disclosing in patent document 1 has a kind of composition containing metal microparticle comprising contains at least one sulphur atom Heterocyclic compound and metal microparticle.
Disclosing in patent document 2 has a kind of curable resin composition, characterized by comprising: contains 2 in [A] molecule The polymer of a above epoxy group, [B] cationically polymerizable compound (still, are somebody's turn to do except [A] ingredient), and [C] is selected from Thiazoles, Thiazoling type, sulfinylamines, dithiocarbamate and thiurams group at least one kind of chemical combination Object.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2008-1844 bulletin
[patent document 2] Japanese Patent Laid-Open 2005-17321 bulletin
Summary of the invention
Subject to be solved by the invention
The hardening thing that the purpose of the present invention is to provide a kind of available mist degrees is small, refractive index is high, and analyticity is excellent Photosensitive polymer combination.
Technical means to solve problem
The above subject of the invention passes through documented hand in<1>below,<12>~<15>,<17>,<18>or<19> Section solves.It records together as<2>~<11>of preferred implementation form and<16>below.
<1>a kind of photosensitive polymer combination, characterized by comprising: (ingredient A) has containing acidic group by sour decomposability Polymer, (ingredient B) heterocyclic compound, (ingredient C) light with 2 or more nitrogen-atoms of the Component units of the base of base protection Acid producing agent, (ingredient D) metal oxide particle and (ingredient E) solvent.
<2>photosensitive polymer combination according to above-mentioned<1>, wherein ingredient B is that have at least to contain on 1,3 There is the compound of the heterocycle structure of nitrogen-atoms.
<3>photosensitive polymer combination according to above-mentioned<1>or<2>, wherein ingredient B is that have on 1,3 At least compound of the 5 circle heterocyclic ring structures containing nitrogen-atoms or 6 circle heterocyclic ring structures.
<4>photosensitive polymer combination according to any one of above-mentioned<1>to<3>, the wherein ring of the heterocycle of ingredient B Member includes carbon atom and nitrogen-atoms.
<5>photosensitive polymer combination according to any one of above-mentioned<1>to<4>, wherein ingredient B is by following formula (1) compound represented by.
(in formula (1), R1And R2Separately indicate the organic group of hydrogen atom, halogen atom or monovalence, R1With R2It can key Tie and be the organic group of divalent, R3And R4Separately indicate the organic group of hydrogen atom or monovalence, L1It indicates to form 5 member rings or 6 The concatenating group of the divalent of member ring, R3Or R4With L1It can be bonded and form ring, in addition, when there is the nitrogenous double bond as documented by dotted line When, the bond of dotted line indicates that R is not present2And R4, when the nitrogenous double bond as documented by dotted line is not present, the bond of dotted line is indicated There are R2And R4)
<6>photosensitive polymer combination according to any one of above-mentioned<1>to<5>, wherein ingredient B contain sulfydryl or Thioketones (thioxo) base.
<7>photosensitive polymer combination according to any one of above-mentioned<1>to<6>, wherein ingredient B is by following formula Compound represented by (1-1) or formula (1-2).
(in formula (1-1) and formula (1-2), R6~R8Separately indicate the organic group of hydrogen atom or monovalence, L2And L3Point The concatenating group of the divalent of 5 member rings of formation or 6 member rings, R are not indicated independently6With L2It can be bonded and form ring, R7Or R3With L3It can key It ties and forms ring)
<8>photosensitive polymer combination according to any one of above-mentioned<1>to<7>, wherein the molecular weight of ingredient B be 1,000 or less.
<9>photosensitive polymer combination according to any one of above-mentioned<1>to<8>, wherein relative to composition Total solid content, the content of ingredient D are 30 mass % or more.
<10>photosensitive polymer combination according to any one of above-mentioned<1>to<9>further includes that (ingredient F) is handed over Join agent.
<11>photosensitive polymer combination according to any one of above-mentioned<1>to<10>further includes that (ingredient G) resists Oxidant.
<12>a kind of manufacturing method of hardening thing at least successively includes step (a)~step (c):
(a) photosensitive polymer combination according to any one of above-mentioned<1>to<11>is coated on the painting on substrate Cloth step；
(b) solvent removal step of solvent is removed from the resin combination being coated with；And
(c) heat treatment step that the resin combination for eliminating solvent is heat-treated.
<13>a kind of resin pattern manufacturing method at least successively includes step (1)~step (5):
(1) photosensitive polymer combination according to any one of above-mentioned<1>to<11>is coated on the painting on substrate Cloth step；
(2) solvent removal step of solvent is removed from the resin combination being coated with；
(3) resin combination for eliminating solvent is exposed into pattern using actinic ray (actinic radiation) The step of exposure of shape；
(4) development step developed using aqueous developer to exposed resin combination；And
(5) heat treatment step that developed resin combination is heat-treated.
<14>a kind of hardening thing, by the manufacturing method of the hardening thing according to above-mentioned<12>or according to it is above-mentioned<13 > described in resin pattern manufacturing method and obtain.
<15>a kind of cured film is to make the photosensitive polymer combination according to any one of above-mentioned<1>to<11> It hardens and is formed.
<16>cured film according to above-mentioned<15>, is interlayer dielectric.
<17>a kind of liquid crystal display device comprising according to cured film described in above-mentioned<15>or<16>.
<18>a kind of organic electroluminescence display device and method of manufacturing same comprising according to cured film described in above-mentioned<15>or<16>.
<19>a kind of touch panel display device comprising according to cured film described in above-mentioned<15>or<16>.
The effect of invention
According to the present invention, it is possible to provide the hardening thing that a kind of available mist degree is small, refractive index is high, and excellent photosensitive of analyticity Property resin combination.
Detailed description of the invention
Fig. 1 shows the composition concept maps of an example of liquid crystal display device.Indicate the active matrix base in liquid crystal display device The constructed profile of plate, and there is the cured film 17 as interlayer dielectric.
Fig. 2 indicates the composition concept map of an example of organic EL display device.Indicate that organic EL of bottom emission type shows dress The constructed profile of substrate in setting, and there is planarization film 4.
Fig. 3 is the sectional view for indicating the composition of capacitive input device.
Fig. 4 is the explanatory diagram for indicating an example of front panel.
Fig. 5 is the explanatory diagram for indicating an example of first transparent electrode pattern and second transparency electrode pattern.
[explanation of symbol]
1:TFT (thin film transistor (TFT))
2: wiring
3: insulating film
4: planarization film
5: first electrode
6: glass substrate
7: contact hole
8: insulating film
10: liquid crystal display device
12: back light unit
14,15: glass substrate
16:TFT
17: cured film
18: contact hole
19:ITO transparent electrode
20: liquid crystal
22: colored filter
30: capacitive input device
31: front panel
32: mask layer
33: first transparent electrode pattern
33a: pad part
33b: coupling part
34: second transparency electrode pattern
35: insulating layer
36: key element of electrical conductivity
37: transparent protective layer
38: opening portion
Specific embodiment
Hereinafter, the contents of the present invention are described in detail.The explanation of documented constitutive requirements is sometimes based upon this below The representative implementation form of invention carries out, but the present invention is not limited to such implementation form.
Furthermore in the present invention, indicate " lower limit~upper limit " of numberical range record indicate " it is more than lower limit, the upper limit with Under ", the record of " upper limit~lower limit " indicates " below the upper limit, more than lower limit ".That is, indicating the numerical value model comprising the upper limit and lower limit It encloses.
In addition, in the present invention, also by " (ingredient A) constitutes list with the base protected containing acidic group by sour decomposability base Polymer of member " etc. referred to as " ingredient A " etc., also by " Component units for the base that (a1) is protected containing acidic group by sour decomposability base " Deng referred to as " Component units (a1) " etc..
In turn, in the present specification in the statement of base (atomic group), the statement packet for being substituted and being unsubstituted is not recorded Containing the base (atomic group) without substituent group, and also comprising the base (atomic group) with substituent group.For example, so-called " alkyl ", It not only include the alkyl (alkyl being unsubstituted) without substituent group, also comprising the alkyl (alkane being substituted with substituent group Base).
In addition, in the present invention, " quality % " is identical as the meaning of " weight % ", the meaning of " mass parts " and " parts by weight " It is identical.
In addition, in the present invention, it is preferred to form combination it is more preferable.
(photosensitive polymer combination)
Photosensitive polymer combination of the invention (hereinafter, also referred to as " resin combination ") be characterized in that include: (at Point A) have the polymer of Component units of the base protected containing acidic group by sour decomposability base, (ingredient B) with 2 or more nitrogen Heterocyclic compound, (ingredient C) photoacid generator, (ingredient D) metal oxide particle and (ingredient E) solvent of atom.
Photosensitive polymer combination of the invention can suitably be used as eurymeric anti-corrosion agent composition.
Photosensitive polymer combination of the invention is preferably the resin combination for the property for having Yin Re and hardening.
In addition, photosensitive polymer combination of the invention is preferably positive type photosensitive organic compound, it is more preferably chemical The positive type photosensitive organic compound (chemically amplified positive photosensitive polymer combination) of amplification type.
Photosensitive polymer combination of the invention is preferably free of 1,2- quinone di-azido compound as induction actinic ray Photoacid generator.1, although 2- quinone di-azido compound generates carboxyl by gradually type photochemical reaction, its quantum is produced Rate must be 1 or less.
In contrast, the acid that (ingredient C) photoacid generator used in the present invention is generated because incuding actinic ray is made It plays a role for catalyst to the deprotection of the acidic group being protected in ingredient A, therefore is given birth to by the effect of 1 light quantum At acid facilitate multiple deprotection reactions, quantum yield is more than 1, such as becomes value big such as more than 10 powers, as institute The chemical amplification of meaning as a result, can get high sensitivity.
In turn, photosensitive polymer combination of the invention is preferably lenticule, optical waveguide, anti-reflective film, light emitting diode (Light Emitting Diode, LED) is coated with the optical component resin combination of material etc. with sealing material and LED chip, Or resin combination is used in the visibility reduction of wiring electrode used in touch screen.Furthermore used in so-called touch screen The visibility of wiring electrode, which reduces, uses resin combination, refers to the visibility for reducing wiring electrode used in touch screen, that is, The component composition for making wiring electrode be not easy to be seen, such as tin indium oxide (Indium Tin Oxide, ITO) electricity can be enumerated The interlayer dielectric etc. of interpolar, photosensitive polymer combination of the invention may be suitably used to the purposes.
In touch screen field, there are the insulating layer (optical isolator (Photo in the ITO wiring of bridge (bridge) type Insulator, PI)) visible or problem that the wiring as caused by tin indium oxide (ITO) is visible.
Described is following phenomenon: difference or ITO and surrounding glass substrate because of the refractive index of ITO and insulating layer Or the difference of the refractive index of protective layer etc., therefore ITO and/or insulating layer poor, and that can be seen transparent are generated in terms of the reflectivity of light. For example, inferring that the refractive index of glass substrate is 1.5 or so, therefore generates refractive index because the refractive index of ITO is up to about 1.9 or so Difference, and transparent ITO and/or insulating layer can be seen.
Although using metal oxide particle known as the material of high refractive index, if present inventor etc. has found Metal oxide particle is filled into the composition of insulating film etc. in order to promote refractive index, especially become 40 mass % with On it is highly-filled after be coated, then metal oxide particle is more, only can not prevent the cohesion of particle by dispersing agent, and produce The cohesion of metal oxide particle when raw so-called coating.Although the situation obtains changing slightly by increasing dispersing agent It is kind, but the value as the mist degree under the film thickness of above-mentioned insulating layer, using 1% mist degree below as target with can not reach on the way At.
It is that present inventor etc. is studied in detail to be made as a result, finding to pass through containing ingredient A~ingredient E photoresist Composition, and the dispersibility of (ingredient D) metal oxide particle is improved, to can get the transparency excellent (mist degree is small), refraction The photosensitive polymer combination that rate is high, analyticity is excellent.
Hereinafter, composition of the invention is described in detail.
(ingredient A) has the polymer of the Component units for the base protected containing acidic group by sour decomposability base
Photosensitive polymer combination of the invention includes that (ingredient A) has the base protected containing acidic group by sour decomposability base The polymer of Component units.
Furthermore " Component units containing the base that acidic group is protected by sour decomposability base " also in the present invention, are known as " (a1) Component units containing the base that acidic group is protected by sour decomposability base ".
Photosensitive polymer combination of the invention be preferably contain comprising meet following (1) and following (2) at least one Polymer component of polymer.
(1) Component units and (a2) with (a1) base protect containing acidic group by sour decomposability base contain bridging property base Component units polymer (being equivalent to ingredient A)
(2) polymer of the Component units for the base protected by sour decomposability base with (a1) containing acidic group (is equivalent to ingredient A) and (ingredient A ') have the Component units of (a2) containing bridging property base polymer
For the viewpoint of the residual film ratio of the transparency (mist degree) and unexposed portion after hardening, photoresist of the invention Composition preferably contains the ingredient for meeting above-mentioned (1).
On the other hand, for the viewpoint of the freedom degree of MOLECULE DESIGN, photosensitive polymer combination of the invention is preferably Contain the ingredient for meeting above-mentioned (2).
It, can also be in turn comprising having (a1) containing acidic group by acid furthermore containing the ingredient for meeting above-mentioned (1) The acrylic resin of the Component units of the base of decomposability base protection and/or with the Component units of (a2) containing bridging property base Acrylic resin.
In addition, when including at least to be equivalent to there is (a1) to contain acidic group containing the ingredient for meeting above-mentioned (2) By sour decomposability base protection base the Component units of Component units and (a2) containing bridging property base polymer ingredient when, Also as person the case where being equivalent to containing the ingredient for meeting above-mentioned (1).
Ingredient A is preferably the resin of addition polymerization type, more preferably containing the structure from (methyl) acrylic acid and/or its ester At the polymer of unit.Furthermore there can also be the composition list other than the Component units from (methyl) acrylic acid and/or its ester Member, the Component units for example originating from styrene or the Component units from vinyl compound etc..
Furthermore also " (methyl) acrylic acid and/or the Component units of its ester will be originated from " and be known as " acrylic acid series Component units ". In addition, " (methyl) acrylic acid " refers to " methacrylic acid and/or acrylic acid ".
<Component units (a1)>
Ingredient A is the polymer of the Component units at least with (a1) base protected containing acidic group by sour decomposability base.It is logical Ingredient A is crossed with Component units (a1), and can be made into the high photosensitive polymer combination of sensitivity.
" base that acidic group is protected as sour decomposability base " in the present invention can be used as well known to acidic group and sour decomposability base Base, be not particularly limited.As specific acidic group, it is preferable to enumerate carboxyl and phenolic hydroxyl group.In addition, being decomposed as acid Property base, can be used be easier to decompose by acid base (such as by the base represented by aftermentioned formula (a1-10) etc. ester structure, The acetals such as oxinane ester group or tetrahydrofuran ester group system functional group) or compare base (such as the tertiary fourth for being difficult to decompose by acid The carbonic acid three-level alkyl such as the three-levels such as ester group alkyl, t-butyl carbonate base ester group).
(a1) Component units for the base protected containing acidic group by sour decomposability base preferably contain carboxyl by sour decomposability base The protection carboxyl of protection Component units (also referred to as " and contain by sour decomposability base protect protection carboxyl Component units ") or The Component units for the protection phenolic hydroxyl group protected by sour decomposability base containing phenolic hydroxyl group are (also referred to as " containing by sour decomposability base The Component units of the protection phenolic hydroxyl group of protection ").
Hereinafter, successively to the Component units (a1-1) containing the protection carboxyl protected by sour decomposability base and containing by acid The Component units (a1-2) of the protection phenolic hydroxyl group of decomposability base protection are illustrated respectively.
<<Component units that (a1-1) contains the protection carboxyl protected by sour decomposability base>>
The above-mentioned Component units (a1-1) containing the protection carboxyl protected by sour decomposability base are containing the structure with carboxyl At the Component units for the protection carboxyl that the carboxyl of unit is protected by the sour decomposability base that will be detailed below.
As above-mentioned the containing that can be used for the above-mentioned Component units (a1-1) containing the protection carboxyl protected by sour decomposability base There are the Component units of carboxyl, well known Component units can be used with no particular limitation.It such as can enumerate: be originated from unsaturated monocarboxylic Have at least in the molecules such as (unsaturation mono carboxylic acid), unsaturated dicarboxylic, unsaturated tricarboxylic acids The Component units (a1-1-1) of the unsaturated carboxylic acid of 1 carboxyl etc., or there is ethylene unsaturated group simultaneously and be originated from acid anhydrides The Component units (a1-1-2) of structure.
Hereinafter, being successively originated from molecule to (a1-1-1) that can be used as the above-mentioned Component units containing carboxyl has at least 1 The Component units of the unsaturated carboxylic acid of a carboxyl etc. and (a1-1-2) have ethylene unsaturated group simultaneously and are originated from the knot of acid anhydrides The Component units of structure are illustrated respectively.
<<<Component units that (a1-1-1) is originated from unsaturated carboxylic acid in molecule at least one carboxyl etc.>>>
It, can as the Component units (a1-1-1) of the above-mentioned unsaturated carboxylic acid from molecule at least one carboxyl etc. Use the unsaturated carboxylic acid lifted as listed below as unsaturated carboxylic acid used in the present invention.That is, as unsaturated single carboxylic Acid, such as can enumerate: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (methyl) acryloxy second Base succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl O-phthalic Acid etc..In addition, as unsaturated dicarboxylic, such as can enumerate: maleic acid, fumaric acid, itaconic acid, citraconic acid, in Health acid etc..In addition, can also be its acid anhydrides for obtaining the unsaturated polybasic carboxylic acid of the Component units containing carboxyl.Specifically, Maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.In addition, unsaturated polybasic carboxylic acid can also be the list of polybasic carboxylic acid (2- methacryloxyalkyl) ester, such as can enumerate: succinic acid list (2- acryloyl-oxyethyl) ester, succinic acid list (2- Methacryloxyethyl) ester, phthalic acid list (2- acryloyl-oxyethyl) ester, phthalic acid list (2- methyl-prop Alkene trimethylammonium) ester etc..In turn, unsaturated polybasic carboxylic acid can also be list (methyl) propylene of its two ends dicarboxyl based polyalcohol Acid esters, such as ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates can be enumerated etc..Separately Outside, as unsaturated carboxylic acid, it is possible to use acrylic acid -2- carboxyethyl, methacrylic acid -2- carboxyethyl, maleic acid Monoalkyl ester, fumaric acid monoalkyl ester, 4- carboxyl styrene etc..
Wherein, above-mentioned from the unsaturation in molecule at least one carboxyl in order to be formed for the viewpoint of developability The Component units (a1-1-1) of carboxylic acid etc., it is preferable to use acrylic acid, methacrylic acid, 2- (methyl) acryloyl-oxyethyl fourth Diacid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid or The acid anhydride etc. of unsaturated polybasic carboxylic acid more preferably uses acrylic acid, methacrylic acid, 2- (methyl) acryloyl-oxyethyl hexahydro Phthalic acid.
The Component units (a1-1-1) of the above-mentioned unsaturated carboxylic acid from molecule at least one carboxyl etc. can be wrapped individually It also may include two or more containing a kind.
<<<Component units that (a1-1-2) has ethylene unsaturated group with the structure for being originated from acid anhydrides simultaneously>>>
There is ethylene unsaturated group and the Component units (a1-1-2) for the structure for being originated from acid anhydrides to be preferably derived from simultaneously makes Hydroxyl in the presence of Component units containing ethylene unsaturated group is reacted with acid anhydrides and the unit of monomer that obtains.
As above-mentioned acid anhydrides, well known acid anhydrides can be used, specifically, can enumerate: maleic anhydride, succinic anhydride, The dibasic acid anhydrides such as itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride；Partially The acid anhydrides such as benzenetricarboxylic acid acid anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.It is just aobvious among these acid anhydrides For the viewpoint of shadow, preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.
For the viewpoint of developability, above-mentioned acid anhydrides is preferably 10 moles of %~100 mole % for the reactivity of hydroxyl, More preferably 30 moles of %~100 mole %.
It can be used for the sour decomposability base-of Component units (a1-1)
As the above-mentioned acid that can be used for the above-mentioned Component units (a1-1) containing the protection carboxyl protected by sour decomposability base Above-mentioned sour decomposability base can be used in decomposability base.
Among these sour decomposability bases, with regard to the basic physical properties of photosensitive polymer combination, especially sensitivity or pattern shape Shape, the formative of contact hole, photosensitive polymer combination storage stability viewpoint for, preferably carboxyl be by acetal The protection carboxyl of form protection.In turn, among sour decomposability base, for the viewpoint of sensitivity, more preferably carboxyl be by with The protection carboxyl of the form protection of acetal represented by following formula (a1-10).It furthermore is by with following formula (a1-10) in carboxyl In the case where the protection carboxyl of the form protection of represented acetal, the entirety of carboxyl is protected to become-(C=O)-O-CR101R102 (OR103) structure.
(in formula (a1-10), R101And R102Separately indicate hydrogen atom or alkyl, wherein exclude R101With R102It is The case where hydrogen atom.R103Indicate alkyl.R101Or R102With R103It can link and form cyclic ether).
In above-mentioned formula (a1-10), R101~R103It separately indicates hydrogen atom or alkyl, abovementioned alkyl can be straight chain It is shape, branched, cricoid any.Herein, R is not present101And R102The case where indicating hydrogen atom, R101And R102At least one A expression alkyl.
In above-mentioned formula (a1-10), work as R101、R102And R103When indicating alkyl, abovementioned alkyl can be straight-chain, branched Or it is cricoid any.
As the alkyl of above-mentioned straight-chain or branched, preferably carbon number is 1~12, and more preferably carbon number is 1~6, into And more preferably carbon number is 1~4.Specifically, can enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, secondary Butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2,3- dimethyl -2- butyl (thexyl), n-heptyl, n-octyl, 2- second Base hexyl, n-nonyl, positive decyl etc..
As above-mentioned cyclic alkyl, preferably carbon number is 3~12, and more preferably carbon number is 4~8, and then more preferably carbon Number is 4~6.As above-mentioned cyclic alkyl, such as can enumerate: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring are pungent Base, norborny, isobornyl etc..
Abovementioned alkyl can also have substituent group, as substituent group, can illustrate halogen atom, aryl, alkoxy.When with halogen When plain atom is as substituent group, R101、R102、R103As halogenated alkyl, when with aryl as substituent group, R101、R102、R103 As aralkyl.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom can be illustrated, among these halogen atoms, Preferably fluorine atom or chlorine atom.
In addition, as above-mentioned aryl, preferably carbon number be 6~20 aryl, more preferably carbon number be 6~12 aryl. Specifically, phenyl, Alpha-Methyl phenyl, naphthalene etc. can be illustrated, it, can example as the alkyl entirety replaced by aryl, i.e. aralkyl Show benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc..
As above-mentioned alkoxy, preferably carbon number be 1~6 alkoxy, more preferably carbon number be 1~4 alkoxy, into And more preferably methoxy or ethoxy.
In addition, it is 1~10 straight-chain or branched that above-mentioned naphthenic base, which can have carbon number, when abovementioned alkyl is naphthenic base Alkyl as substituent group, when alkyl is the alkyl of straight-chain or branched, can have carbon number is 3~12 naphthenic base conduct Substituent group.
These substituent groups can also be further substituted with by above-mentioned substituent group.
In above-mentioned formula (a1-10), work as R101、R102And R103When indicating aryl, above-mentioned aryl is preferably that carbon number is 6~12, more Preferably carbon number is 6~10.Above-mentioned aryl can have substituent group, as above-mentioned substituent group, it is preferable to which illustrating carbon number is 1~6 Alkyl.As aryl, such as phenyl, tolyl, xylyl, cumenyl, 1- naphthalene can be illustrated etc..
In addition, R101、R102And R103It can mutually be bonded, and the carbon atom being bonded with these is formed together ring.As R101 With R102、R101With R103Or R102With R103Ring structure when bond, such as can enumerate: cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl Base, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc..
Furthermore in above-mentioned formula (a1-10), preferably R101And R102Either one or two of be hydrogen atom or methyl.
It is used to form the free-radical polymerised list containing the Component units by the protection carboxyl represented by above-mentioned formula (a1-10) Commercially available free radical polymerization monomer can be used in body, it is possible to use passes through free-radical polymerised list synthesized by well known method Body.For example, documented synthesis in 0037~paragraph of paragraph 0040 of Japanese Patent Laid-Open 2011-221494 bulletin can be passed through Method etc. synthesizes.
The first preferred form of the above-mentioned Component units (a1-1) containing the protection carboxyl protected by sour decomposability base For by the Component units represented by following formula.
(in formula, R1And R2Separately indicate hydrogen atom, alkyl or aryl, at least R1And either one or two of R2 be alkyl or Aryl, R3Indicate alkyl or aryl, R1Or R2With R3It can link and form cyclic ether, R4 indicates that hydrogen atom or methyl, X indicate single Key or arlydene).
Work as R1And R2When for alkyl, preferably carbon number be 1~10 alkyl.Work as R1And R2When for aryl, preferably phenyl.R1 And R2It is separately preferably hydrogen atom or alkyl that carbon number is 1~4.
R3The alkyl that the alkyl that expression alkyl or aryl, preferably carbon number are 1~10, more preferably carbon number are 1~6.
X indicates singly-bound or arlydene, preferably singly-bound.
Second of preferred form of the above-mentioned Component units (a1-1) containing the protection carboxyl protected by sour decomposability base For the structural unit of following formula.
(in formula, R121Indicate the alkyl that hydrogen atom or carbon number are 1~4, L1Indicate carbonyl or phenylene, R122~R128Respectively Independently indicate the alkyl that hydrogen atom or carbon number are 1~4).
R121Preferably hydrogen atom or methyl.
L1Preferably carbonyl.
R122~R128Preferably hydrogen atom.
As it is above-mentioned containing by sour decomposability base protect protection carboxyl Component units (a1-1) preferred concrete example, Following Component units can be illustrated.Furthermore R indicates hydrogen atom or methyl.
<<Component units that (a1-2) contains the protection phenolic hydroxyl group protected by sour decomposability base>>
The above-mentioned Component units (a1-2) containing the protection phenolic hydroxyl group protected by sour decomposability base are containing phenolic hydroxyl group Component units have will be detailed below by sour decomposability base protection protection phenolic hydroxyl group Component units.
<<<Component units of (a1-2-1) containing phenolic hydroxyl group>>>
As the above-mentioned Component units containing phenolic hydroxyl group, hydroxy styrenes system Component units or novolaks system can be enumerated Resin in Component units, among these Component units, for the viewpoint of sensitivity, be preferably derived from hydroxy styrenes or The Component units of Alpha-Methyl hydroxy styrenes.In addition, as the Component units containing phenolic hydroxyl group, with regard to sensitivity viewpoint and Speech, by the Component units represented by following formula (a1-20) it is also preferred that.
(in formula (a1-20), R220Indicate hydrogen atom or methyl, R221Indicate the concatenating group of singly-bound or divalent, R222Indicate halogen The alkyl for the straight or branched that plain atom or carbon number are 1~5, a indicate that 1~5 integer, b indicate 0~4 integer, a+b 5 Below.Furthermore when there are 2 or more R222When, these R222Mutually can be different, can also be identical).
In above-mentioned formula (a1-20), R220Indicate hydrogen atom or methyl, preferably methyl.
In addition, R221Indicate the concatenating group of singly-bound or divalent.Work as R221When for singly-bound, sensitivity can be promoted, and then can be promoted The transparency of cured film, therefore it is preferred that.As R221Divalent concatenating group, alkylidene can be illustrated, as R221For the tool of alkylidene Body example can be enumerated: methylene, ethylidene, propylidene, isopropylidene, sub- normal-butyl, isobutylidene, sub- tert-butyl, pentylidene, Isoamylidene, sub- neopentyl, hexylidene etc..Wherein, R221Preferably singly-bound, methylene or ethylidene.In addition, above-mentioned divalent Concatenating group can have substituent group, as substituent group, can enumerate halogen atom, hydroxyl, alkoxy etc..In addition, a expression 1~5 is whole Number, but for the viewpoint of effect of the invention or this point easy to manufacture, preferably a is 1 or 2, and more preferably a is 1.
In addition, when will be with R221When the carbon atom being bonded is as benchmark (1), the binding site of the hydroxyl in phenyl ring It is preferably bonded on 4.
R222Separately indicate the alkyl for the straight or branched that halogen atom or carbon number are 1~5.Specifically, Can enumerate: fluorine atom, chlorine atom, bromine atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, Isopentyl, neopentyl etc..Wherein, it is easy for for manufacture this point, preferably chlorine atom, bromine atom, methyl or ethyl.
In addition, b indicates 0 or 1~4 integer.
It can be used for the sour decomposability base-of Component units (a1-2)
As can be used for the upper of the above-mentioned Component units (a1-2) containing the protection phenolic hydroxyl group protected by sour decomposability base State sour decomposability base, with can be used for it is above-mentioned containing by sour decomposability base protect protection carboxyl Component units (a1-1) it is above-mentioned Sour decomposability base similarly, can be used well known sour decomposability base, be not particularly limited.Among sour decomposability base, with regard to photonasty The basic physical properties of resin combination, especially sensitivity or pattern form, the storage stability of photosensitive polymer combination, contact For the viewpoint of the formative in hole, preferably contain the Component units for the protection phenolic hydroxyl group protected by acetal.In turn, acid decomposes Property base among, for the viewpoint of sensitivity, more preferably phenolic hydroxyl group be by with the acetal represented by above-mentioned formula (a1-10) The protection phenolic hydroxyl group of form protection.Furthermore it is protected in the form of being by the acetal represented by above-mentioned formula (a1-10) in phenolic hydroxyl group In the case where the protection phenolic hydroxyl group of shield, the entirety of phenolic hydroxyl group is protected to become-Ar-O-CR101R102(OR103) structure.Again Person, Ar indicate arlydene.
The preference of the acetal ester structure of phenolic hydroxyl group can illustrate R101=R102=R103The combination of=methyl or R101= R102=methyl and R103The combination of=benzyl.
In addition, as the Component units for being used to form the protection phenolic hydroxyl group protected containing phenolic hydroxyl group by the form of acetal Free radical polymerization monomer, such as can enumerate recorded in the paragraph 0042 of Japanese Patent Laid-Open 2011-215590 bulletin Free radical polymerization monomer etc..
Among these free radical polymerization monomers, for the viewpoint of the transparency, preferably methacrylic acid 4- hydroxy benzenes The THP trtrahydropyranyl protective of the 1- alkoxyalkyl protective of ester, methacrylic acid 4- hydroxylphenyl ester.
The concrete example of acetal protecting group as phenolic hydroxyl group can enumerate 1- alkoxyalkyl, such as can enumerate 1- ethoxy Base ethyl, 1- methoxy ethyl, 1- n-butoxyethyl, 1- isobutoxyethy, 1- (2- chloroethoxy) ethyl, 1- (2- second Base hexyloxy) ethyl, 1- positive propoxy ethyl, 1- cyclohexyloxy ethyl, 1- (2- cyclohexylethoxy radical) ethyl, 1- benzyloxy second Base etc., these bases, which can be used alone, or two or more to be applied in combination by a kind.
It is used to form the freedom of the above-mentioned Component units (a1-2) containing the protection phenolic hydroxyl group protected by sour decomposability base Commercially available free radical polymerization monomer can be used in base polymerizable monomer, it is possible to use passes through free radical synthesized by well known method Polymerizable monomer.For example, can be by the presence of acid catalyst carrying out the compound containing phenolic hydroxyl group and vinyl ethers Reaction is to synthesize.Above-mentioned synthesis can also be such that in advance the monomer containing phenolic hydroxyl group is copolymerized with other monomers, then urge in acid It is reacted in the presence of agent with vinyl ethers.
Preferred tool as the above-mentioned Component units (a1-2) containing the protection phenolic hydroxyl group protected by sour decomposability base Body example can illustrate following Component units, but the present invention is not limited to these Component units.In following concrete examples, R indicates hydrogen Atom or methyl.
The preferred form-of Component units (a1)
When the polymer containing above-mentioned Component units (a1) is substantially free of Component units (a2), containing above-mentioned composition In the polymer of unit (a1), Component units (a1) are preferably 20 moles of %~100 mole %, more preferably 30 moles of %~90 Mole %.
When containing following Component units (a2) containing the polymer of above-mentioned Component units (a1), with regard to sensitivity viewpoint and Speech, in the polymer containing above-mentioned Component units (a1) and Component units (a2), the content of Component units (a1) is preferably 31 Mole %~70 mole %, more preferably 10 moles of %~60 mole %.In addition, especially above-mentioned Component units (a1) be containing In the case where the Component units for the protection carboxyl that carboxyl is protected by the form of acetal, preferably 20 moles of %~50 mole %.
Furthermore in the present invention, when the content with molar ratio to provide " Component units ", it is somebody's turn to do the meaning of " Component units " It is identical as " monomeric unit ".In addition, in the present invention, being somebody's turn to do " monomeric unit " can be carried out after polymerisation by high molecular weight reactive etc. Modification.It is also the same such below.
With it is above-mentioned containing the Component units (a1-2) for the protection phenolic hydroxyl group protected by sour decomposability base compared with, it is above-mentioned containing There is this fast feature of developing by the Component units (a1-1) of the protection carboxyl of sour decomposability base protection.Therefore, it is being intended to quickly show In the case where shadow, preferably containing the Component units (a1-1) for protecting carboxyl protected by sour decomposability base.On the contrary, making Develop it is slack-off in the case where, it is preferable to use the Component units (a1- containing the protection phenolic hydroxyl group protected by sour decomposability base 2)。
Component units > of the < (a2) containing bridging property base
Ingredient A is preferably and then with the Component units (a2) containing bridging property base.In addition, containing when ingredient A does not have When Component units (a2) of bridging property base, photosensitive polymer combination of the invention preferably includes that (ingredient A ') has containing friendship The polymer of the Component units (a2) of connection property base.
As long as above-mentioned bridging property base generates the base of sclerous reaction by heating, then it is not particularly limited.As The form of Component units preferably containing bridging property base, can enumerate containing selected from by epoxy group, oxetanylmethoxy, by-NH- CH2Group composed by base and ethylene unsaturated group represented by-O-R (R indicates the alkyl that hydrogen atom or carbon number are 1~20) The Component units of at least one in group are preferably selected from by epoxy group, oxetanylmethoxy and by-NH-CH2(R indicates hydrogen to-O-R The alkyl that atom or carbon number are 1~20) represented by base composed by it is at least one kind of in group.Wherein, photonasty of the invention It includes the Component units containing at least one in epoxy group and oxetanylmethoxy that resin combination, which is more preferably mentioned component A,.More Specifically, following person can be enumerated.
< < (a2-1) has the Component units > > of epoxy group and/or oxetanylmethoxy
Ingredient A includes preferably the polymer containing Component units (Component units (a2-1)), and the Component units (are constituted Unit (a2-1)) there is epoxy group and/or oxetanylmethoxy.The cyclic ether group of above-mentioned 3 member ring is also referred to as epoxy group, 4 member rings Cyclic ether group be also referred to as oxetanylmethoxy.
The above-mentioned Component units (a2-1) with epoxy group and/or oxetanylmethoxy in 1 Component units as long as have extremely Few 1 epoxy group or oxetanylmethoxy, can have 1 or more epoxy group and 1 or more oxetanylmethoxy, 2 with On epoxy group or 2 or more oxetanylmethoxies, be not particularly limited, but preferably with the ring for adding up to 1~3 Oxygroup and/or oxetanylmethoxy more preferably have epoxy group and/or the oxetanylmethoxy for adding up to 1 or 2, Jin Ergeng Preferably there is 1 epoxy group or oxetanylmethoxy.
As the concrete example for the free radical polymerization monomer for being used to form the Component units with epoxy group, such as can enumerate Glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-propyl acrylic acid contracting Water glyceride, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid -3,4- epoxy group butyl ester, methacrylic acid -3,4- epoxy group Butyl ester, acrylic acid -3,4- epoxycyclohexanecarboxylate, methacrylic acid -3,4- epoxycyclohexanecarboxylate, α-ethylacrylate -3, 4- epoxycyclohexanecarboxylate, vinylbenzyl glycidyl ether, contracts to vinyl benzyl at adjacent vinylbenzyl glycidyl ether Water glycerin ether, No. 4168443 bulletins of Japanese Patent No. 0031~paragraph of paragraph 0035 in documented by contain ester ring type epoxy The compound etc. of base skeleton.
As the concrete example for the free radical polymerization monomer for being used to form the Component units with oxetanylmethoxy, such as can There is oxetanylmethoxy documented by enumerating in 0011~paragraph of paragraph 0016 of Japanese Patent Laid-Open 2001-330953 bulletin (methyl) acrylate etc..
As the free radical polymerization for being used to form the above-mentioned Component units (a2-1) with epoxy group and/or oxetanylmethoxy The concrete example of property monomer, the preferably monomer containing metacrylic acid ester structure, the monomer containing acrylate structural.
Among these, preferably glycidyl methacrylate, acrylic acid 3,4- epoxycyclohexanecarboxylate, metering system 3,4- of acid epoxycyclohexanecarboxylate, acrylic acid (3- Ethyloxetane -3- base) methyl esters and methacrylic acid (3- ethyl oxygen Azetidine -3- base) methyl esters.These Component units, which can be used alone, or two or more to be applied in combination by a kind.
As the preferred concrete example of the Component units (a2-1) with epoxy group and/or oxetanylmethoxy, can illustrate down The Component units stated.Furthermore R indicates hydrogen atom or methyl.
< < (a2-2) has the Component units > > of ethylene unsaturated group
As a kind of the above-mentioned Component units (a2) containing bridging property base, the structure with ethylene unsaturated group can be enumerated At unit (a2-2) (hereinafter also referred to as " Component units (a2-2) ").As the above-mentioned composition list with ethylene unsaturated group First (a2-2), with the Component units of ethylene unsaturated group preferably on side chain, more preferably end has ethylene insatiable hunger With base and with carbon number be 3~16 side chain Component units, and then more preferably have by following formula (a2-2-1) represented by Side chain Component units.
(in formula (a2-2-1), R301Indicate that carbon number is the concatenating group of 1~13 divalent, R302Indicate hydrogen atom or methyl, wave Shape line part indicates the position linked with the main chain of the Component units (a2) containing crosslinking group).
R301For the concatenating group for the divalent that carbon number is 1~13, comprising alkenyl, cycloalkenyl, arlydene or these are composed Base, the keys such as ester bond, ehter bond, amido bond, urethane bond can also be contained.In addition, the concatenating group of divalent can be in arbitrary position It sets with substituent groups such as hydroxyl, carboxyls.As R301Concrete example, the concatenating group of following divalent can be enumerated.
Among the side chain represented by above-mentioned formula (a2-2-1), comprising by above-mentioned R301The concatenating group of represented divalent, it is excellent It is selected as aliphatic side chain.
In addition, having the Component units of ethylene unsaturated group about (a2-2), Japanese Patent Laid-Open 2011- can refer to The record of 0072~paragraph of paragraph 0090 of No. 215580 bulletins.
< < (a2-3) has by-NH-CH2Base represented by-O-R (R indicates the alkyl that hydrogen atom or carbon number are 1~20) Component units > >
Copolymer used in the present invention, which preferably also contains, to be had by-NH-CH2(R indicates hydrogen atom or carbon number to-O-R Alkyl for 1~20) represented by base Component units (a2-3).By containing Component units (a2-3), using mitigation Heat treatment generates sclerous reaction, and can get the excellent cured film of various characteristics.Herein, R is preferably the alkane that carbon number is 1~20 Base, more preferably carbon number be 1~9 alkyl, and then more preferably carbon number be 1~4 alkyl.In addition, alkyl can be straight chain, divide Any, but alkyl of preferably straight chain or branch of branch or cricoid alkyl.Component units (a2) more preferably have under State the Component units of base represented by formula (a2-30).
(in formula (a2-30), R31Indicate hydrogen atom or methyl, R32Indicate that carbon number is 1~20 alkyl).
R32Preferably carbon number be 1~9 alkyl, more preferably carbon number be 1~4 alkyl.In addition, alkyl can for straight chain, Any, but alkyl of preferably straight chain or branch of branch or cricoid alkyl.
As R32Concrete example, can enumerate: methyl, ethyl, normal-butyl, isobutyl group, cyclohexyl and n-hexyl.Wherein, excellent It is selected as isobutyl group, normal-butyl, methyl.
The preferred form-of Component units (a2)
When the polymer containing above-mentioned Component units (a2) is substantially free of Component units (a1), containing above-mentioned composition In the polymer of unit (a2), the content of Component units (a2) is preferably 5 moles of %~90 mole %, more preferably 20 moles of % ~80 moles of %.
When the polymer containing above-mentioned Component units (a2) contains above-mentioned Component units (a1), with regard to the sight of chemical-resistant For point, in the polymer containing above-mentioned Component units (a1) and Component units (a2), the content of Component units (a2) is preferred For 3 moles of %~70 mole %, more preferably 10 moles of %~60 mole %.
Which kind of in turn, in the present invention, no matter form, in all Component units of ingredient A, preferably rub containing 3 The Component units (a2) of your %~70 mole %, the Component units (a2) more preferably containing 10 moles of %~60 mole %.
In the range of above-mentioned numerical value, then by transparent and resistance toization of photosensitive polymer combination cured film obtained Learning moral character becomes good.
< (a3) other Component units >
In the present invention, ingredient A can also have these in addition to above-mentioned Component units (a1) and/or Component units (a2) Other Component units (a3) in addition.Component units (a3) contain the component of polymer for meeting above-mentioned (1) or above-mentioned (2). In addition, the component of polymer containing ingredient A also may include essence in addition to the component of polymer for meeting above-mentioned (1) or above-mentioned (2) The upper component of polymer for containing other Component units (a3) without Component units (a1) and Component units (a2).On except meeting Other than the component of polymer for stating (1) or above-mentioned (2), contain comprising being substantially free of Component units (a1) and Component units (a2) When the component of polymer of other Component units (a3), in all component of polymer, the blending amount of above-mentioned component of polymer is preferred For 60 mass % hereinafter, more preferably 40 mass % hereinafter, be more preferably 20 mass % or less in turn.Additionally, it is preferred that being 1 matter Measure % or more, more preferably 5 mass % or more.
As the monomer for becoming other Component units (a3), there is no particular restriction, such as can enumerate: phenylethylene, (first Base) it is alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, double Ring unsaturated compound class, maleimide compounds class, unsaturated aromatic compound, conjugated diene based compound, Unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.In addition, may be used also as be described hereinafter With the Component units containing acidic group.Monomer as other Component units (a3) can be used alone a kind or by two or more group It closes and uses.
Hereinafter, enumerating the preferred implementation form of the component of polymer containing ingredient A in the present invention, but the present invention is not It is defined in these implementation forms.
- the 1 implementation form-
Meet the component of polymer of (1) and then there is the form of other one kind or two or more Component units (a3).
- the 2 implementation form-
Meet the Component units for the base of the component of polymer of (2) protected containing acidic group by sour decomposability base with (a1) Polymer has the form of other one kind or two or more Component units (a3) in turn.
- the 3 implementation form-
Meet the polymer with the Component units of (a2) containing bridging property base of the component of polymer of (2) and then has 1 The form of kind or other Component units (a3) of more than two kinds.
- the 4 implementation form-
In any implementation form of above-mentioned 1st implementation form~the 3rd implementation form, have extremely in any polymer Form of few Component units for containing acidic group as other Component units (a3).
- the 5 implementation form-
In addition to the component of polymer for meeting above-mentioned (1) or above-mentioned (2), and then has and be substantially free of Component units (a1) And the form of Component units (a2) and the polymer containing other Component units (a3).
- the 6 implementation form-
Combined form of more than two kinds comprising above-mentioned 1st implementation form~the 5th implementation form.
Specifically, Component units (a3) can be enumerated by the Component units of the formation such as following compound: styrene, tertiary fourth oxygen Base styrene, methyl styrene, hydroxy styrenes, α-methylstyrene, acetoxy-styrene, methoxy styrene, ethoxy Base styrene, chlorostyrene, vinylbenzoate, vinyl benzoic acid ethyl ester, 4-HBA (3- methacryl Oxygroup propyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid positive third Ester, (methyl) isopropyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) third Olefin(e) acid benzyl ester, (methyl) isobornyl acrylate, acrylonitrile, ethylene glycol single acetyl acetic acid esters list (methyl) acrylate.Except this In addition, documented compound in 0021~paragraph of paragraph 0024 of Japanese Patent Laid-Open 2004-264623 bulletin can be enumerated.
In addition, for the viewpoint of electrical characteristics, being preferably derived from phenylethylene or tool as other Component units (a3) There are the Component units of the monomer of aliphatic ring type skeleton.Specifically, can enumerate: styrene, t-butoxystyrene, methylbenzene Ethylene, hydroxy styrenes, α-methylstyrene, (methyl) dicyclopentanyl acrylate, (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid isobornyl thiocyanoacetate, (methyl) benzyl acrylate etc..
In turn, as other Component units (a3), for the viewpoint of adhesion, it is preferably derived from (methyl) alkyl acrylate The Component units of base ester.Specifically, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid can be enumerated Propyl ester, (methyl) n-butyl acrylate etc., more preferably (methyl) methyl acrylate.In the Component units for constituting polymer, on The containing ratio for stating Component units (a3) is preferably 60 moles of % hereinafter, more preferably 50 moles of % hereinafter, be more preferably 40 in turn Mole % or less.It can be 0 mole of % as lower limit value, but for example preferably be set as 1 mole of % or more, more preferably be set as 5 and rub You are % or more.In the range of above-mentioned numerical value, then become by the various characteristics of photosensitive polymer combination cured film obtained It obtains well.
Polymer contained in ingredient A preferably has the Component units for containing acidic group as other Component units (a3).Polymer is easy in the developer solution for being dissolved in alkalinity by containing acidic group, and effect of the invention is more effectively sent out It waves.Acidic group in the present invention refers to proton dissociation base of the pKa less than 10.5.In general, use can be formed the monomer of acidic group as Component units containing acidic group, and acidic group is directed into polymer.By in the polymer including such structure containing acidic group At unit, and there is the tendency in the developer solution for being easy to be dissolved in alkalinity.
As acidic group used in the present invention, the acidic group from carboxylic acid group, the acidic group from sulfoamido, source can be illustrated From the acidic group of phosphonic acid base, from sulfonic acidic group, the acidic group from phenolic hydroxyl group, sulfoamido, sulfonyl imide etc., It is preferably derived from the acidic group of carboxylic acid group and/or the acidic group from phenolic hydroxyl group.
Component units used in the present invention containing acidic group are more preferably the Component units for being originated from styrene or are originated from The Component units of vinyl compound are originated from (methyl) acrylic acid and/or the Component units of its ester.
In the present invention, with regard to the viewpoint of sensitivity, particularly preferably containing the Component units with carboxyl or with phenol The Component units of hydroxyl.
Component units containing acidic group are preferably 1 mole of %~80 mole % of the Component units of all component of polymer, More preferably 1 mole of %~50 mole %, and then more preferably 5 moles of %~40 mole %, particularly preferably 5 moles of %~30 Mole %, most preferably 5 moles of %~20 mole %.
It in the present invention, also may include being substantially free of in addition to the component of polymer for meeting above-mentioned (1) or above-mentioned (2) Component units (a1) and Component units (a2) and contain other Component units (a3) polymer.
As such polymer, with the resin of carboxyl preferably on side chain.Such as it can enumerate such as Japanese Patent Laid-Open No. Sho No. 59-44615, Japan Patent examined patent publication 54-34327, Japan Patent examined patent publication 58-12577, Japan Patent examined patent publication No. 54-25957, Japanese Patent Laid-Open No. Sho 59-53836, Japanese Patent Laid-Open No. Sho 59-71048 each bulletin in it is recorded As methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, acid/maleic acid copolymers, Acid cellulose derivative on partial esterification acid/maleic acid copolymers etc. and side chain with carboxyl, with hydroxyl Addition acid anhydrides is into person etc. in polymer, and then can also enumerate the high molecular polymer on side chain with (methyl) acryloyl group and make For preferred polymer.
Such as it can enumerate: (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2- hydroxyl second Documented by ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer, Japanese Patent Laid-Open 7-140654 bulletin (methyl) acrylic acid 2- hydroxy propyl ester/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer, third Olefin(e) acid 2- hydroxyl -3- phenoxy-propyl/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer Object, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc..
In addition to this, Japanese Patent Laid-Open 7-207211 bulletin, Japanese Patent Laid-Open 8-259876 also can be used Number bulletin, Japanese Patent Laid-Open 10-300922 bulletin, Japanese Patent Laid-Open 11-140144 bulletin, Japan Patent are special Open flat 11-174224 bulletin, Japanese Patent Laid-Open 2000-56118 bulletin, Japanese Patent Laid-Open 2003-233179 public affairs Documented well known high-molecular compound in report, Japanese Patent Laid-Open 2009-52020 bulletin etc..
These polymer can only contain a kind, can also contain two or more.
As these polymer, it is possible to use commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (more than, Sartomer (Sartomer) company manufacture), A Lufeng (ARUFON) UC-3000, A Lufeng (ARUFON) UC-3510, A Lufeng (ARUFON) UC-3900, A Lufeng (ARUFON) UC-3910, Ah Lu Feng (ARUFON) UC-3920, A Lufeng (ARUFON) UC-3080 (more than, East Asia synthesizes (share) manufacture), Zhuan Chen (JONCRYL) 690, Zhuan Chen (JONCRYL) 678, Zhuan Chen (JONCRYL) 67, Zhuan Chen (JONCRYL) 586 (more than, BASF (BASF) company manufactures) etc..
The molecular weight-of polymer in ingredient A
The molecular weight of polymer in ingredient A with polystyrene convert Weight-average molecular meter, preferably 1,000~200, 000, more preferably 2,000~50,000 range.In the range of above-mentioned numerical value, then various characteristics are good.The equal molecule of number The ratio (dispersion degree, Mw/Mn) for measuring Mn and weight average molecular weight Mw is preferably 1.0~5.0, and more preferably 1.5~3.5.
Furthermore the measurement of weight average molecular weight or number-average molecular weight in the present invention preferably utilizes gel permeation chromatography (Gel Permeation Chromatography, GPC) is measured.The measurement using gel permeation chromatography in the present invention HLC-8020GPC (Tosoh (Tosoh) (share) manufacture) preferably is used, and uses TSKgel Super HZ M-H, TSK Gel Super HZ4000, TSKgel SuperHZ200 (Tosoh (share) manufacture, 4.6mmID × 15cm) are used as tubing string, use Tetrahydrofuran (Tetrahydrofuran, THF) is used as eluent.
The manufacturing method-of polymer in ingredient A
In addition, the synthetic method about the polymer in ingredient A, it is also known that have various methods, if enumerating an example, can pass through Using radical polymerization initiator, make at least containing be used to form above-mentioned Component units (a1) and above-mentioned Component units (a3) from It is polymerize in organic solvent by the free radical polymerization monomer mixture of base polymerizable monomer to synthesize.In addition, can also lead to So-called high molecular weight reactive is crossed to synthesize.
Ingredient A relative to the total solid content of photosensitive polymer combination, in photosensitive polymer combination of the invention Content be preferably the 10 mass % of mass %~99.9, the more preferably 25 mass % of mass %~98, and then more preferably 35 matter Measure the mass of %~95 %.If the content is in this range, then patternability when being developed becomes well, in addition, can get The higher hardening thing of refractive index.Furthermore the solid content of so-called photosensitive polymer combination, refer to except the volatility such as solvent at Amount other than point.
In addition, the total solid content relative to photosensitive polymer combination, in photosensitive polymer combination of the invention The total content of component of polymer containing ingredient A is preferably the 20 mass % of mass %~99.9, more preferably 50 mass %~98 Quality %, and then more preferably 70 mass of mass %~95 %.Patternability if above range, then when being developed Become good, in addition, can get the higher hardening thing of refractive index.
The heterocyclic compound of (ingredient B) with 2 or more nitrogen-atoms
Photosensitive polymer combination of the invention contains the heterocyclic compound of (ingredient B) with 2 or more nitrogen-atoms.It pushes away Break because ingredient B is adsorbed in the surface of metal oxide particle, therefore generates the mutual electrostatic repulsion of metal oxide particle or solid Repel, the cohesion of metal oxide when especially preventing coating composition and having carried out dry, therefore mist degree becomes smaller.
As ingredient B, in addition to 2 or more nitrogen-atoms, there is no particular restriction, but preferably has 2 or more Nitrogen-atoms as heterocycle ring person heterocyclic compound, more preferably have on 1,3 at least containing the miscellaneous of nitrogen-atoms The compound of ring structure, so more preferably have on 1,3 at least the 5 circle heterocyclic ring structures containing nitrogen-atoms or 6 yuan it is miscellaneous The compound of ring structure.If above-mentioned form, then the dispersibility of available metal oxide particle is more excellent, mist degree is smaller hard Compound.
Furthermore so-called " at least containing the heterocycle structure of nitrogen-atoms on 1,3 ", as long as the nitrogen-atoms key in heterocycle It ties in the structure of the two sides of carbon atom, also may not be 1 on the heterocycle in formal nomenclature and 3.
It includes carbon atom and nitrogen-atoms that the ring person of heterocycle in ingredient B, which is preferably at least, can contain oxygen atom or sulphur in turn Atom particularly preferably includes carbon atom and nitrogen-atoms as ring person.
The quantity of nitrogen-atoms possessed by ingredient B is 2 or more, preferably 2~6, more preferably 2~4.Separately Outside, ingredient B preferably has 2~4 ring persons of the nitrogen-atoms as heterocycle, more preferably has 2 or 3 nitrogen-atoms conducts The ring person of heterocycle, and then more preferably there are 2 ring persons of the nitrogen-atoms as heterocycle.
Heterocycle in ingredient B can be saturated heterocyclic, can also be unsaturated heterocycle, can also be heteroaromatic.
In addition, the heterocycle in ingredient B can and then be condensed with other rings.In addition, being not only as other above-mentioned rings Heterocycle can be aliphatic ring, can also be aromatic rings.
Concrete example as heterocycle structure possessed by ingredient B, it is preferable to enumerate selected from by glyoxaline structure, benzimidazole Structure, 1,2,4- triazole structures, 4,5- dihydro -1,2,4- triazole structure, tetrazolium structure, 2- imidazoline structure, 4- imidazoline knot Structure (2,3- glyoxalidine structure), imidazoles alkyl structure, pyrimidine structure, quinoxaline structure, purine formation, pyridine structure of talking endlessly and pyridine pah (perimidine) ring structure in group composed by structure, it may be more preferable to which ground is enumerated selected from by glyoxaline structure, benzimidazole Structure, 1,2,4- triazole structures, 4,5- dihydro -1,2,4- triazole structure, tetrazolium structure, 2- imidazoline structure, 4- imidazoline knot Ring structure in group composed by structure, imidazoles alkyl structure and pyrimidine structure, can particularly preferably enumerate benzimidazole structure or Imidazoles alkyl structure.If above-mentioned form, then it can get dispersed more excellent, the smaller hardening of mist degree of metal oxide particle Object.
Ingredient B preferably has sulfydryl (- SH) or thioketones base (=S).If above-mentioned form, then it can get metal oxide Dispersed more excellent, the smaller hardening thing of mist degree of particle.
In addition, as ingredient B, preferably by the compound represented by following formula (1).
(in formula (1), R1And R2Separately indicate the organic group of hydrogen atom, halogen atom or monovalence, R1With R2It can key Tie and be the organic group of divalent, R3And R4Separately indicate the organic group of hydrogen atom or monovalence, L1It indicates to form 5 member rings or 6 The concatenating group of the divalent of member ring, R3Or R4With L1It can be bonded and form ring, in addition, when there is the nitrogenous double bond as documented by dotted line When, the bond of dotted line indicates that R is not present2And R4, when the nitrogenous double bond as documented by dotted line is not present, the bond of dotted line is indicated There are R2And R4)。
As R1~R4In monovalence organic group, alkyl (comprising naphthenic base, bicyclic alkyl, tricyclic alkyl), alkene can be enumerated Base (including cycloalkenyl, bicyclic alkenyl), alkynyl, aryl, heterocycle (heterocyclic ring) base (also referred to as heterocycle (heterocycle) base), cyano, hydroxyl, nitro, carboxyl, alkoxy, aryloxy group, siloxy, heterocyclic oxy group, acyloxy, ammonia Formyloxy, alkoxy carbonyloxy group, aryloxy group carbonyloxy group, amino (include alkyl amino, arylamino, heterocyclic amino group), ammonium, Acyl amino, amino carbonyl amino, alkoxycarbonyl amino, aryloxycarbonylamino, sulphamoylamino, alkyl sulphonyl ammonia Base and arlysulfonylamino, sulfydryl, alkylthio group, arylthio, heterocyclethio, alkyl-dithio, aryl disulfide group, miscellaneous epidithio Base, sulfamoyl, sulfo group, alkyl sulphinyl and aryl sulfonyl kia, alkyl sulphonyl and aryl sulfonyl, acyl group, fragrant oxygen Base carbonyl, alkoxy carbonyl, carbamyl, arylazo base and heterocycle azo base, imide, phosphino-, phosphinyl, phosphinyl Oxygroup, phosphinyl amino, phosphono, silylation, diazanyl, urea groups, ghiourea group, boric acid foundation (- B (OH)2), phosphoric acid foundation (- OPO(OH)2), sulphate groups (- OSO3H), other well known substituent groups are as an example.In addition, above-mentioned base can be further by replacing Base replaces.
As R1And R2In monovalence organic group, among these bases, particularly preferably sulfydryl.
In addition, R1And R2In the carbon number of organic group of monovalence be preferably 0~20, more preferably 0~8, particularly preferably 0.
In addition, as R1With R2Bond is formed by the organic group of divalent, can enumerate the work such as side oxygroup, thioketones base, alkylidene For example.Among these bases, particularly preferably thioketones base.
R1And R2It is separately particularly preferably hydrogen atom or sulfydryl, in addition, working as R1With R2It is bonded and forms divalent When organic group, particularly preferably thioketones base.
As R3And R4In monovalence organic group, preferably alkyl or aryl, more preferably morpholinyl methyl or phenyl. In addition, abovementioned alkyl or aryl can be replaced by substituent group.
R3And R4In the carbon number of organic group of monovalence be preferably 0~20, more preferably 1~10, and then more preferably 4~ 8。
R3And R4It is preferably separately hydrogen atom, alkyl or aryl, more preferably hydrogen atom, methyl, morpholinyl A Base or phenyl, and then more preferably hydrogen atom, methyl or phenyl, particularly preferably hydrogen atom or methyl.
L1The concatenating group for indicating the divalent of 5 member rings of formation or 6 member rings, with the carbon atom and 2 nitrogen-atoms one in formula (1) With formation heterocycle.
As the concatenating group of divalent, as long as in formula (1) carbon atom and 2 nitrogen-atoms be formed together 5 circle heterocyclic rings or 6 The base of circle heterocyclic ring, then there is no particular restriction, but its ring person is preferably formed by base by carbon atom and/or nitrogen-atoms, more preferably For the base of the concrete example of the above-mentioned heterocycle structure of formation.Wherein, and then more preferably the base of benzimidazole structure is formed, i.e. 1,2- is sub- Phenyl forms the base of imidazoles alkyl structure, i.e. 1,2- ethylidene, 1,1- dimethyl -1,2- ethylidene or ethylene -1,2- diyl are special It You Xuanwei not 1,2- ethylidene, 1,1- dimethyl -1,2- ethylidene or ethylene -1,2- diyl.
In turn, as ingredient B, more preferably by the compound represented by following formula (1-1) or formula (1-2).
(in formula (1-1) and formula (1-2), R6~R8Separately indicate the organic group of hydrogen atom or monovalence, L2And L3Point The concatenating group of the divalent of 5 member rings of formation or 6 member rings, R are not indicated independently6With L2It can be bonded and form ring, R7Or R8With L3It can key It ties and forms ring).
R in formula (1-1) or formula (1-2)6~R8Meaning and above-mentioned formula (1) in R3And R4It is identical, preferred form It is identical.
In addition, the L in formula (1-1) or formula (1-2)2And L3Meaning and above-mentioned formula (1) in L1It is identical, preferred form Also identical.
The preferred concrete example (AF-1~AF-14) of following presentation ingredient B.But in the present invention, do not had by these The limitation of body example.
Among these, preferably AF-3~AF-14, more preferably AF-3, AF-5, AF-6, AF-9, AF-12, AF-13 or AF-14, particularly preferably AF-5, AF-9, AF-12, AF-13 or AF-14.
The molecular weight of ingredient B is preferably 68~2,000, more preferably 68~1,000, and then more preferably 100~800 Range.In the range of above-mentioned numerical value, then various characteristics are good.
In addition, ingredient B can be used alone a kind, can also be used in combination of two or more.
Relative to the total solid content of resin combination of the invention, ingredient B's in resin combination of the invention contains Amount is preferably the 0.1 mass % of mass %~20, the more preferably 0.5 mass % of mass %~15, and then more preferably 0.5 mass % ~10 mass %.If above range, then it can get dispersed more excellent, the smaller hardening of mist degree of metal oxide particle Object.
(ingredient C) photoacid generator
Photosensitive polymer combination of the invention contains (ingredient C) photoacid generator.As light used in the present invention Acid producing agent, preferably induction wavelength be 300nm or more, preferably wavelength be 300nm~450nm actinic ray and generate acid Compound, but do not limited by its chemical structure.In addition, about directly induction wavelength is not the photoactinic of 300nm or more Photoacid generator, if by with sensitizer and be used to incude wavelength be 300nm or more actinic ray and generate acid chemical combination Object is preferably used after can also then combining with sensitizer.As photoacid generator used in the present invention, preferably generate PKa is the photoacid generator of 4 acid below, and the photoacid generator that more preferably generation pKa is 3 acid below most preferably produces Raw pKa is the photoacid generator of 2 acid below.In addition, pKa is preferably -15 or more.
As the example of photoacid generator, can enumerate: trichloromethyl-s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, Diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc..Among these photoacid generators, just absolutely For the viewpoint of edge and sensitivity, it is preferable to use oxime sulfonate compounds.These photoacid generators can be used alone a kind, Or two or more is applied in combination.As trichloromethyl-s-triazine, two virtue base Iodonium salts, triaryl matte salt, quarternary ammonium salt The concrete example of class and diazomethane derivative can illustrate 0083~section of paragraph of Japanese Patent Laid-Open 2011-221494 bulletin Fall documented compound in 0088.
As oxime sulfonate compounds, i.e., with the compound of oxime sulfonates structure, it is preferable to illustrate containing by following The compound of oxime sulfonates structure represented by formula (B1).
(in formula (B1), R21Indicate alkyl or aryl, wave-like line part indicates the bond position with other bases).
Any base can be substituted, R21In alkyl can be straight-chain, can also be branch-like, can also for ring-type.It says below Bright allowed substituent group.
As R21Alkyl, preferably carbon number be 1~10 straight-chain alkyl or branch-like alkyl.R21Alkyl can be by The alkoxy or naphthenic base that aryl that carbon number is 6~11, carbon number are 1~10 (include 7,7- dimethyl -2- oxo norborny Equal endocyclics alcyl, preferably bicyclic alkyl etc.) replace.
As R21Aryl, preferably carbon number be 6~11 aryl, more preferably phenyl or naphthyl.R21Aryl can be by The alkoxy or halogen atom that alkyl that carbon number is 1~10, carbon number are 1~10 replaces.
Containing by the above compound of the oxime sulfonates structure represented by above-mentioned formula (B1) be by following formula (B2) represented by Oxime sulfonate compounds it is also preferred that.
(in formula (B2), R42Indicate alkyl or aryl, X indicate alkyl, alkoxy or halogen atom, m4 indicate 0~3 it is whole Number, when m4 is 2 or 3, multiple X can be identical, can also be different).
Alkyl as X is preferably the straight-chain alkyl or branch-like alkyl that carbon number is 1~4.
Alkoxy as X is preferably the straight-chain alkoxy or branch-like alkoxy that carbon number is 1~4.
Halogen atom as X is preferably chlorine atom or fluorine atom.
M4 is preferably 0 or 1.In above-mentioned formula (B2), particularly preferably m4 is that 1, X is methyl, and the position of substitution of X is ortho position, R42For carbon number be 1~10 straight-chain alkyl, 7,7- dimethyl -2- oxo norbornylmethyl or to the change of toluyl groups Close object.
Containing by the compound of the oxime sulfonates structure represented by above-mentioned formula (B1) be by following formula (B3) represented by oxime Sulfonate compound it is also preferred that.
(in formula (B3), R43Meaning and formula (B2) in R42It is identical, X1Indicate that halogen atom, hydroxyl, carbon number are 1~4 Alkyl, alkoxy, cyano or the nitro that carbon number is 1~4, n4 indicate 0~5 integer).
As the R in above-mentioned formula (B3)43, preferably methyl, ethyl, n-propyl, normal-butyl, n-octyl, trifluoromethyl, five Fluoro ethyl, perfluor-n-propyl, perfluor-normal-butyl, p-methylphenyl, 4- chlorphenyl or pentafluorophenyl group, particularly preferably n-octyl.
X1Preferably carbon number is 1~5 alkoxy, more preferably methoxyl group.
N4 is preferably 0~2 integer, and particularly preferably 0 or 1.
As the concrete example by the compound represented by above-mentioned formula (B3), can enumerate: α-(methylsulfonyloxyimino) Benzyl cyanide, α-(ethylsulfonyloxy imino group) benzyl cyanide, α-(n-propyl sulfonyloxyimino) benzyl cyanide, α-(normal-butyl Sulfonyloxyimino) benzyl cyanide, α-(4- tosyloxy imino group) benzyl cyanide, α-[(methylsulfonyloxyimino)- 4- methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxy imino group) -4- methoxyphenyl] acetonitrile, α-[(n-propyl sulphonyl oxygen Base imino group) -4- methoxyphenyl] acetonitrile, α-[(normal-butyl sulfonyloxyimino) -4- methoxyphenyl] acetonitrile, α - [(4- tosyloxy imino group) -4- methoxyphenyl] acetonitrile.
As the concrete example of preferred oxime sulfonate compounds, following compounds (i)~compound (viii) etc. can be enumerated, These compounds can be used alone a kind, or be used in combination of two or more.Compound (i)~compound (viii) can be used as commercially available product and obtain ?.In addition, can be also applied in combination with other kinds of (C) photoacid generator.
The compound of oxime sulfonates structure represented by as containing by above-mentioned formula (B1), represented by following formula (OS-1) Compound it is also preferred that.
In above-mentioned formula (OS-1), R101Indicate hydrogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl Base, sulfamoyl, sulfo group, cyano, aryl or heteroaryl.R102Indicate alkyl or aryl.
X101Expression-O- ,-S- ,-NH- ,-NR105-、-CH2-、-CR106H- or-CR105R107, R105~R107Indicate alkane Base or aryl.
R121~R124Separately indicate hydrogen atom, halogen atom, alkyl, alkenyl, alkoxy, amino, alkoxy carbonyl Base, alkyl-carbonyl, aryl carbonyl, amide groups, sulfo group, cyano or aryl.R121~R124In 2 can mutually be bonded respectively and Form ring.
As R121~R124, it is separately preferably hydrogen atom, halogen atom or alkyl, in addition, also preferably Enumerate R121~R124In at least two be mutually bonded and formed the form of aryl.Wherein, for the viewpoint of sensitivity, preferably For R121~R124It is the form of hydrogen atom.
Already described functional group can further have substituent group.
Compound represented by being more preferably by the compound represented by above-mentioned formula (OS-1) by following formula (OS-2).
In above-mentioned formula (OS-2), R101、R102、R121~R124Meaning respectively with the R in formula (OS-1)101、R102、R121~ R124It is identical, additionally, it is preferred that example is also identical.
R among these, in more preferably above-mentioned formula (OS-1) and above-mentioned formula (OS-2)101For the shape of cyano or aryl State is most preferably indicated by above-mentioned formula (OS-2), and R101For the form of cyano, phenyl or naphthyl.
In addition, in oxime sulfonate compounds in the present invention, about oxime or stereochemical structure (E, Z of benzothiazole ring Deng), it respectively can be any stereochemical structure, can also be mixture.
As the concrete example that may be suitably used to the compound represented by (OS-1) of the invention by above-mentioned formula, can enumerate day Documented compound (exemplary compounds b-1 in 0128~paragraph of paragraph 0132 of this patent special open 2011-221494 bulletin ~exemplary compounds b-34), but the present invention is not limited to this.
In the present invention, as containing the compound by the oxime sulfonates structure represented by above-mentioned formula (B1), preferably by Oxime sulfonate compounds represented by following formula (OS-3), following formula (OS-4) or following formula (OS-5).
(in formula (OS-3)~formula (OS-5), R22、R25And R28Separately indicate alkyl, aryl or heteroaryl, R23、 R26And R29Separately indicate hydrogen atom, alkyl, aryl or halogen atom, R24、R27And R30Separately indicate halogen Atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X1~X3Separately indicate oxygen atom or Sulphur atom, n1~n3Separately indicate 1 or 2, m1~m3Separately indicate 0~6 integer).
In above-mentioned formula (OS-3)~formula (OS-5), R22、R25And R28In alkyl, aryl or heteroaryl can have substituent group.
In above-mentioned formula (OS-3)~formula (OS-5), as R22、R25And R28In alkyl, can preferably have substituent group The alkyl that total carbon number is 1~30.
In addition, in above-mentioned formula (OS-3)~formula (OS-5), as R22、R25And R28In aryl, can preferably have substitution The aryl that total carbon number of base is 6~30.
In addition, in above-mentioned formula (OS-3)~formula (OS-5), as R22、R25And R28In heteroaryl, can preferably have and take The heteroaryl that total carbon number of Dai Ji is 4~30.
In above-mentioned formula (OS-3)~formula (OS-5), R22、R25And R28As long as heteroaryl at least one ring in is miscellaneous aromatic rings , such as miscellaneous aromatic rings and phenyl ring can also carry out contracting ring.
In above-mentioned formula (OS-3)~formula (OS-5), R23、R26And R29Preferably hydrogen atom, alkyl or aryl, more preferably hydrogen Atom or alkyl.
In above-mentioned formula (OS-3)~formula (OS-5), there are 2 or more R preferably in compound23、R26And R29In 1 It is a or 2 be alkyl, aryl or halogen atom, more preferably 1 be alkyl, aryl or halogen atom, particularly preferably 1 is Alkyl and remaining as hydrogen atom.
As R23、R26And R29In alkyl, can preferably have substituent group total carbon number be 1~12 alkyl, more preferably For that can have the alkyl that total carbon number of substituent group is 1~6.
As R23、R26And R29In aryl, can preferably have substituent group total carbon number be 6~30 aryl.
In above-mentioned formula (OS-3)~formula (OS-5), X1~X3Separately indicate O or S, preferably O.
In above-mentioned formula (OS-3)~formula (OS-5), contain X1~X3Ring as ring person is 5 member rings or 6 member rings.
In above-mentioned formula (OS-3)~formula (OS-5), n1~n3It separately indicates 1 or 2, works as X1~X3When for O, n1~n3 It is preferably separately 1, in addition, working as X1~X3When for S, n1~n3It is preferably separately 2.
In above-mentioned formula (OS-3)~formula (OS-5), R24、R27And R30Separately indicate halogen atom, alkyl, alcoxyl Base, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.Wherein, preferably R24、R27And R30It is separately alkyl or alkane Oxygroup.
R24、R27And R30In alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl can have substitution Base.
In above-mentioned formula (OS-3)~formula (OS-5), as R24、R27And R30In alkyl, can preferably have substituent group The alkyl that total carbon number is 1~30.
In above-mentioned formula (OS-3)~formula (OS-5), as R24、R27And R30In alkoxy, can preferably have substituent group Total carbon number be 1~30 alkoxy.
In addition, in above-mentioned formula (OS-3)~formula (OS-5), m1~m3The separately integer of expression 0~6, preferably 0~ 2 integer, more preferably 0 or 1, particularly preferably 0.
In addition, about each substituent group of above-mentioned formula (OS-3)~formula (OS-5), Japanese Patent Laid-Open 2011-221494 The preferred range of the substituent group of (OS-3)~(OS-5) documented by 0092~paragraph of paragraph 0109 of bulletin is similarly excellent Choosing.
In addition, the compound of the oxime sulfonates structure represented by containing by above-mentioned formula (B1) is particularly preferably by following formula (OS-6) oxime sulfonate compounds represented by either one or two of~formula (OS-11).
(in formula (OS-6)~formula (OS-11), R301~R306Indicate alkyl, aryl or heteroaryl, R307Indicate hydrogen atom or Bromine atom, R308~R310、R313、R316And R318Separately indicate hydrogen atom, the alkyl that carbon number is 1~8, halogen atom, chlorine Methyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, R311And R314Separately indicate hydrogen atom, halogen Atom, methyl or methoxy, R312、R315、R317And R319Separately indicate hydrogen atom or methyl).
Preferred range and Japanese Patent Laid-Open 2011-221494 bulletin in above-mentioned formula (OS-6)~formula (OS-11) 0110~paragraph of paragraph 0112 in documented by (OS-6)~(OS-11) preferred range it is identical.
As the concrete example by the oxime sulfonate compounds represented by above-mentioned formula (OS-3)~above-mentioned formula (OS-5), can enumerate Documented compound in 0114~paragraph of paragraph 0120 of Japanese Patent Laid-Open 2011-221494 bulletin, but the present invention is simultaneously It is not limited to these compounds.
In photosensitive polymer combination of the invention, relative to poly- containing ingredient A in photosensitive polymer combination 100 mass parts of polymer component, (ingredient C) photoacid generator preferably use 0.1 mass parts~10 mass parts, more preferably use 0.5 mass parts~10 mass parts.
In addition, ingredient C can be used alone a kind, can also be used in combination of two or more.
(ingredient D) metal oxide particle
Resin combination of the invention contains metal oxide particle for the purpose of adjusting refractive index or translucency.Gold Category oxide particle can get refractive index height, transparent excellent normal Photosensitive resin because the transparency is high, has translucency Composition.
Ingredient D is preferably the refractive index person that refractive index is higher than the resin combination comprising the material in addition to the particle, tool For body, the particle that the refractive index more preferably in the light of the wavelength with 400nm~750nm is 1.50 or more, so that it is more excellent Be selected as refractive index be 1.70 or more particle, particularly preferably refractive index be 1.90 or more particle.Additionally, it is preferred that being refractive index For 2.80 particles below.
Herein, the refractive index in the light of the so-called wavelength with 400nm~750nm is 1.50 or more, is referred to above-mentioned Mean refractive index in the light of the wavelength of range is 1.50 or more, without the folding in all light of the wavelength with above range Penetrating rate is 1.50 or more.In addition, mean refractive index is by the measurement of the refractive index of each light for the wavelength with above range The summation of value divided by measuring point the resulting value of quantity.
Furthermore the metal of the metal oxide particle in the present invention also includes the semimetals such as B, Si, Ge, As, Sb, Te.
The metal oxide particle high as translucency, refractive index, preferably comprising Be, Mg, Ca, Sr, Ba, Sc, Y, La, The equiatomic oxide of Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te Particle, more preferably titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin-oxide, antimony/tin-oxide, Jin Ergeng Preferably titanium oxide, titanium composite oxide, zirconium oxide, particularly preferably titanium oxide, zirconium oxide, most preferably titanium dioxide.Make For titanium dioxide, the preferably extra high rutile-type of refractive index.In order to assign dispersion stabilization, organic material pair can also be used The surface of these metal oxide particles is handled.
The average primary particle diameter of metal oxide particle is preferably 1nm~200nm, more preferably 1nm~100nm, in turn More preferably 1nm~80nm, particularly preferably 1nm~50nm.If above range, then can get particle dispersibility it is excellent and Refractive index height and the superior hardening thing of the transparency.
The average primary particle diameter of metal oxide particle can observe dispersed metal oxygen by transmission electron microscope Compound particle, and found out according to photo obtained.Specifically, the projected area of metal oxide particle is found out, it will be right The area diameter projected of Ying Yuqi is set as the average primary particle diameter of metal oxide particle.Furthermore by average one in the present invention Secondary partial size is set as the arithmetic mean of instantaneous value to area diameter projected calculated by 300 metal oxide particles.
In addition, in the present invention, it is possible to use index of the number average particle size as average primary particle diameter.In the present invention The number average particle size of metal oxide particle refers to following value: by that will contain metal using propylene glycol methyl ether acetate The mixed liquor or dispersion liquid of oxide particle are diluted to 80 times, and are surveyed using dynamic light scattering method to dilution obtained Fixed value obtained.Preferably the measurement is carried out using Mai Qike (Microtrac) UPA-EX150 of day machine dress (share) manufacture Number average particle size obtained.
There is no particular restriction for the refractive index of metal oxide particle, but for the viewpoint with regard to obtaining high refractive index, preferably 1.70~2.80, more preferably 1.90~2.70.
In addition, the specific surface area of metal oxide particle is preferably 10m2/ g~400m2/ g, more preferably 20m2/ g~ 200m2/ g, most preferably 30m2/ g~150m2/g。
There is no particular restriction for the shape of metal oxide particle.It may be, for example, rice-shaped, spherical, cubic, fusiform Or indefinite shape.
Metal oxide particle can also be carry out surface treatment person by organic compound.For having for surface treatment The example of machine compound includes: polyalcohol, alkanolamine, stearic acid, silane coupling agent and titanate esters coupling agent.Wherein, preferably Stearic acid.
Surface treatment can be implemented by independent a kind of surface treating agent, can also be subject to surface treating agent of more than two kinds Combination is to implement.
In addition, the surface of metal oxide particle by the oxides such as aluminium, silicon, zirconium oxide cover it is also preferred that.Weatherability as a result, Further promoted.
As the metal oxide particle in the present invention, it is preferable to use commercially available product.Specifically, can for example enumerate: TTO series (TTO-51 (A), TTO-51 (C) etc.), TTO-S, V system of industry (share) manufacture are originated in as the stone of Titanium particles It arranges (TTO-S-1, TTO-S-2, TTO-V-3 etc.), the MT of Supreme Beingization (Tayca) (share) manufacture is serial (MT-01, MT-05 etc.), makees It opens up Lake (Optolake) TR-502, Ao Pu for the Ao Pu of stannic oxide-titanium oxide compound particle and opens up Lake (Optolake) TR- 504, the Ao Pu as silica-titania compound particle open up Lake (Optolake) TR-503, Ao Pu and open up Lake (Optolake) TR-513, Ao Pu, which open up Lake (Optolake) TR-520, Ao Pu and open up Lake (Optolake) TR-521, Ao Pu, opens up Lake (Optolake) TR-527, Zirconia particles (high-purity chemical research institute (share) manufacture), tin oxide-zirconium oxide is compound Particle (waves catalyst chemical conversion industry (share) manufacture day), Bellaire (Biral) Nb-X10 (Duo Muhua as niobium oxide particle Learn (share) manufacture) etc..
In addition, ingredient D can be used alone a kind, can also be used in combination of two or more.
As long as the content consideration of the metal oxide particle in resin combination of the invention is obtained to by resin combination Refractive index or translucency etc. required by the optical component obtained, and it is suitable for decision, but relative to resin combination of the invention The total solid content of object, preferably 10 mass % or more, more preferably 30 mass % or more, so more preferably 40 mass % with On.Additionally, it is preferred that being 80 mass % hereinafter, more preferably 70 mass % or less.
In the present invention, particle can be used as following dispersion liquid also come for using, above-mentioned dispersion liquid is by appropriate Dispersing agent and solvent in, carry out the prepared dispersion liquid of mixing dispersion using mixing arrangements such as ball mill, rod mills.About Dispersing agent, will be aftermentioned.
Solvent used in preparation as above-mentioned dispersion liquid, such as in addition to aftermentioned (ingredient E) solvent, can enumerate 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-2-propanol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 3- methyl-1-butanol, Alcohols such as 2- methyl -2- butanol, neopentyl alcohol, cyclopentanol, 1- hexanol, cyclohexanol etc..
These solvents, which can be used alone, or to be used in mixed way two or more by a kind.
(ingredient E) solvent
Photosensitive polymer combination of the invention contains (ingredient E) solvent.Photosensitive polymer combination of the invention is preferred To be made as making essential component of the invention and aftermentioned arbitrary ingredient be dissolved in solution made of in (ingredient E) solvent It is standby.
As solvent used in photosensitive polymer combination of the invention, well known solvent can be used, can illustrate: second Glycol monoalkyl ethers, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, the third two Alcohol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate Class, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone, Amides, lactone etc..In addition, the concrete example as solvent used in photosensitive polymer combination of the invention, it can also Enumerate documented solvent in 0174~paragraph of paragraph 0178 of Japanese Patent Laid-Open 2011-221494 bulletin.
In addition, optionally can also further add benzyl ether, two hexyl ethers, ethyleneglycol monophenylether acetic acid into these solvents Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, benzylalcohol, fennel Ether, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, propene carbonate etc. are molten Agent.
These solvents, which can be used alone, or to be used in mixed way two or more by a kind.Solvent for use in the present invention is preferably single Solely using a kind or and with 2 kinds.
In addition, preferably boiling point is 130 DEG C or more, less than 160 DEG C of solvent as ingredient E, boiling point is 160 DEG C or more Solvent or these mixture.
Be 130 DEG C or more, less than 160 DEG C of solvent as boiling point, can illustrate: (boiling point is propylene glycol methyl ether acetate 146 DEG C), propylene glycol monoethyl ether acetate (boiling point is 158 DEG C), propylene glycol methyl-n-butyl ether (boiling point is 155 DEG C), propylene glycol Methyl-positive propyl ether (boiling point is 131 DEG C).
The solvent for being 160 DEG C or more as boiling point, can illustrate: 3- ethoxyl ethyl propionate (boiling point is 170 DEG C), diethyl two Alcohol methyl ethyl ether (boiling point is 176 DEG C), propylene glycol monomethyl ether propionate (boiling point is 160 DEG C), dipropylene glycol methyl ether acetic acid esters (boiling point is 213 DEG C), 3- methoxyl group butyl ether acetic acid esters (boiling point is 171 DEG C), diethylene glycol diethyl ether (boiling point is 189 DEG C), two Glycol dimethyl ether (boiling point is 162 DEG C), propylene-glycol diacetate (boiling point is 190 DEG C), diethylene glycol monoethyl ether acetic acid esters (boiling Point be 220 DEG C), dimethyl ether (boiling point is 175 DEG C), 1,3-BDO diacetate esters (boiling point is 232 DEG C).
Among these, as solvent, preferably propylene-glycol monoalky lether acetate esters, particularly preferably propylene glycol monomethyl ether Acetic acid esters.
Relative to 100 mass parts of component of polymer containing ingredient A in photosensitive polymer combination, of the invention is photosensitive The content of (ingredient E) solvent in property resin combination is preferably 50 mass parts~95 mass parts, and more preferably 60 mass parts~ 90 mass parts.
(ingredient F) crosslinking agent
Optionally, photosensitive polymer combination of the invention preferably contains crosslinking agent.By add crosslinking agent, can make by Photosensitive polymer combination of the invention cured film obtained becomes stronger film.
As crosslinking agent, as long as Yin Re and generate cross-linking reaction person, then there is no restriction (still, except ingredient A).Example Such as, can add intramolecular as described below has 2 or more epoxy groups or the compound of oxetanylmethoxy, contains alkoxy first The crosslinking agent of base, the compound at least one ethylene unsaturated double-bond or blocked isocyanate compound etc..
Relative to 100 mass parts of total solid content of photosensitive polymer combination, photosensitive polymer combination of the invention In the additive amount of crosslinking agent be preferably 0.01 mass parts~50 mass parts, more preferably 0.1 mass parts~30 mass parts, in turn More preferably 0.5 mass parts~20 mass parts.By being added in the range, it can get mechanical strength and solvent resistance be excellent Different cured film.Crosslinking agent can also be used together by more than one, and in the case, all crosslinking agents be added up to calculate content.
<intramolecular is with 2 or more epoxy groups or the compound of oxetanylmethoxy (oxetanyl)>
The concrete example of compound as intramolecular with 2 or more epoxy groups, can enumerate: bisphenol A type epoxy resin, Bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin Deng.
These compounds can be used as commercially available product and obtain.Such as it can enumerate: JER157S70, JER157S65 (Mitsubishi Chemical (share) manufacture) etc., documented commercially available product etc. in the paragraph 0189 of Japanese Patent Laid-Open 2011-221494 bulletin.
In addition to this, it can also enumerate: Ai Dike resin (ADEKA RESIN) EP-4000S, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike resin (ADEKA RESIN) EP-4010S, Ai Dike resin (ADEKA RESIN) EP- 4011S (more than, Ai Dike (ADEKA) (share) manufacture), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (more than, Ai Dike (share) manufacture), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、 EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX- 212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、 DLC-301, DLC-402 (more than, long rapids chemical conversion (Nagase chemteX) (share) manufacture), YH-300, YH-301, YH- 302, YH-315, YH-324, YH-325 (more than, Nippon Steel chemistry (share) manufacture) etc..
These compounds can be used alone or above section level to be applied in combination 2 by a kind.
Among these compounds, it may be more preferable to which bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolac are enumerated in ground Type epoxy resin and aliphatic epoxy resin can particularly preferably enumerate bisphenol A type epoxy resin.
Sub- imperial oxa- ring fourth can be used in the concrete example of compound as intramolecular with 2 or more oxetanylmethoxies Alkane (ARON OXETANE) OXT-121, OXT-221, OX-SQ, PNOX (more than, East Asia synthesizes (share) manufacture).
In addition, the compound containing oxetanylmethoxy is preferably used alone or mixes with the compound containing epoxy group It uses.
In addition, it may also be preferred to use the paragraph of Japanese Patent Laid-Open 2012-8223 bulletin as other crosslinking agents In 0107~paragraph 0108 documented by the crosslinking agent containing alkoxy methyl and have at least one ethylene unsaturated double-bond Compound etc..As the crosslinking agent containing alkoxy methyl, preferably aikoxymethytated glycolurils.
<blocked isocyanate compound>
In photosensitive polymer combination of the invention, it also may be preferable for ground uses the conduct of blocked isocyanate based compound Crosslinking agent.As long as blocked isocyanate compound has the compound of blocked isocyanate base, then there is no particular restriction, But for indurative viewpoint, compound of preferably 1 intramolecular with 2 or more blocked isocyanate bases.
Furthermore the blocked isocyanate base in the present invention refers to the base that isocyanate group can be generated because of heat, for example, can Preferably illustrating makes sealer be reacted the base to protect isocyanate group with isocyanate group.In addition, above-mentioned enclosed type is different Cyanic acid ester group is preferably the base that isocyanate group can be generated because of 90 DEG C~250 DEG C of heat.
In addition, as blocked isocyanate compound, skeleton is not particularly limited, as long as having 2 in 1 molecule The compound of isocyanate group then can be any compound, can be aliphatic, alicyclic or aromatic polyisocyanate, example It can such as properly use: 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI), isophorone diisocyanate, 1,6- Hexamethylene diisocyanate, 1,3- trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4- trimethyls Hexamethylene diisocyanate, 2,4,4- trimethyl hexamethylene diisocyanates, 1,9-, nine methylene diisocyanate, 1, 10- decamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-diethyl ether diisocyanate, diphenyl methane- 4,4 '-diisocyanate, ortho-xylene diisocyanate, m xylene diisocyanate, paraxylene diisocyanate, methylene Base bis- (cyclohexyl isocyanates), hexamethylene -1,3- dimethylene diisocyanate, hexamethylene-two isocyanide of Isosorbide-5-Nitrae-dimethylene Acid esters, 1,5- naphthalene diisocyanate, paraphenylene diisocyanate, 3,3 '-xylene -4,4 '-diisocyanate, 4,4 ' - Diphenyl ether diisocyanate, tetrachloro phenylene vulcabond, norbornene alkyl diisocyanate, hydrogenation 1,3- xylylene two Isocyanates hydrogenates the isocyanate compounds such as Isosorbide-5-Nitrae-eylylene diisocyanate and derives from these compounds pre- The compound of the skeleton of polymers type.Among these, particularly preferably toluene di-isocyanate(TDI) (Tolylene Diisocyanate, ) or methyl diphenylene diisocyanate (Diphenyl Methane Diisocyanate, MDI), two isocyanide of hexa-methylene TDI Acid esters (Hexamethylene Diisocyanate, HDI), isophorone diisocyanate (Isophorone Diisocyanate, IPDI).
As the parent structure of the blocked isocyanate compound in photosensitive polymer combination of the invention, can enumerate: Biuret form, isocyanurate type, adduct type, two functional prepolymer types etc..
It as the sealer for the enclosed construction for forming above-mentioned blocked isocyanate compound, can enumerate: oxime compound, interior Amide compound, phenolic compounds, alcoholic compound, amine compounds, activity methene compound, pyrazole compound, mercaptan compound, Imidazole compound, imide series compound etc..Among these, it is particularly preferably selected from oxime compound, lactam compound, phenol Compound, alcoholic compound, amine compounds, activity methene compound, the sealer in pyrazole compound.
As above-mentioned oxime compound, aldoxime and ketoxime can be enumerated, specifically, can illustrate: acetoxime, formaldoxime, hexamethylene Alkane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diphenyl-ketoxime etc..
It as above-mentioned lactam compound, can illustrate: epsilon-caprolactams, butyrolactam etc..
It as above-mentioned phenolic compounds, can illustrate: phenol, naphthols, cresols, xylenol, halogen-substituted phenol etc..
It as above-mentioned alcoholic compound, can illustrate: methanol, ethyl alcohol, propyl alcohol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, third Glycol monoalkyl ether, lactic acid alkyl ester etc..
As above-mentioned amine compounds, level-one amine and secondary amine can be enumerated, can be aromatic amine, aliphatic amine, cycloaliphatic amines It is any, can illustrate: aniline, diphenylamine, aziridine, polyethyleneimine etc..
It as above-mentioned activity methene compound, can illustrate: diethyl malonate, dimethyl malenate, acetoacetate second Ester, methyl acetoacetate etc..
It as above-mentioned pyrazole compound, can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc..
It as above-mentioned mercaptan compound, can illustrate: alkyl hydrosulfide, aryl mercaptan etc..
The blocked isocyanate compound of photosensitive polymer combination for use in the present invention can be used as commercially available product and obtain , such as preferably use: the Crow AP of resistance to moral Si Tebu (Coronate AP Stable) M, the resistance to moral in Crow (Coronate) 2503,2515,2507,2513,2555, the resistance to moral of rice Leo (Millionate) MS-50 (more than, Japanese polyurethane industry (Nippon Polyurethane Industry) (share) manufacture), the resistance to moral of Plutarch (Takenate) B-830, B-815N, B- 820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (more than, Mitsui Chemicals (share) manufacture), Duo Naide (Duranate)17B-60PX、17B-60P、TPA-B80X、TPA-B80E、MF-B60X、MF-B60B、MF-K60X、MF-K60B、 E402-B80B, SBN-70D, SBB-70P, K6000 (more than, Asahi Chemical Industry's chemistry (Asahi Kasei Chemicals) (share) Manufacture), De Shimo all (Desmodur) BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Su meter Dou (Sumidur) BL3175 (more than, firmly change Baeyer polyurethane (Sumika Bayer Urethane) (share) manufacture) etc..
(ingredient G) antioxidant
Photosensitive polymer combination of the invention preferably contains antioxidant.Well known antioxidant can be contained as anti- Oxidant.By adding antioxidant, has the advantage that the coloring that can prevent cured film or can reduce and drawn by decomposing The film thickness risen is reduced, in addition, heat resistant transparent is excellent.
As such antioxidant, such as can enumerate: phosphorous antioxidant, amides, hydrazides, amine system of being obstructed are anti-oxidant Agent, sulfur antioxidant, phenolic antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thio sulphur Hydrochlorate, hydroxylamine derivative etc..Among these antioxidants, with regard to the coloring of cured film, film thickness reduction viewpoint for, particularly preferably For phenolic antioxidant, acyl amine antioxidant, hydrazides system antioxidant, sulfur antioxidant.These antioxidants can be independent Using a kind, two or more can also be used in mixed way.
It as the commercially available product of phenolic antioxidant, such as can enumerate: Ai Di Coase tower wave (Adekastab) AO-15, Ai Di Coase tower wave (Adekastab) AO-18, Ai Di Coase tower wave (Adekastab) AO-20, Ai Di Coase tower wave (Adekastab) AO-23, Ai Di Coase tower wave (Adekastab) AO-30, Ai Di Coase tower wave (Adekastab) AO-37, Ai Di Coase tower wave (Adekastab) AO-40, Ai Di Coase tower wave (Adekastab) AO-50, Ai Di Coase tower wave (Adekastab) AO-51, Chinese mugwort Enlightening Coase tower wave (Adekastab) AO-60, Ai Di Coase tower wave (Adekastab) AO-70, Ai Di Coase tower wave (Adekastab) AO-80, Ai Di Coase tower wave (Adekastab) AO-330, Ai Di Coase tower wave (Adekastab) AO- 412S, Ai Di Coase tower wave (Adekastab) AO-503, Ai Di Coase tower wave (Adekastab) A-611, Ai Di Coase tower wave (Adekastab) A-612, Ai Di Coase tower wave (Adekastab) A-613, Ai Di Coase tower wave (Adekastab) PEP-4C, Ai Di Coase tower wave (Adekastab) PEP-8, Ai Di Coase tower wave (Adekastab) PEP-8W, Ai Di Coase tower wave (Adekastab) PEP-24G, Ai Di Coase tower wave (Adekastab) PEP-36, Ai Di Coase tower wave (Adekastab) PEP- 36Z, Ai Di Coase tower wave (Adekastab) HP-10, Ai Di Coase tower wave (Adekastab) 2112, Ai Di Coase tower wave (Adekastab) 260, Ai Di Coase tower wave (Adekastab) 522A, Ai Di Coase tower wave (Adekastab) 1178, Ai Dike Si Tabo (Adekastab) 1500, Ai Di Coase tower wave (Adekastab) C, Ai Di Coase tower wave (Adekastab) 135A, Chinese mugwort Enlightening Coase tower wave (Adekastab) 3010, Ai Di Coase tower wave (Adekastab) TPP, Ai Di Coase tower wave (Adekastab) CDA-1, Ai Di Coase tower wave (Adekastab) CDA-6, Ai Di Coase tower wave (Adekastab) ZS-27, Ai Di Coase tower wave (Adekastab) ZS-90, Ai Di Coase tower wave (Adekastab) ZS-91 (more than, Ai Dike (share) manufacture), Yi Jialesi (Irganox) 245FF, Yi Jialesi (Irganox) 1010FF, Yi Jialesi (Irganox) 1010, Yi Jialesi (Irganox) MD1024, Yi Jialesi (Irganox) 1035FF, Yi Jialesi (Irganox) 1035, Yi Jialesi (Irganox) 1098, Yi Jialesi (Irganox) 1330, Yi Jialesi (Irganox) 1520L, Yi Jialesi (Irganox) 3114, Yi Jialesi (Irganox) 1726, easily plus Floex (Irgafos) 168, Yi Jiamode (Irgamod) 295 (BASF is public Department's manufacture), slave refined (Tinuvin) 405 (BASF AG's manufacture) etc..Wherein, Ai Di Coase tower wave can be properly used (Adekastab) AO-60, Ai Di Coase tower wave (Adekastab) AO-80, Yi Jialesi (Irganox) 1726, Yi Jialesi (Irganox) 1035, Yi Jialesi (Irganox) 1098, refined (Tinuvin) 405 of slave.
Relative to the total solid content of photosensitive polymer combination, the content of antioxidant is preferably 0.1 mass %~10 Quality %, the more preferably 0.2 mass % of mass %~5, particularly preferably 0.5 mass of mass %~4 %.By setting it as the range Interior, the sensitivity for being formed by film when can get the adequately transparency and pattern formation also becomes good.
In addition, can also will be documented various in " new development (Nikkan Kogyo Shimbun (share)) of polymeric additive " Ultraviolet absorbing agent or matal deactivator etc. are added to photoresist of the invention as the additive other than antioxidant In composition.
(ingredient H) dispersing agent
Photosensitive polymer combination of the invention preferably contains (ingredient H) dispersing agent.By containing dispersing agent, and can be into One step promotes the dispersibility of ingredient C in the composition.
Furthermore whether ingredient B is used as dispersing agent to function and indefinite, but (ingredient H) dispersing agent in the present invention is Compound other than ingredient B.
As (ingredient H) dispersing agent, for example, can be suitable for select well known pigment dispersing agent come using, but particularly preferably after (the ingredient S) stated is indicated by formula (S) and the dispersing agent at least one kind of acidic group.
As (ingredient H) dispersing agent, it is preferable to use macromolecule dispersing agent.Furthermore so-called macromolecule dispersing agent, refers to The dispersing agent that molecular weight (weight average molecular weight) is 1,000 or more.
As (ingredient H) dispersing agent, multiple compounds can be used, specifically, can for example enumerate: organosiloxane polymerization Object KP341 (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), (methyl) acrylic acid series (co) polymer Po Lifuluo (Polyflow) No.75, No.90, No.95 (common prosperity society chemistry (share) manufacture), the cationic systems interface such as W001 (abundant quotient's (share) manufacture) are living Property agent；Polyoxyethylene laurel ether, polyoxyethylene stearyl base ether, polyoxyl 10 oleyl ether, polyoxethylene octylphenyl phenylate, polyoxyethylene nonyl Nonionic systems circle such as base phenylate, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid esters Face activating agent；The anionic systems interfacial agents such as W004, W005, W017 (abundant quotient's (share) manufacture)；Efka (EFKA) -46, Efka (EFKA) -47, Efka (EFKA) -47EA, Efka polymer (EFKA Polymer) 100, Efka polymer (EFKA Polymer) 400, Efka polymer (EFKA Polymer) 401, Efka polymer (EFKA Polymer) 450 (being the manufacture of Ciba (Ciba Specialty Chemicals) company), this Paasche of enlightening Ai De (Disperse Aid) 6, This Paasche of enlightening Ai De (Disperse Aid) 8, this Paasche of enlightening Ai De (Disperse Aid) 15, this Paasche of enlightening Ai De Macromolecule dispersing agents such as (Disperse Aid) 9100 (being Sheng Nuopuke (San Nopco) (share) manufacture)；Suo Sipa (Solsperse) 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000,41000 etc. is each Kind Suo Sipa (Solsperse) dispersing agent (manufacture of Lu Borun (Lubrizol) company)；Ai Dike pluronic (Adeka Pluronic)L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、 L121, P-123 (Ai Dike (share) manufacture) and Yi Nengte (IONET) S-20 (Sanyo's chemical conversion industry (share) manufacture), Di Si Pa Bike (DISPERBYK) 3,000 101,103,106,108,109,111,112,116,130,140,142,162,163, 164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (Bi Ke chemistry (BYK-Chemie) Company's manufacture).In addition, the oligomer or poly- in molecular end or side chain with polar group such as acrylic acid series copolymer can be enumerated Close object.
Resin combination of the invention, which preferably contains (ingredient S), to be indicated by following formula (S) and has at least one kind of acidic group Dispersing agent be used as (ingredient H) dispersing agent.Resin combination of the invention is by containing ingredient S, in metal oxide particle Oversize grain is few when dispersion, also there is no dispersion liquid is mixed with component of polymer when cohesion, therefore can be formed refractive index height, The excellent hardening thing of the transparency.
(in formula (S), R3The concatenating group of (m+n) valence of expression, R4And R5Separately indicate the concatenating group of singly-bound or divalent, A2Indicate containing at least one kind of following part-structure monovalence organic group, above-mentioned part-structure be selected from by organic pigment structure, Heterocycle structure, acidic group, the base with basic nitrogen atom, urea groups, carbamate groups, the base with coordinating oxygen atom, carbon number For group composed by 4 or more alkyl, alkoxysilane group, epoxy group, isocyanate group and hydroxyl, n A2、R4Can be identical, Can also be different, m indicates that 0~8, n indicates that 2~9, m+n is 3~10, P2Indicate macromolecular scaffold, m P2、R5Can be identical, it can also not Together).
Ingredient S is the dispersing agent at least one kind of acidic group.Infer by with acidic group, and as absorption base to metal oxygen Compound particle plays a role, and the dispersibility of metal oxide particle is excellent.
As acidic group, carboxylic acid group's (carboxyl), sulfonic group, phosphate, phenolic hydroxyl group etc. can be enumerated, just for metal oxide For the adsorption capacity of particle and the viewpoint of dispersibility, it is preferably selected from the group as composed by carboxylic acid group, sulfonic group and phosphate In at least one kind of, particularly preferably carboxylic acid group.Acidic group in above-mentioned dispersing agent can individually containing a kind in these acidic groups or contain There is combination of more than two kinds.
Acidic group in ingredient S can have any structure of formula (S).Specifically, such as acidic group may be included in above-mentioned formula (S) A in2In, in addition, may be included in by P2In represented macromolecular scaffold, A also may be included in2And P2In the two, but just For the viewpoint of effect, it is preferably contained in A2In.
In above-mentioned formula (S), A2Indicate the organic group of the monovalence containing at least one kind of following part-structure, above-mentioned part knot Structure is selected from by organic pigment structure, heterocycle structure, acidic group, the base with basic nitrogen atom, urea groups, carbamate groups, has Base, the carbon number of coordinating oxygen atom are made of 4 or more alkyl, alkoxysilane group, epoxy group, isocyanate group and hydroxyl Group.In addition, there are n A in formula (S)2Difference can be identical, can also be different.
That is, above-mentioned A2Indicate containing at least one kind of following structure or functional group monovalence organic group, above structure be as The structure with the adsorption capacity for metal oxide particle as organic pigment structure, heterocycle structure, above-mentioned functional group are If acidic group, the base with basic nitrogen atom, urea groups, carbamate groups, the base with coordinating oxygen atom, carbon number are 4 or more Alkyl, alkoxysilane group, epoxy group, there is adsorption energy for metal oxide particle as isocyanate group and hydroxyl The functional group of power.
Furthermore hereinafter, this to be had to part-structure (above structure and the official of the adsorption capacity for metal oxide particle Energy base) it is suitable for being collectively referred to as " adsorption site " to be illustrated.
As long as in 1 A2In contain at least one kind of above-mentioned adsorption site, two or more can also be contained.
In addition, in the present invention, " organic group of the monovalence containing at least one kind of adsorption site " be above-mentioned adsorption site with by 1~200 carbon atoms, 0~20 nitrogen-atoms, 0~100 oxygen atoms, 1~400 hydrogen atoms and The organic group of monovalence made of the concatenating group bond that 0~40 sulphur atoms are constituted.Furthermore when adsorption site itself may make up When the organic group of monovalence, adsorption site itself can be for by A2The organic group of represented monovalence.
Firstly, below to constituting above-mentioned A2Adsorption site be illustrated.
As above-mentioned " organic pigment structure ", such as phthalocyanine system, insoluble azo system, azo lake system, anthraquinone can be enumerated System, quinacridone, dioxazines system, diketopyrrolo-pyrrole system, anthracene pyridine system, anthanthrone system, indanthrene (indanthrone) system, yellow scholar's ketone system, purple cyclic ketones (perinone) system, be, the pigmentary structures of thioindigo system are as preferred Example, the more preferably pigmentary structures of phthalocyanine system, azo lake system, anthraquinone system, dioxazines system, diketopyrrolo-pyrrole system, especially The preferably pigmentary structures of phthalocyanine system, anthraquinone system, diketopyrrolo-pyrrole system.
In addition, as above-mentioned " heterocycle structure ", as long as the base with heterocycle more than at least one.As above-mentioned Hetero atom in " heterocycle structure ", preferably at least one containing O (oxygen atom), N (nitrogen-atoms) or S (sulphur atom), it is more excellent It is selected as containing at least one nitrogen-atoms.As the heterocycle in above-mentioned " heterocycle structure ", such as can enumerate selected from by thiophene, furans, two Benzo piperazine mutters, pyrroles, pyrrolin, pyrrolidines, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles, oxazole, thiazole, dislikes two Azoles, triazole, thiadiazoles, pyrans, pyridine, piperidines, dioxanes, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, iso-indoles Quinoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, in second Heterocycle in group composed by uride, indoles, quinoline, carbazole, acridine and acridone is more preferably selected from as preference By pyrrolin, pyrrolidines, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, three Piperazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, two formyl of naphthalene Heterocycle in group composed by imines, hydantoins, carbazole, acridine and acridone.
Furthermore above-mentioned " organic pigment structure " or " heterocycle structure " can have substituent group in turn, as above-mentioned substituent group, example It can such as enumerate: methyl, the alkyl that ethyl carbon number is 1~20, the aryl that the carbon numbers such as phenyl, naphthalene are 6~16, hydroxyl, amino, Carboxyl, sulfoamido, N- sulfonyl amide groups, the acyloxy that the carbon numbers such as acetoxyl group are 1~6, the carbon numbers such as methoxyl group, ethyoxyl For 1~20 alkoxy, the halogen atoms such as chlorine atom, bromine atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl etc. The alkoxy carbonyl that carbon number is 2~7, cyano, carbonate groups such as t-butyl carbonate base etc..Herein, these substituent groups can be under The structural unit stated above structure unit combines constituted concatenating group and is bonded with organic pigment structure or heterocycle structure.
As above-mentioned " acidic group ", for example, can enumerate carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group, Boronate is and then more excellent as preference, more preferably carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group It is selected as carboxylic acid group, sulfonic group, phosphate, particularly preferably carboxylic acid group.
In addition, as above-mentioned " base with basic nitrogen atom ", such as amino (- NH can be enumerated2), substituted imido (- NHR8、-NR9R10, herein, R8、R9And R10Separately indicate the aryl that alkyl, carbon number that carbon number is 1~20 are 6 or more, carbon Number be 7 or more aralkyl, preferably carbon number be 1~20 alkyl, carbon number be 6~20 aryl or carbon number be 7~20 virtue Alkyl), by represented by following formula (a1) guanidine radicals, preference is used as by amidino groups represented by following formula (a2) etc..
In formula (a1), R11And R12Separately indicate the aryl, carbon that alkyl, carbon number that carbon number is 1~20 are 6 or more Number be 7 or more aralkyl, preferably carbon number be 1~20 alkyl, carbon number be 6~20 aryl or carbon number be 7~20 virtue Alkyl.
In formula (a2), R13And R14Separately indicate the aryl, carbon that alkyl, carbon number that carbon number is 1~20 are 6 or more Number be 7 or more aralkyl, preferably carbon number be 1~20 alkyl, carbon number be 6~20 aryl or carbon number be 7~20 virtue Alkyl.
Among these, more preferably amino (- NH2), substituted imido (- NHR8、-NR9R10, herein, R8、R9And R10Respectively Independently indicate the alkyl that carbon number is 1~10, phenyl, benzyl), by represented by above-mentioned formula (a1) guanidine radicals (in formula (a1), R11And R12Separately indicate the alkyl that carbon number is 1~10, phenyl, benzyl), by the amidino groups (formula (a2) represented by above-mentioned formula (a2) In, R13And R14Separately indicate the alkyl that carbon number is 1~10, phenyl, benzyl) etc..
Especially, it is preferable to use amino (- NH2), substituted imido (- NHR8、-NR9R10, herein, R8、R9And R10Respectively Independently indicate the alkyl that carbon number is 1~5, phenyl, benzyl), by represented by above-mentioned formula (a1) guanidine radicals (in formula (a1), R11And R12Separately indicate the alkyl that carbon number is 1~5, phenyl, benzyl), by the amidino groups (formula (a2) represented by above-mentioned formula (a2) In, R13And R14Separately indicate the alkyl that carbon number is 1~5, phenyl, benzyl) etc..
As above-mentioned " urea groups ", such as-NR can be enumerated15CONR16R17(herein, R15、R16And R17Separately indicate hydrogen The aralkyl that the aryl or carbon number that alkyl that atom, carbon number are 1~20, carbon number are 6 or more are 7 or more, preferably carbon number are 1 The aralkyl that the aryl or carbon number that~20 alkyl, carbon number are 6~20 are 7~20) it is used as preference, more preferably- NR15CONHR17(herein, R15And R17Separately indicate the virtue that alkyl, carbon number that hydrogen atom, carbon number are 1~10 are 6 or more The aryl or carbon number that alkyl that the aralkyl that base or carbon number are 7 or more, preferably carbon number are 1~10, carbon number are 6~20 are 7 ~20 aralkyl), particularly preferably-NHCONHR17(herein, R17Indicate that alkyl, carbon number that hydrogen atom, carbon number are 1~10 are 6 or more aryl or carbon number be 7 or more aralkyl, preferably carbon number be 1~10 alkyl, carbon number be 6~20 aryl, Or carbon number is 7~20 aralkyl).
As above-mentioned " carbamate groups ", such as-NHCOOR can be enumerated18、-NR19COOR20、-OCONHR21、- OCONR22R23(herein, R18、R19、R20、R21、R22And R23Separately indicate carbon number be 1~20 alkyl, carbon number be 6 with On aryl or carbon number be 7 or more aralkyl, preferably carbon number be 1~20 alkyl, carbon number be 6~20 aryl or carbon Number be 7~20 aralkyl) etc. be used as preference, more preferably-NHCOOR18、-OCONHR21(herein, R18And R21Independently Ground indicates the aralkyl that the aryl that the alkyl that carbon number is 1~20, carbon number are 6 or more or carbon number are 7 or more, and preferably carbon number is 1 The aralkyl that the aryl or carbon number that~20 alkyl, carbon number are 6~20 are 7~20) etc., particularly preferably-NHCOOR18、- OCONHR21(herein, R18And R21Separately indicate the aryl or carbon number that alkyl, carbon number that carbon number is 1~10 are 6 or more For 7 or more aralkyl, preferably carbon number be 1~10 alkyl, carbon number be 6~12 aryl or carbon number be 7~10 aralkyl Base) etc..
It as above-mentioned " base with coordinating oxygen atom ", such as can enumerate: levulinic ketone group, the base with crown ether structures Deng.
As above-mentioned " carbon number be 4 or more alkyl ", the virtue that alkyl, carbon number that carbon number is 4 or more are 6 or more can be enumerated Base, aralkyl etc. that carbon number is 7 or more are used as preference, more preferably carbon number be 4~20 alkyl, carbon number be 6~20 virtue Base, aralkyl that carbon number is 7~20 etc., particularly preferably alkyl (such as octyl, dodecyl etc.), carbon number of the carbon number for 4~15 Aryl (such as phenyl, naphthalene etc.), the aralkyl (such as benzyl etc.) that carbon number is 7~15 etc. for 6~15.
It as above-mentioned " alkoxysilane group ", such as can enumerate: trimethoxy silane base, triethoxysilicane alkyl etc..
As the concatenating group being bonded with above-mentioned adsorption site, preferably singly-bound, or by 1~100 carbon atom, 0 What~10 nitrogen-atoms, 0~50 oxygen atoms, 1~200 hydrogen atoms and 0~20 sulphur atoms were constituted Concatenating group, the concatenating group can be unsubstituted, and can also have substituent group in turn.As the concrete example of the concatenating group, can enumerate following Structural unit or above structure unit combine constituted base.
When above-mentioned concatenating group has substituent group, as above-mentioned substituent group, such as can enumerate: the carbon numbers such as methyl, ethyl are 1 ~20 alkyl, the aryl that the carbon numbers such as phenyl, naphthalene are 6~16, hydroxyl, amino, carboxyl, sulfoamido, N- sulfonyl amide Base, the acyloxy that the carbon numbers such as acetoxyl group are 1~6, the alkoxy that the carbon numbers such as methoxyl group, ethyoxyl are 1~6, chlorine atom, bromine are former The halogen atoms such as son, the alkoxy carbonyl that the carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are 2~7, cyano, Carbonate groups such as t-butyl carbonate base etc..
Among above-mentioned, as above-mentioned A2, preferably containing at least one kind of selected from by organic pigment structure, heterocycle structure, acid The monovalence of part-structure in group composed by the alkyl that base, the base with basic nitrogen atom, urea groups and carbon number are 4 or more Organic group, particularly preferably containing at least one kind of acidic group monovalence organic group.
As above-mentioned A2, organic group more preferably by the monovalence represented by following formula (4).
In above-mentioned formula (4), B1Indicate above-mentioned adsorption site (that is, selected from by organic pigment structure, heterocycle structure, acidic group, tool There are base, urea groups, carbamate groups, the base with coordinating oxygen atom, the alkyl that carbon number is 4 or more, alkane of basic nitrogen atom Part-structure in group composed by oxysilane base, epoxy group, isocyanate group and hydroxyl), R24Indicate singly-bound or (a+ 1) concatenating group of valence.A indicates 1~10 integer, and there are a B in formula (4)1Difference can be identical, can also be different.
As by above-mentioned B1The A of above-mentioned formula (S) can be enumerated and be constituted to represented adsorption site2Adsorption site it is identical Person, preference are also identical.
Wherein, be preferably selected from by organic pigment structure, heterocycle structure, acidic group, the base with basic nitrogen atom, urea groups, And carbon number be 4 or more alkyl composed by part-structure in group, particularly preferably acidic group.
R24The concatenating group of expression singly-bound or (a+1) valence, the integer of a expression 1~10, preferably 1~7 integer, more preferably For 1~5 integer, particularly preferably 1~3 integer.
As the concatenating group of (a+1) valence, comprising by 1~100 carbon atom, 0~10 nitrogen-atoms, 0~ 50 oxygen atoms, 1~200 hydrogen atoms and 0~20 the base that constitutes of sulphur atom, can be unsubstituted, can also be into And there is substituent group.
The concrete example of concatenating group as above-mentioned (a+1) valence can enumerate following structural unit or by above structure unit Combine constituted base (ring structure can be formed).
As R24, preferably singly-bound, or by 1~50 carbon atoms, 0~8 nitrogen-atoms, 0~25 The concatenating group of (a+1) valence that oxygen atom, 1~100 hydrogen atoms and 0~10 sulphur atoms are constituted, more preferably singly Key, or it is former by 1~30 carbon atoms, 0~6 nitrogen-atoms, 0~15 oxygen atoms, 1~50 hydrogen The concatenating group of (a+1) valence that son and 0~7 sulphur atoms are constituted, particularly preferably singly-bound, or it is former by 1~10 carbon Son, 0~5 nitrogen-atoms, 0~10 oxygen atoms, 1~30 hydrogen atoms and 0~5 sulphur atom structures At (a+1) valence concatenating group.
Among above-mentioned, when the concatenating group of (a+1) valence has substituent group, as above-mentioned substituent group, such as it can enumerate: first The alkyl that the carbon numbers such as base, ethyl are 1~20, the aryl that the carbon numbers such as phenyl, naphthalene are 6~16, hydroxyl, amino, carboxyl, sulfonamide Base, N- sulfonyl amide groups, the acyloxy that the carbon numbers such as acetoxyl group are 1~6, the alkane that the carbon numbers such as methoxyl group, ethyoxyl are 1~6 Oxygroup, the halogen atoms such as chlorine atom, bromine atom, the carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are 2~7 Alkoxy carbonyl, cyano, carbonate groups such as t-butyl carbonate base etc..
In above-mentioned formula (S), R4And R5Separately indicate the concatenating group of singly-bound or divalent.There are n R4Difference can phase It together, can also be different.Additionally, there are m R5Difference can be identical, can also be different.
As R4And R5In divalent concatenating group, comprising by 1~100 carbon atom, 0~10 nitrogen-atoms, The base that 0~50 oxygen atoms, 1~200 hydrogen atoms and 0~20 sulphur atoms are constituted, can be unsubstituted, There can also be substituent group in turn.
The concrete example of concatenating group as above-mentioned divalent can enumerate following structural units or combine above structure unit The base constituted.
R4And R5Preferably separately indicate singly-bound, or by 1~50 carbon atoms, 0~8 nitrogen-atoms, The concatenating group for the divalent that 0~25 oxygen atoms, 1~100 hydrogen atoms and 0~10 sulphur atoms are constituted, more Preferably singly-bound, or by 1~30 carbon atoms, 0~6 nitrogen-atoms, 0~15 oxygen atoms, 1~50 Hydrogen atom and the concatenating group of divalent that constitutes of 0~7 sulphur atoms, particularly preferably singly-bound, or by 1~10 Carbon atom, 0~5 nitrogen-atoms, 0~10 oxygen atoms, 1~30 hydrogen atoms and 0~5 sulphur are former The concatenating group for the divalent that son is constituted.
Among above-mentioned, when the concatenating group of divalent has substituent group, as above-mentioned substituent group, such as it can enumerate: methyl, second The alkyl that the carbon numbers such as base are 1~20, the aryl that the carbon numbers such as phenyl, naphthalene are 6~16, hydroxyl, amino, carboxyl, sulfoamido, N- Sulfonyl amide groups, the acyloxy that the carbon numbers such as acetoxyl group are 1~6, the alkoxy that the carbon numbers such as methoxyl group, ethyoxyl are 1~6, The halogen atoms such as chlorine atom, bromine atom, the alcoxyl that the carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are 2~7 Base carbonyl, cyano, carbonate groups such as t-butyl carbonate base etc..
In above-mentioned formula (S), R3The concatenating group of (m+n) valence of expression.M+n meets 3~10.
As by above-mentioned R3The concatenating group of represented (m+n) valence, comprising by 1~60 carbon atom, 0~10 Nitrogen-atoms, 0~50 oxygen atoms, 1~100 hydrogen atoms and 0~20 the base that constitutes of sulphur atom, can It is unsubstituted, can also have substituent group in turn.
The concrete example of concatenating group as above-mentioned (m+n) valence can enumerate following structural unit or by above structure unit Combine constituted base (ring structure can be formed).
As the concatenating group of (m+n) valence, preferably by 1~60 carbon atoms, 0~10 nitrogen-atoms, 0~ The base that 40 oxygen atoms, 1~120 hydrogen atoms and 0~10 sulphur atoms are constituted, more preferably by 1~50 A carbon atom, 0~10 nitrogen-atoms, 0~30 oxygen atoms, 1~100 hydrogen atoms and 0~7 The base that constitutes of sulphur atom, particularly preferably for by 1~40 carbon atoms, 0~8 nitrogen-atoms, 0~20 oxygen The base that atom, 1~80 hydrogen atoms and 0~5 sulphur atoms are constituted.
Among above-mentioned, when the concatenating group of (m+n) valence has substituent group, as above-mentioned substituent group, such as it can enumerate: first The alkyl that the carbon numbers such as base, ethyl are 1~20, the aryl that the carbon numbers such as phenyl, naphthalene are 6~16, hydroxyl, amino, carboxyl, sulfonamide Base, N- sulfonyl amide groups, the acyloxy that the carbon numbers such as acetoxyl group are 1~6, the alkane that the carbon numbers such as methoxyl group, ethyoxyl are 1~6 Oxygroup, the halogen atoms such as chlorine atom, bromine atom, the carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are 2~7 Alkoxy carbonyl, cyano, carbonate groups such as t-butyl carbonate base etc..
Following presentation is by above-mentioned R3Concrete example [the concrete example (1)~concrete example of the concatenating group of represented (m+n) valence (17)].But in the present invention, it is not limited by these concrete examples.
Among above-mentioned concrete example, with regard to acquired, synthesis the easiness of raw material, for the deliquescent viewpoint of various solvents For, the concatenating group of most preferred (m+n) valence is following base.
In above-mentioned formula (S), m indicates 0~8.As m, preferably 0.5~5, more preferably 0.5~4, particularly preferably 0.5 ~3.
In addition, n indicates 2~9 in above-mentioned formula (S).As n, preferably 2~8, more preferably 2~7, particularly preferably 3 ~6.
In addition, the P in formula (S)2It indicates macromolecular scaffold, can be selected according to purpose etc. from well known polymer etc.. There are m P in formula (S)2Difference can be identical, can also be different.In addition, P2The preferably macromolecular scaffold of monovalence.
As constitute macromolecular scaffold polymer chain, be preferably selected from by vinyl monomer homopolymer or copolymer, Ester based polymer, ether based polymer, carbamate based polymer, amide based polymer, epoxy based polymer, silicone-based polymerization Object and these modifier or copolymer [such as it is poly- comprising polyethers/polyurethane co-polymer, polyethers/vinyl monomer Closing copolymer of object etc. (can be any, more preferably random copolymerization of random copolymer, block copolymer, graft copolymer Object)] composed by it is at least one kind of in group, more preferably polymerize selected from polymer or copolymer by vinyl monomer, ester system At least 1 in group composed by object, ether based polymer, carbamate based polymer and these modifier or copolymer Kind, and then the polymer or copolymer of more preferably vinyl monomer, particularly preferably acrylic resin ((methyl) acrylic acid list The polymer or copolymer of body).
In turn, above-mentioned polymer preferably dissolves in organic solvent.In addition, ingredient S preferably dissolves in organic solvent In.If the compatibility with organic solvent is low, for example die down sometimes with the compatibility of decentralized medium, is unable to ensure and is enough to realize point Dissipate the stabilized adsorption layer that metal oxide particle surface is formed in by ingredient S.
In the present invention, above-mentioned P2In macromolecular scaffold can have a kind or more of acidic group, can also not have acidic group.
It as the polymer with the acidic group for constituting above-mentioned macromolecular scaffold, such as can enumerate: the polyamide with acidic group Amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethanes, modified poly ester, modified poly- (first Base) acrylate, (methyl) acrylic acid series copolymer, naphthalene sulfonic acid-formaldehyde condensation product and polyoxyethylene alkyl phosphate, polyoxy second Allylic alkylation amine, alkanolamine, pigment derivative etc..Among these, preferably (methyl) acrylic copolymer.
Into macromolecular scaffold, there is no particular restriction for the method for importing acidic group, can be used through the vinyl list with acidic group Method of the body to import, method by importing acidic group addition using bridging property side chain etc., as be described hereinafter as, be easy for controlling For the viewpoint of the import volume of acidic group, the viewpoint of synthesis cost, contains preferably by macromolecular scaffold and be originated from acidic group The Component units of vinyl monomer and constitute to import the form of acidic group.
Herein, " acidic group " can similarly enumerate above-mentioned A2Explanation in be used as " acidic group " ones listed, preferably carboxyl.
As above-mentioned vinyl monomer, there is no particular restriction, such as preferably are as follows: (methyl) esters of acrylic acid, crotonates Class, vinyl ester, maleic acid ester class, two esters of fumaric acid, two esters of itaconic acid, (methyl) acrylamide Class, vinyl ethers, vinyl ketones, olefines, maleimide class, (methyl) acrylonitrile, has acid at phenylethylene The vinyl monomer etc. of base.
Hereinafter, the preference to these vinyl monomers is illustrated.
As the example of (methyl) esters of acrylic acid, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) cyclohexyl acrylate, (first Base) t-butylcyclohexyl ester, (methyl) 2-EHA, the tertiary monooctyl ester of (methyl) acrylic acid, (methyl) acrylic acid Ten diester, (methyl) octadecyl acrylate, (methyl) acrylic acid acetoxyethyl, (methyl) phenyl acrylate, (methyl) third Olefin(e) acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxyl Base butyl ester, (methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- (2- first Oxygroup ethyoxyl) ethyl ester, (methyl) acrylic acid 3- phenoxy group -2- hydroxy propyl ester, (methyl) acrylic acid 2- chloroethene ester, (methyl) third Olefin(e) acid ethylene oxidic ester, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylate, (methyl) vinyl acrylate, (methyl) acrylic acid 2- phenylethylene ester, (methyl) acrylic acid 1- acrylic ester, (methyl) allyl acrylate, (methyl) acrylic acid 2- allyloxy second Ester, (methyl) propargylacrylate, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether, (methyl) propylene Acid diethylene glycol monoethyl ether, (methyl) acrylic acid triethylene glycol monomethyl ether, (methyl) acrylic acid Triethylene glycol ethyl ether, (methyl) Polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ether, (methyl) propenoic acid beta-phenoxy group second Ester, (methyl) nonylphenol acrylate phenoxy group polyethylene glycol, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl Oxygroup ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) perfluoroethyl octyl ethyl ester, (methyl) dicyclopentanyl acrylate, (methyl) tribromophenyl acrylate, (methyl) acrylic acid tribromophenoxy ethyl ester, (methyl) third Olefin(e) acid gamma-butyrolacton -2- base ester etc..
It as the example of crotonic acid esters, can enumerate: butyl crotonate and cetyl crotonate etc..
It as the example of vinyl ester, can enumerate: vinyl acetate, vinyl chloroacetate, vinyl propionate, butyric acid second Enester, vinyl methoxyacetate ester and vinyl benzoate etc..
As the example of maleic acid ester class, can enumerate: dimethyl maleate, diethyl maleate, And dibutyl maleate etc..
As the example of two esters of fumaric acid, can enumerate: dimethyl fumarate, diethyl fumarate, And dibutyl fumarate etc..
It as the example of two esters of itaconic acid, can enumerate: two fourth of dimethyl itaconate, diethyl itaconate and itaconic acid Ester etc..
It as (methyl) acrylic amide, can enumerate: (methyl) acrylamide, N- methyl (methyl) acrylamide, N- second Base (methyl) acrylamide, N- propyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N- normal-butyl (methyl) third Acrylamide, N- tert-butyl (methyl) acrylamide, N- cyclohexyl (methyl) acrylamide, N- (2- methoxy ethyl) (methyl) third Acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- phenyl (methyl) acryloyl Amine, N- nitrophenylacrylamide, N- ethyl, N-phenyl acrylamide, N- benzyl (methyl) acrylamide, (methyl) acryloyl Base morpholine, diacetone acrylamide, N hydroxymethyl acrylamide, N- hydroxyethyl acrylamide, vinyl (methyl) acrylamide, N, N- diallyl (methyl) acrylamide, N- allyl (methyl) acrylamide etc..
It as the example of phenylethylene, can enumerate: styrene, methyl styrene, dimethyl styrene, trimethylbenzene second Alkene, ethyl styrene, isopropyl styrene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethylene, second Acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, by acidic materials remove-insurance can be passed through Hydroxy styrenes, vinylbenzoate and the Alpha-Methyl benzene of base (such as tert-butoxycarbonyl (t-Boc) etc.) protection of shield Ethylene etc..
It as the example of vinyl ethers, can enumerate: methyl vinyl ether, ethyl vinyl ether, 2- chloroethyl vinyl base Ether, hydroxyethyl vinylethers, propyl vinyl ether, butyl vinyl ether, hexylvinyl ether, octyl vinyl ether, methoxyl group Ethyl vinyl ether and Vinyl phenyl ether etc..
It as the example of vinyl ketones, can enumerate: methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, benzene Base vinyl ketone etc..
It as the example of olefines, can enumerate: ethylene, propylene, isobutene, butadiene, isoprene etc..
As the example of maleimide class, can enumerate: maleimide, butyl maleimide, Cyclohexylmaleimide, phenylmaleimide etc..
(methyl) acrylonitrile also can be used, replace hetero ring type base (such as the vinylpyridine, N- vinylpyridine for having vinyl Pyrrolidone, vinyl carbazole etc.), N- vinyl formamide, N- vinyl acetamide, N- vinyl imidazole, vinyl caprolactam Deng.
In addition to above compound, also it can be used for example sub- with carbamate groups, urea groups, sulfoamido, phenolic group, acyl The vinyl monomer of the functional groups such as amido.As such monomer with carbamate groups or urea groups, such as using isocyanide The addition reaction of acidic group and hydroxyl or amino and be suitable for synthesis.Specifically, by the monomer containing isocyanate group and 1 can be contained The addition reaction of the compound of a hydroxyl or the compound containing 1 level-one amino or second level amino, or the list containing hydroxyl Body or the addition reaction of monomer and monoisocyanates containing level-one amino or second level amino etc. and be suitable for synthesis.
Secondly, to being used for macromolecular scaffold P2The middle vinyl monomer with acidic group for importing acidic group is illustrated.
As the example of the above-mentioned vinyl monomer with acidic group, the vinyl monomer with carboxyl can be enumerated or there is sulphur The vinyl monomer of acidic group.
As the vinyl monomer with carboxyl, can enumerate: (methyl) acrylic acid, vinyl benzoic acid, maleic acid, Maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer etc..In addition, can also benefit There is the monomer and maleic anhydride or phthalic anhydride, such as hexamethylene of hydroxyl with (methyl) acrylic acid 2- hydroxy methacrylate etc. The addition reaction of cyclic anhydride as dicarboxylic anhydride, ω-carboxy-polycaprolactone list (methyl) acrylate etc..In addition, as carboxylic The monomers containing acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride also can be used in the predecessor of base.Furthermore these it In, for the viewpoint of copolymerizable or cost, dissolubility etc., particularly preferably (methyl) acrylic acid.
In addition, 2- acrylamide-2-methyl propane sulfonic etc. can be enumerated as with sulfonic vinyl monomer, as Vinyl monomer with phosphate can enumerate mono phosphoric acid ester (2- acryloyloxyethyl ester), mono phosphoric acid ester (1- methyl -2- acryloyl Oxygroup ethyl ester) etc..
In turn, it as the vinyl monomer with acidic group, goes back using the vinyl monomer containing phenolic hydroxyl group or contains The vinyl monomer etc. of sulfoamido.
As macromolecular scaffold P2When monomeric unit comprising being originated from the vinyl monomer containing acidic group, from containing acidic group Content of the monomeric unit of vinyl monomer in macromolecular scaffold is in terms of mass conversion, relative to the entirety of macromolecular scaffold, The preferably 3 mass % of mass %~40, the more preferably range of 5 mass of mass %~20 %.
It is indicated by above-mentioned formula (S) and is had among the dispersing agent of at least one kind of acidic group, most preferably meet following institute simultaneously The R shown3、R4、R5、P2, m and n person.
R3: above-mentioned concrete example (1), concrete example (2), concrete example (10), concrete example (11), concrete example (16) or concrete example (17)
R4: singly-bound or by following structural unit or combine above structure unit constituted " 1~10 Carbon atom, 0~5 nitrogen-atoms, 0~10 oxygen atoms, 1~30 hydrogen atoms and 0~5 sulphur are former The concatenating group for the divalent that son " is constituted (can have substituent group, as above-mentioned substituent group, such as can enumerate: the carbon numbers such as methyl, ethyl For 1~20 alkyl, the aryl that the carbon numbers such as phenyl, naphthalene are 6~16, hydroxyl, amino, carboxyl, sulfoamido, N- sulfonyl acyl Amido, the acyloxy that the carbon numbers such as acetoxyl group are 1~6, the alkoxy that the carbon numbers such as methoxyl group, ethyoxyl are 1~6, chlorine atom, bromine The halogen atoms such as atom, the alkoxy carbonyl that the carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are 2~7, cyanogen Base, carbonate groups such as t-butyl carbonate base etc.)
R5: singly-bound, ethylidene, propylidene, following bases (a) or following bases (b)
Furthermore in following bases, R12Indicate that hydrogen atom or methyl, L indicate 1 or 2.
P2: the copolymer of vinyl monomer and other vinyl monomers with carboxyl；Vinyl list without acidic group The polymer or copolymer of body；Selected from by ester based polymer, ether based polymer and carbamate based polymer and these Modifier composed by group, and contain at least one kind of acidic group polymer
M:0.5~3
N:3~6
The content of acidic group in ingredient S is the acid value possessed by ingredient S to be suitable for decision.It is excellent as the acid value of ingredient S It is selected as 20mgKOH/g~300mgKOH/g, more preferably 50mgKOH/g~250mgKOH/g, particularly preferably 50mgKOH/g~ 210mgKOH/g.If acid value is 20mgKOH/g or more, the alkali-developable of photosensitive polymer combination can be sufficiently obtained, if sour Value is 300mgKOH/g hereinafter, then the dispersibility of metal oxide particle and dispersion stabilization are excellent.
As the molecular weight of ingredient S, with Weight-average molecular meter, preferably 2,000~200,000, more preferably 2,000~ 15,000, particularly preferably 2,500~10,000.If weight average molecular weight is to be directed into the end of polymer in above range The effects of multiple above-mentioned adsorption sites fully played, and play the adsorptivity for the surface of solids.Tree of the invention Ingredient S contained by oil/fat composition can be only a kind, can also be two or more.In situation of more than two kinds, preferably it is added up to Above range.
Hereinafter, the exemplary compounds of ingredient S are enumerated, but the present invention is not limited to this, as long as being contained in formula (S), Arbitrary structure can be used.In addition, arbitrary value can be used in P1 and P2 respectively in following exemplary compounds.In addition, following In exemplary compounds, with macromolecular scaffold (P2) bond sulphur atom can be bonded with any one monomeric unit, above-mentioned high-molecular bone Frame (P2) include the monomeric unit with carboxylate and the monomeric unit with carboxyl, macromolecular scaffold not with sulphur atom key Although another end of knot is not stated in following chemical formulas, but as long as being in the end of macromolecular scaffold is usually to be allowed Atom or base.
The monomer list with carboxylate in the exemplary compounds of mentioned component S, in terms of mass conversion, in macromolecular scaffold Member contains the range for than (P1: P2) being preferably 100: 0~80: 20 with the monomeric unit with carboxyl.
Ingredient S for example can refer to Japanese Patent Laid-Open 2008-96678 bulletin or Japanese Patent Laid-Open 2007-277514 Documented method synthesizes in number bulletin.
Dispersing agent can be used alone a kind, can also be used in combination of two or more.
Dispersing agent relative to the total solid content of photosensitive polymer combination, in photosensitive polymer combination of the invention Content be preferably 5 mass of mass %~70 % range, the more preferably range of 10 mass of mass %~50 %.
<other compositions>
In photosensitive polymer combination of the invention, in addition to mentioned component, optionally preferably (ingredient I) is added Sensitizer, (ingredient J) touch modifying agent, (ingredient K) alkali compounds, (ingredient L) interfacial agent.In turn, of the invention In photosensitive polymer combination, above-mentioned ultraviolet absorbing agent, matal deactivator or acid proliferation generator, development accelerant, modeling can be added Agent, hot radical producing agent, thermal acid generator, tackifier and organic or inorganic antisettling agent etc. well known to additive.
(ingredient I) sensitizer
Photosensitive polymer combination of the invention contains increasing sense preferably in the combination with (ingredient C) photoacid generator Agent, to promote the decomposition of photoacid generator.Sensitizer absorbs actinic ray or radioactive ray and becomes electron excitation state.As electricity The sensitizer of sub- excited state is contacted with photoacid generator, and generates the effects of electronics is mobile, energy is mobile, fever.Light as a result, Acid producing agent generates chemical change and decomposes, and generates acid.As the example of preferred sensitizer, it can enumerate and belong to belowization Close species and in any one of the wavelength region of 350nm~450nm with the compound of absorbing wavelength.
The polynuclear aromatic same clan (such as pyrene, triphenylene, anthracene, 9,10- dibutoxy anthracene 9,10- diethoxy anthracene, 3,7- Dimethoxy anthracene, 9,10- dipropoxy anthracene), dibenzo piperazine mutters (xanthene) class (such as fluorescein (fluorescein), daybreak Red, erythrosine (erythrosine), rhodamine B (Rhodamine B), Bengal rose red (Rose Bengal)), xanthene Ketone (such as xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class (such as thia carbonyl flower Green, oxa- carbocyanine), merocyanine class (such as merocyanine, carbonyl merocyanine) if, red cyanines class, oxonols class, thiazide (such as thiophene Give repeated exhortations, methylenum careuleum, toluidine blue), acridine (such as acridine orange, chloroflavin, acriflavine), acridine ketone (such as acridone, 10- butyl -2- chloro-acridine ketone), Anthraquinones (such as anthraquinone), squarylium type (such as side sour cyanines), styrene base class, alkaline benzene second Alkenyl class (such as 2- [2- [4- (dimethylamino) phenyl] vinyl] benzoxazoles), Coumarins (such as 7- lignocaine 4- Methylcoumarin, 7- hydroxyl 4- methylcoumarin, 2,3,6,7- tetrahydro -9- methyl-1 H, 5H, 11H [1] chromenes simultaneously [6,7, 8-ij] quinolizine -11- ketone).
Among these sensitizers, preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, Coumarins, more preferably the polynuclear aromatic same clan.
Relative to 100 mass parts of photoacid generator of photosensitive polymer combination, photosensitive polymer combination of the invention In the additive amount of sensitizer be preferably 0 mass parts~1,000 mass parts, more preferably 10 mass parts~500 mass parts, in turn More preferably 50 mass parts~200 mass parts.
In addition, sensitizer can be used alone a kind, can also be used in combination of two or more.
(ingredient J) touches modifying agent
Photosensitive polymer combination of the invention can touch modifying agent containing (ingredient J).
(ingredient J) contiguity modifying agent of photosensitive polymer combination for use in the present invention is to be promoted to become the inorganic of substrate The compound of the adhesion of object (such as silicon compounds such as silicon, silica, silicon nitride, the metals such as gold, copper, aluminium) and insulating film.Tool For body, silane coupling agent, mercaptan based compound etc. can be enumerated.It is even as the silane for touching modifying agent used in the present invention Mixture is not particularly limited using the modification at interface as purpose person, and well known silane coupling agent can be used.
It as preferred silane coupling agent, such as can enumerate: gamma-amino propyl trimethoxy silicane, gamma-amino propyl three Ethoxysilane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl alkyl dialkoxy silicon Alkane, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4- epoxycyclohexyl) ethyl trialkoxy Silane, vinyl trialkyl oxysilane.
Among these, more preferably γ-glycidyloxypropyl silane or γ-methacryloxy third Base trialkoxy silane, and then more preferably γ-glycidyloxypropyl silane.
In addition, also preferably using following compounds.Furthermore Ph indicates phenyl.
These compounds, which can be used alone, or two or more to be applied in combination by a kind.These compounds are for promotion and substrate Adhesion it is effective, and for adjust it is also effective with angle cone (taper) of substrate.
Relative to 100 parts by weight of ingredient A, (ingredient J) in photosensitive polymer combination of the invention touches modifying agent Content is preferably 0.1 parts by weight~20 parts by weight, more preferably 0.5 parts by weight~10 parts by weight.
(ingredient K) alkali compounds
Photosensitive polymer combination of the invention can contain (ingredient K) alkali compounds.As (ingredient K) alkaline chemical combination Object can arbitrarily be selected from the alkali compounds used in Chemical amplification resist to use.Such as it can enumerate: aliphatic Amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, quarternary ammonium salt of carboxylic acid etc..As these concrete example, can enumerate day Documented compound in 0204~paragraph of paragraph 0207 of this patent special open 2011-221494 bulletin.
Specifically, as aliphatic amine, such as can enumerate: trimethylamine, diethylamine, triethylamine, two-n-propylamines, three-are just Propylamine, two-n-amylamines, three-n-amylamines, diethanol amine, triethanolamine, dicyclohexyl amine, dicyclohexylmethylamine etc..
It as aromatic amine, such as can enumerate: aniline, benzyl amine, n,N-Dimethylaniline, diphenylamine etc..
It as hetero ring type amine, such as can enumerate: pyridine, 2- picoline, 4- picoline, 2- ethylpyridine, 4- ethyl Pyridine, 2- phenylpyridine, 4- phenylpyridine, N- methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4- Methylimidazole, 2-Phenylbenzimidazole, 2,4,5- triphenylimidazolyls, nicotine, niacin, niacinamide, quinoline, 8-hydroxyquinoline, pyrrole Piperazine, pyrazoles, pyridazine, purine, pyrrolidines, piperidines, piperazine, morpholine, 4- methyl morpholine, N- cyclohexyl-N '-[2- (4- morpholinyl) Ethyl] thiocarbamide, 1,5- diazabicyclo [4.3.0] -5- nonene, 1,8- diazabicyclo [5.3.0] -7- hendecene etc..
As hydroxide level Four ammonium, such as can enumerate: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide four-are just Butyl ammonium, hydroxide four-n-hexyl ammonium etc..
It as the quarternary ammonium salt of carboxylic acid, such as can enumerate: acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid four-positive fourth Base ammonium, benzoic acid four-normal-butyl ammonium etc..
Alkali compounds for use in the present invention can be used alone a kind, can also be used in combination of two or more.
Relative to 100 mass parts of total solid content in photosensitive polymer combination, photosensitive resin composition of the invention The content of alkali compounds in object is preferably 0.001 mass parts~3 mass parts, more preferably 0.005 mass parts~1 mass Part.
(ingredient L) interfacial agent
Photosensitive polymer combination of the invention can contain (ingredient L) interfacial agent.
As (ingredient L) interfacial agent, anionic system, cationic system, nonionic system or any of both sexes can be used Kind, but preferred interfacial agent is alcohol nonionic surfactant.
It as the example of alcohol nonionic surfactant, can enumerate: polyoxyethylene higher alkyl ether, polyoxyethylene higher Alkyl phenyl ethers, the higher aliphatic acid diesters class of polyoxyethylene glycol, silicone-based, fluorine system interfacial agent.As fluorine system circle The example of face activating agent, silicone-based interfacial agent, specifically, Japanese Patent Laid-Open No. Sho 62-36663, Japan can be enumerated Open patent is No. 61-226746 clear, Japanese Patent Laid-Open No. Sho 61-226745, Japanese Patent Laid-Open No. Sho No. 62-170950, day This patent tekiaki 63-34540, Japanese Patent Laid-Open 7-230165, Japanese Patent Laid-Open 8-62834, Japan Open patent is No. 9-54432 flat, each public affairs of Japanese Patent Laid-Open 9-5988, Japanese Patent Laid-Open 2001-330953 etc. The interfacial agent recorded in report, it is possible to use commercially available interfacial agent.In addition, following trade name can be enumerated: KP (SHIN-ETSU HANTOTAI Learn industrial (share) manufacture), Po Lifuluo (Polyflow) (common prosperity society chemistry (share) manufacture), Ai Futuo (Eftop) (Mitsubishi Compound material electronics is melted into the manufacture of (JEMCO) company), Mei Jiafa (Megafac) (DIC (DIC) (share) manufacture), Fu La Moral (Fluorad) (Sumitomo 3M (share) manufacture), A Sajia (Asahi Guard), Sha Fulong (Surflon) (Asahi Glass (stock Part) manufacture), Pohle Floex (PolyFox) (manufacture of Ou Nuofa (OMNOVA) company), SH-8400 (the beautiful DOW CORNING silicone (Dow in east Corning Toray Silicone) (share) manufacture) etc. each series.
In addition, as preference, which contains by following formula the copolymer that can be listed below as interfacial agent (L-1) Component units A and Component units B represented by, and when by tetrahydrofuran (THF) as solvent by gel permeation chromatography The weight average molecular weight (Mw) for the polystyrene conversion that method is measured is 1,000 or more, 10,000 or less.
(in formula (L-1), R401And R403Separately indicate hydrogen atom or methyl, R402Indicate carbon number be 1 or more, 4 with Under straight-chain alkyl-sub, R404It indicates hydrogen atom or carbon number is 1 or more, 4 alkyl below, L indicates that carbon number is 3 or more, 6 or less Alkylidene, p and q are the quality percentage for indicating polymerization ratio, and p indicates 10 mass % or more, 80 mass % numerical value below, q Indicate that 20 mass % or more, 90 mass % numerical value below, r indicate that 1 or more, 18 integers below, s indicate 1 or more, 10 or less Integer).
Above-mentioned L is preferably by the branched alkylene groups represented by following formula (L-2).R in formula (L-2)405Indicate that carbon number is 1 Above, 4 alkyl below, with regard to compatibility with for the viewpoint for the wetability for being applied face, preferably carbon number is 1 or more, 3 The alkyl that alkyl below, more preferably carbon number are 2 or 3.P and q's and (p+q) be preferably p+q=100, as 100 matter Measure %.
The weight average molecular weight (Mw) of above-mentioned copolymer is more preferably 1,500 or more, 5,000 or less.
These interfacial agents, which can be used alone, or to be used in mixed way two or more by a kind.
Relative to 100 mass parts of total solid content in photosensitive polymer combination, photosensitive resin composition of the invention The additive amount of interfacial agent in object is preferably 10 below the mass more preferably 0.001 mass parts~10 mass parts, in turn More preferably 0.01 mass parts~3 mass parts.
(ingredient M) acid proliferation generator
In order to promote sensitivity, acid proliferation generator is can be used in photosensitive polymer combination of the invention.
Acid proliferation generator for use in the present invention is can to react further to generate acid and make reaction system by acid catalyst The compound that interior acid concentration rises, and be steadily existing compound in the state of there is no acid.Such compound is logical It crosses 1 secondary response and increases by a kind or more of acid, therefore with the progress of reaction, reaction post carries out, but generated meeting of acid itself Induce selfdecomposition, therefore the intensity of acid generated here is in terms of acid ionization constant, pKa, preferably 3 hereinafter, more preferably 2 with Under.Additionally, it is preferred that being -15 or more, more preferably -10 or more.
It as the concrete example of acid proliferation generator, can enumerate: 0203~section of paragraph of Japanese Patent Laid-Open 10-1508 bulletin Fall 0223,0016~paragraph of paragraph 0055 of Japanese Patent Laid-Open 10-282642 bulletin and the flat 9- of Japanese patent special table Documented compound in No. 512498 bulletins the 2nd row of the 12nd row~47th page of page 39.
As acid proliferation generator for use in the present invention, it can enumerate and be decomposed because of the acid caused by photoacid generator, and produce The pKa such as raw dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid are the chemical combination of 3 acid below Object.
Specifically, following compound etc. can be enumerated.
It, will relative to 100 parts by weight of photoacid generator for the viewpoint of exposure portion and the dissolution contrast in unexposed portion Content of the acid proliferation generator in photosensitive polymer combination is preferably set as 10 parts by weight~1,000 parts by weight, more preferably sets For 20 parts by weight~500 parts by weight.
(ingredient N) development accelerant
Photosensitive polymer combination of the invention can contain development accelerant.
As development accelerant, the arbitrary compound with development accelaration effect can be used, but preferably have and be selected from The compound of at least one of the group as composed by carboxyl, phenolic hydroxyl group and alkylene oxide group structure more preferably has carboxylic The compound of base or phenolic hydroxyl group, most preferably with the compound of phenolic hydroxyl group.
As development accelerant, 0171~paragraph of paragraph of Japanese Patent Laid-Open 2012-042837 bulletin can refer to 0172 record, content can be incorporated into present specification.
Development accelerant can be used alone a kind, can also be used in combination of two or more.
For sensitivity and the viewpoint of residual film ratio, relative to 100 mass parts of total solid content of photosensitive composite, originally The additive amount of development accelerant in the photosensitive polymer combination of invention is preferably 0 mass parts~30 mass parts, more preferably 0.1 mass parts~20 mass parts, most preferably 0.5 mass parts~10 mass parts.
(ingredient O) plasticiser
Resin combination of the invention can contain (ingredient O) plasticiser.
It as plasticiser, such as can enumerate: dibutyl phthalate, dioctyl phthalate, phthalic acid two- Ten diester, polyethylene glycol, glycerol, dimethyl glyceryl phthalate, dibutyl tartrate, dioctyl adipate, triacetyl Base glycerol etc..
Relative to 100 mass parts of content of ingredient A, the content of the plasticiser in resin combination of the invention is preferably 0.1 mass parts~30 mass parts, more preferably 1 mass parts~10 mass parts.
In addition, also can be used recorded in 0120~paragraph of paragraph 0121 of Japanese Patent Laid-Open 2012-8223 bulletin Hot radical producing agent, documented nitrogenous compound and thermal acid generator's conduct in International Publication No. 2011/136074 Other additives.
(manufacturing method (resin pattern manufacturing method) of cured film)
Secondly, being illustrated to the manufacturing method of cured film (resin pattern) of the invention.
The manufacturing method of cured film of the invention preferably comprises the step of (1) below~(5).
(1) application step being coated on photosensitive polymer combination of the invention on substrate；
(2) solvent removal step of solvent is removed from the resin combination being coated with；
(3) the resin combination exposure of solvent will be eliminated into the step of exposure of pattern-like using actinic ray；
(4) development step developed using aqueous developer to exposed resin combination；And
(5) heat treatment step that developed resin combination is heat-treated.
Next coming in order are illustrated each step.
In the application step of (1), preferably photosensitive polymer combination of the invention is coated on substrate and is made Wet film containing solvent.Photosensitive polymer combination is preferably being coated on preceding progress alkali cleaning or plasma on substrate Cleaning etc. substrates cleaning, more preferably after base-plate cleaning so using hexamethyldisilazane to substrate surface at Reason.By carrying out the processing, photosensitive polymer combination promotes the adhesion of substrate.As utilize hexamethyldisilazane It to the method that substrate surface is handled, is not particularly limited, such as can enumerate makes substrate be exposed to two silicon nitrogen of hexamethyl in advance Method etc. in alkane steam.
It as aforesaid substrate, can enumerate: inorganic substrate, resin, resin composite materials, ITO, Cu substrate, poly- terephthaldehyde The plastic base of sour second diester, cellulose triacetate (Cellulose Triacetate, TAC) etc..
As inorganic substrate, such as can enumerate: glass, quartz, silicone, silicon nitride, and on the substrate such as these Composite substrate made of molybdenum, titanium, aluminium, copper etc. is deposited.
As resin, the substrate comprising following resin: polybutylene terephthalate, poly terephthalic acid second two can be enumerated Ester, polyethylene naphthalate, poly- naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyether sulfone, polyarylate, alkene Propyl diglycol carbonates, polyimides, polyamidoimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, are gathered polyamide The fluororesin such as cycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone Resin, ionomeric resins, cyanate ester resin, crosslinking fumaric acid diester resin, cyclic polyolefin, aromatic ether tree The synthetic resin such as rouge, maleimide-olefin resin, cellulose, episulfide resin (episulfide resin).
The case where these substrates use directly in the form of above-mentioned is few, generally according to the form of final product, such as is formed with Such as the multilayer laminated construction as thin film transistor (TFT) (Thin Film Transistor, TFT) element.
The method being coated on towards substrate is not particularly limited, such as can be used: slot coated method, spray-on process, rolling method, rotation Turn the methods of rubbing method, cast coating method, slit and rotation (slit and spin) method.It in turn, can also be using such as Japan Patent Documented so-called (prewet) method of prewetting in special open 2009-145395 bulletin.
Coating film thickness is not particularly limited, can with correspond to purposes film thickness be coated, but preferably 0.5 μm~ It is used in the range of 10 μm.
In the solvent removal step of (2), removed by decompression (vacuum) and/or heating from applied above-mentioned film Solvent, to form dry coating on substrate.The heating condition of solvent removal step preferably heats at 70 DEG C~130 DEG C 30 seconds~300 seconds or so.When temperature and time is above range, the adhesion of pattern is good and can also reduce residue.
In the step of exposure of (3), the substrate for being provided with film is irradiated across the mask with defined pattern photochemical Ray.In this step, photoacid generator decomposes and generates acid.It applies caused by sour decomposability gene contained in film component Acid catalyst action and hydrolyze, to generate acidic group (such as carboxyl or phenolic hydroxyl group).
As utilize photoactinic exposure light source, can be used Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, Chemical lamp, light emitting diode (Light Emitting Diode, LED) light source, excimer laser generation device etc., it is preferable to There is the light of 300nm or more, 450nm wavelength below using g ray (436nm), i ray (365nm), h ray (405nm) etc. Change ray.In addition, optionally can also be by such as long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter Filter is divided to adjust irradiation light.
As exposure device, mirror surface projection alignment exposer (mirror projection aligner), stepping can be used Machine, scanner, the exposure machine of the various modes such as close induction type, contact, microlens array formula, laser explosure formula.
In generating the region for having acid catalyst, in order to accelerate above-mentioned hydrolysis, heat after being exposed: exposing (Post Exposure Bake) (hereinafter also referred to as " PEB ") is toasted after light.By PEB, can promote from sour decomposability base The generation of carboxyl or phenolic hydroxyl group.Temperature when carrying out PEB is preferably 30 DEG C or more, 130 DEG C hereinafter, more preferably 40 DEG C with It is upper, 110 DEG C hereinafter, particularly preferably 50 DEG C or more, 100 DEG C or less.
But the activation energy that the sour decomposability base in the present invention is decomposed due to acid is low, is easy source caused by reason exposure It is decomposed from the acid of photoacid generator, and generates acidic group (such as carboxyl or phenolic hydroxyl group), therefore not necessarily to carry out PEB, Erect image (positive image) can also be formed by development.
In the development step of (4), using alkaline-based developer to the copolymer with the carboxyl to have dissociated or phenolic hydroxyl group Develop.It will be comprising having the resin combination for being easy to be dissolved in the acidic group (such as carboxyl or phenolic hydroxyl group) in alkaline-based developer The exposure portion region of object removes, and erect image is consequently formed.
Contain alkali compounds in developer solution preferably used in development step.As alkali compounds, such as It can be used: the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide；The alkali such as sodium carbonate, potassium carbonate, cesium carbonate Metal carbonate salt；The alkaline metal bicarbonates class such as sodium bicarbonate, potassium bicarbonate；Tetramethyl ammonium hydroxide, tetraethylammonium hydroxide base The tetraalkylammonium hydroxides class such as ammonium, tetrapropylammonium hydroxide, tetrabutylammonium, diethyldimethylammonhydroxide hydroxide: choline Equal hydroxides (hydroxyalkyl) trialkyl ammonium class；The silicates such as sodium metasilicate, sodium metasilicate；Ethamine, propylamine, diethylamine, triethylamine Equal alkyl amines；The alcamines such as dimethylethanolamine, triethanolamine；1,8- diazabicyclo [5.4.0] -7- hendecene, 1,5- The ester ring types amines such as diazabicyclo [4.3.0] -5- nonene.
Among these, preferably sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide Tetrapropyl ammonium, tetrabutylammonium, choline (hydroxide 2- ethoxy trimethyl ammonium).
In addition, it is water-soluble organic will also to add suitable methanol or ethyl alcohol etc. into the aqueous solution of above-mentioned alkali compounds Aqueous solution made of solvent or interfacial agent is used as developer solution.
As preferred developer solution, can enumerate: 0.4 mass % aqueous solution of tetraethyl ammonium hydroxide, 0.5 mass % are water-soluble Liquid, 0.7 mass % aqueous solution or 2.38 mass % aqueous solutions.
The pH of developer solution is preferably 9.0~14, and more preferably 10.0~14.0.The concentration of developer solution is preferably 0.1 matter Measure the mass % of %~20, more preferably 0.1 mass of mass %~5.0 %.Developing time is preferably 30 seconds~500 seconds, more preferably It is 30 seconds~180 seconds.The method of development can be any methods such as covering liquid (puddle) method, infusion process, spray process.After development, Flowing water cleaning can be carried out, and forms desired pattern.The time of flowing water cleaning is preferably 30 seconds~300 seconds, more preferably 30 Second~90 seconds.
After development, rinsing step can also be carried out.In rinsing step, using the cleanings such as pure water development after substrate, by This removes accompanying developer solution, and development residue is removed.Well known method can be used in ELUTION METHOD.Such as spray can be enumerated It is dripping wash or impregnate elution etc..
In the heat treatment step (rear baking) of (5), by heating to erect image obtained, sour decomposability base can be made It is thermally decomposed and generates acidic group (such as carboxyl or phenolic hydroxyl group), and be crosslinked with bridging property base, crosslinking agent etc., thus shape At cured film.The heating preferably uses the heating devices such as heating plate or baking oven, in defined temperature, such as 180 DEG C~250 DEG C Under, with the defined time, such as if in heating plate, then carry out heat treatment in 5 minutes~90 minutes, if baking oven, then into Row heat treatment in 30 minutes~120 minutes.By carrying out cross-linking reaction, and the excellent guarantor such as can form heat resistance, hardness Cuticula or interlayer dielectric.In addition, can also carry out in a nitrogen environment when being heated, the transparency is thus promoted.When When using plastic base, heat treatment in 5 minutes~120 minutes is carried out preferably at 80 DEG C~140 DEG C.
Can also be carried out before heat treatment step (rear baking), after being toasted with relatively low temperature heat treatment step (in Between baking procedure addition).When carrying out intermediate baking, heated preferably at 90 DEG C~150 DEG C 1 minute~after sixty minutes, It is toasted after being carried out at a high temperature of 200 DEG C or more.In addition, centre baking, rear baking can also be divided into 3 it is more than the stage multistage Section is heated.By such intermediate baking, afterwards the design toasted, can adjust the cone angle of pattern.These heating, which can be used, to be added Heating means well known to hot plate, baking oven, infrared heater etc..
Furthermore (rear exposure can be exposed again comprehensively to figuratum substrate progress is formed using actinic ray before rear baking Light), it is toasted after then carrying out, thus generates acid from the photoacid generator being present in unexposed portion, and be used as it and promote The catalyst of cross-linking step functions, to can promote the sclerous reaction of film.It is preferred when as comprising post-exposure step Light exposure, preferably 100mJ/cm2~3,000mJ/cm2, particularly preferably 100mJ/cm2~500mJ/cm2。
In turn, dry-etching resist also is used as from photosensitive polymer combination cured film obtained of the invention (dry etching resist).Resist when by the cured film for carrying out thermmohardening through the heat treatment step and obtaining as dry-etching It when losing agent, can be ashed, the dry-etchings processing such as plasma etching, ozone etching is as etching process.
(cured film)
Cured film of the invention is the cured film for hardening photosensitive polymer combination of the invention and obtaining.
Cured film of the invention can suitably be used as interlayer dielectric.In addition, cured film of the invention is preferably by this The forming method of the cured film of invention cured film obtained.
Photosensitive polymer combination according to the present invention, can get that insulating properties is excellent, also has when being toasted at high temperature There is the interlayer dielectric of high transparency.There is high transparency using interlayer dielectric made of photosensitive polymer combination of the invention Property, and cured film physical properties excellent, therefore it is useful for the purposes of organic EL display device or liquid crystal display device.
(hardening thing and its manufacturing method)
Hardening thing of the invention is the hardening thing for hardening photosensitive polymer combination of the invention and obtaining, institute as above It states, shape can not be film, as long as being arbitrary shape.
There is no particular restriction for the manufacturing method of hardening thing of the invention, but is preferably at least and successively includes the following steps (a)~step (c).
(a) application step being coated on photosensitive polymer combination of the invention on substrate；
(b) solvent removal step of solvent is removed from the resin combination being coated with；And
(c) heat treatment step that the resin combination for eliminating solvent is heat-treated.
The meaning of step (a) and step (b) is identical as above-mentioned application step and above-mentioned solvent removal step respectively, preferably Form is also identical.
Except the object being heat-treated be by step (b) it is obtained eliminate the resin combination of solvent in addition to, step Suddenly (c) is the step identical as above-mentioned heat treatment step, heating temperature, heating time, heating side in above-mentioned heat treatment step The preferred form of method etc. is similarly preferred.
Hardening thing or cured film of the invention can suitably be used as lenticule, optical waveguide, anti-reflective film, LED sealing material And hardening thing is used in the visibility reduction of LED wiring electrode used in the optical components such as chip coating material or touch screen.
In addition, hardening thing or cured film of the invention for example may be suitably used to liquid crystal display device as described later or have The protective film of planarization film or interlayer dielectric, colored filter in machine EL device etc., to will be in liquid crystal display device Distance piece that the thickness of liquid crystal layer is kept constant, MEMS (Micro Electro Mechanical System, MEMS the construction component etc. of element) is used.
(liquid crystal display device)
Liquid crystal display device of the invention is characterized in that the cured film for having of the invention.
As liquid crystal display device of the invention, except flat with being formed by using photosensitive polymer combination of the invention Other than smoothization film or interlayer dielectric, there is no particular restriction, can enumerate the well known liquid crystal display device using various constructions.
For example, the TFT's (Thin-Film Transistor) having as liquid crystal display device of the invention is specific Example, can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention is due to electric special Property is excellent, therefore is preferably used after can combining with these TFT.
In addition, can be enumerated: twisted nematic as the adoptable liquid crystal drive mode of liquid crystal display device of the invention (Twisted Nematic, TN) mode, vertical orientation (Vertical Alig nment, VA) mode, coplanar switching (In- Plane Switching, IPS) mode, fringing field switching (Fringe Field Switching, FFS) mode, optical compensation (Optically Compensated Bend, the OCB) mode of bending etc..
In panel composition, the even liquid of colorful optical filter array (Color Filter on Array, COA) mode Crystal device, it is possible to use cured film of the invention can be used, for example, as institute in Japanese Patent Laid-Open 2005-284291 bulletin Documented organic insulating film in the organic insulating film (115) or Japanese Patent Laid-Open 2005-346054 bulletin of record (212)。
In addition, can be arranged as the specific aligned of the adoptable liquid crystal orientation film of liquid crystal display device of the invention Lift friction orientation method, process for optical alignment etc..In addition, can also be special by Japanese Patent Laid-Open 2003-149647 bulletin or Japan Documented polymer stabilizing orientation in sharp special open 2011-257734 bulletin (Polymer Sustained Alignment, PSA) technology and obtain polymer orientation support.
In addition, photosensitive polymer combination of the invention and cured film of the invention do not limit sub- such use, can use In various uses.For example, in addition to planarization film or interlayer dielectric, also may be suitably used to colored filter protective film, Or it is set in distance piece or solid photographic element the thickness of the liquid crystal layer in liquid crystal display device to be kept constant The lenticule etc. of colorized optical filtering on piece.
Fig. 1 is the concept sectional view for indicating an example of liquid crystal display device 10 of active matrix mode.The color liquid crystal is aobvious Showing device 10 is the liquid crystal display panel that the back side has back light unit 12, and liquid crystal panel, which has, is being pasted with the 2 of light polarizing film with configuration The element of the corresponding TFT16 of all pixels between sheet glass substrate 14, glass substrate 15.On being formed in glass substrate In each element, the ito transparent electrode 19 of the tangible pixel electrode of wiring and contact hole 18 being formed in cured film 17.? The layer of liquid crystal 20 and the RGB color optical filter 22 configured with black matrix" are provided on ito transparent electrode 19.
It as the light source of backlight, is not particularly limited, well known light source can be used.Such as it can enumerate: White LED, indigo plant The multi-colored led of color red green etc., fluorescent lamp (cold-cathode tube), organic EL etc..
In addition, liquid crystal display device may be made as the device of 3D (stereopsis) type or the device of touch screen type.In turn, It can be set to flexible type, and can be used as documented 2nd interlayer dielectric in Japanese Patent Laid-Open 2011-145686 bulletin (48) documented interlayer dielectric (520) or in Japanese Patent Laid-Open 2009-258758 bulletin.
(organic EL display device)
Organic EL display device of the invention is characterized in that the cured film for having of the invention.
As organic EL display device of the invention, it is formed by except having using photosensitive polymer combination of the invention Other than planarization film or interlayer dielectric, there is no particular restriction, can enumerate aobvious using well known various organic EL of various constructions Showing device or liquid crystal display device.
For example, the tool for the TFT (Thin-Film Transistor) having as organic EL display device of the invention Body example can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..Cured film of the invention is due to electricity Excellent, therefore be preferably used after being combined with these TFT.
Fig. 2 is the composition concept map of an example of organic EL display device.Indicate the organic EL display device of bottom emission type In substrate constructed profile, and have planarization film 4.
The TFT1 of bottom gate polar form is formed on glass substrate 6, and being formed in the state of covering the TFT1 includes Si3N4's Insulating film 3.It is formed after the contact hole of diagram is omitted here, is formed on the insulating film 3 via the contact hole on the insulating film 3 It is connected to the wiring 2 (being highly 1.0 μm) of TFT1.Wiring 2 be to by between TFT1 or by thereafter the step of in formed it is organic The line that EL element is connect with TFT1.
In turn, in order to planarize the bumps as caused by the formation of wiring 2, in embedment bumps as caused by wiring 2 In the state of, planarization film 4 is formed on the insulating film 3.
The organic EL element of bottom emission type is formed on planarization film 4.That is, making the first electrode 5 comprising ITO via connecing Contact hole 7 is connected to wiring 2 and is formed on planarization film 4.In addition, first electrode 5 is equivalent to the anode of organic EL element.
The insulating film 8 for forming the shape of the periphery of covering first electrode 5 can prevent the first electricity by the way that the insulating film 8 is arranged Short circuit between pole 5 and thereafter second electrode the step of formed in.
In turn, although it is not shown in Fig. 2, it is successively deposited across desired pattern mask hole is arranged and passes Defeated layer, organic luminous layer, electron transfer layer then form the second electrode comprising Al, then in the entire surface above substrate It is bonded by using ultraviolet ray hardening type epoxy resin to seal, and is obtained in each organic EL member with glass for sealing plate The organic EL display device to active array type made of the TFT1 that is driven to it is connected on part.
Photosensitive polymer combination of the invention is of the invention by using due to hardenability and cured film excellent Photosensitive polymer combination be formed by resist pattern be made dividing wall as MEMS use element construction component or as A part of Mechanical Driven part uses after being assembled.It as such MEMS element, such as can enumerate: surface acoustic wave filtering Device (Surface Acoustic Wave Filter), bulk accoustic wave filter (Bulk Acoustic Wave Filter), gyro Instrument sensor (gyro sensor), display micro- shutter, imaging sensor, Electronic Paper, ink gun, biochip, sealant Equal parts.More specific example is at Japanese patent special table 2007-522531 bulletin, Japanese Patent Laid-Open No. 2008-250200 number There is illustration in bulletin, Japanese Patent Laid-Open 2009-263544 bulletin etc..
Photosensitive polymer combination of the invention can also be used for being formed such as day since flatness or the transparency are excellent Documented stack layer (16) and planarization film (57), Japan Patent are special in Fig. 2 of this patent special open 2011-107476 bulletin Open documented dividing wall (12) and planarization film (102), Japanese Patent Laid-Open in Fig. 4 (a) of 2010-9793 bulletin Documented stack layer (221) and the 3rd interlayer dielectric (216b), Japanese Patent Laid-Open in Figure 10 of 2010-27591 bulletin 2nd interlayer dielectric (125) documented by Fig. 4 (a) of 2009-128577 bulletin and the 3rd interlayer dielectric (126), day Documented planarization film (12) and pixel separation insulating film (14) etc. in Fig. 3 of this patent special open 2010-182638 bulletin.
In addition, photosensitive polymer combination of the invention is suitable for use as micro- since the transparency or refractive index are excellent Mirror or prism component, light-output component.It can be used, for example, as the use of prism used in the back light unit of display plate The joining member of component or prism and light guide plate.In addition, for example also acting as changing for the light-output efficiency of organic el display Kind component.
(touch panel display device)
Touch panel display device of the invention has hardening thing made of making photosensitive polymer combination hardening of the invention. In addition, touch screen of the invention has hardening thing made of making photosensitive polymer combination hardening of the invention.
Capacitive input device of the invention is characterized by having keeping photosensitive polymer combination of the invention hard Hardening thing made of change.
Capacitive input device of the invention preferably has a front panel, and the non-contact side of above-mentioned front panel extremely Less with the element of following (1)~following (5), and above-mentioned (4) are heat treatment object of the invention.
(1) mask layer
(2) multiple pad parts extend in a first direction via coupling part is formed by multiple first transparency electrode figures Case
(3) it is electrically insulated and is included on the direction intersected with above-mentioned first direction with above-mentioned first transparent electrode pattern Extend the multiple second transparency electrode patterns for being formed by multiple pad parts
(4) insulating layer that above-mentioned first transparent electrode pattern and above-mentioned second transparency electrode pattern are electrically insulated
(5) be electrically connected at least one of above-mentioned first transparent electrode pattern and above-mentioned second transparency electrode pattern and Key element of electrical conductivity (the conductive different from above-mentioned first transparent electrode pattern and above-mentioned second transparency electrode pattern element)
Capacitive input device of the invention be preferably with cover the element of above-mentioned (1)~above-mentioned (5) whole or Transparent protective layer is arranged in the mode of a part in turn, and more preferably above-mentioned transparent protective layer is cured film of the invention.
Firstly, the composition to capacitive input device is illustrated.Fig. 3 indicates capacitive input device The sectional view of composition.In Fig. 3, capacitive input device 30 includes: front panel 31, mask layer 32, first transparency electrode Pattern 33, second transparency electrode pattern 34, insulating layer 35, key element of electrical conductivity 36 and transparent protective layer 37.
Front panel 31 is made of light-transmitting substrates such as glass substrates, and the gorilla with healthy and free from worry (Corning) company can be used Glass (Gorilla Glass) is the strengthened glass etc. of representative.In addition, in Fig. 3, by front panel 31 be provided with each element it Side is known as non-contact face.In capacitive input device 30 of the invention, keep finger etc. and the contact surface of front panel 31 (non- The opposing face of contact surface) contact etc. inputted.Hereinafter, front panel is known as " substrate " sometimes.
In addition, being provided with mask layer 32 on the non-contact face of plate 31 in front.Mask layer 32 is formed at before touch screen The pattern of border shape around the display area of the non-contact side of plate, forms to be not seen lead etc..
In capacitive input device of the invention, as shown in figure 4, to cover the region of a part of front panel 31 The mode in (region in Fig. 4 other than input face) is provided with mask layer 32.In turn, in front in plate 31, as shown in figure 4, can be Opening portion 38 is set in a part.In opening portion 38, the settable mechanical switch using pressing.
As shown in figure 5, multiple first transparent electrode patterns 33, multiple second are formed on the contact surface of plate 31 in front thoroughly Prescribed electrode pattern 34 and insulating layer 35, above-mentioned multiple first transparent electrode patterns 33 be multiple pad parts via coupling part and Extend institute former in a first direction, above-mentioned multiple second transparency electrode patterns 34 are electrical with first transparent electrode pattern 33 It insulate and is included in upwardly extend with the side that first direction intersects and be formed by multiple pad part persons, above-mentioned insulating layer 35 is to make First transparent electrode pattern 33 and 34 person of being electrically insulated of second transparency electrode pattern.Above-mentioned first transparent electrode pattern 33, second Transparent electrode pattern 34 and aftermentioned key element of electrical conductivity 36 are for example using ITO (Indium Tin Oxide) or indium zinc oxide The conductive metal oxidation films of translucency such as (Indium Zinc Oxide, IZO) makes.As such metal film, can arrange It lifts: ito film；The metal film of Al, Zn, Cu, Fe, Ni, Cr, Mo etc.；SiO2Deng metal oxide film etc..At this point, the film of each element Thickness can be set as 10nm~200nm.In addition, because making the ito film of amorphous become polycrystalline ito film by calcining, therefore can also reduce Resistance.In addition, above-mentioned first transparent electrode pattern 33, second transparency electrode pattern 34 and aftermentioned key element of electrical conductivity 36 can also It is manufactured using photosensitive transfer printing material, which has the photoresist group using above-mentioned conducting fibre Close object.In addition, can refer to No. 4506785 bulletins of Japanese Patent No. when forming first conductive pattern etc. using ITO etc. 0014~paragraph of paragraph 0016 etc..
In addition, at least one of first transparent electrode pattern 33 and second transparency electrode pattern 34 can be across front panels 31 Non-contact face and mask layer 32 are arranged with front panel 31 is the two regions of the face of opposite side.In Fig. 3, second is indicated Transparent electrode pattern across front panel 31 non-contact face and mask layer 32 with front panel 31 be the two areas of the face of opposite side Domain is come the figure that is arranged.
First transparent electrode pattern 33 and second transparency electrode pattern 34 are illustrated using Fig. 5.Fig. 5 is to indicate this hair The explanatory diagram of an example of first transparent electrode pattern and second transparency electrode pattern in bright.As shown in figure 5, first transparency electrode Pattern 33 is that pad part 33a extends via coupling part 33b in a first direction to be formed.In addition, second transparency electrode figure Case 34 is electrically insulated with first transparent electrode pattern 33 by insulating layer 35 and is included in the direction intersected with first direction Extend in (second direction in Fig. 5) and is formed by multiple pad parts.It herein, can when forming first transparent electrode pattern 33 Above-mentioned pad part 33a and coupling part 33b is made as integrally, can also only make coupling part 33b, and by pad part 33a and second transparency electrode pattern 34 make (patterning) as integrally.When by pad part 33a and second transparency electrode pattern 34 as integrally come when making (patterning), as shown in figure 5, being formed as follows each layer: a part of coupling part 33b and A part of pad part 33a is connected and first transparent electrode pattern 33 and second transparency electrode pattern 34 pass through insulating layer 35 And it is electrically insulated.
In Fig. 3, the surface side of opposite side is provided with key element of electrical conductivity 36 with front panel 31 in mask layer 32.Electric conductivity Element 36 be at least one of first transparent electrode pattern 33 and second transparency electrode pattern 34 be electrically connected and with first thoroughly Prescribed electrode pattern 33 and the different element of second transparency electrode pattern 34.In Fig. 3, key element of electrical conductivity 36 and second transparent is indicated The figure that electrode pattern 34 connects.
In addition, being provided with transparent protective layer 37 in a manner of all covering each component in Fig. 3.It is transparency protected Layer 37 can be constituted in a manner of only covering a part of each component.Insulating layer 35 can be identical with transparent protective layer 37 Material can also be different material.
<capacitive input device and the touch panel display device for having capacitive input device>
By the manufacturing method of the present invention capacitive input device obtained and has capacitance type input dress Setting can be using " newest touch screen technology " (distribution on July 6th, 2009, when technology as the touch panel display device of constituent element Generation (Techno Times) (share)), three paddy hero two supervize, " technology and exploitation of touch screen ", CMC publish (2004,12), put down (2009 Forum of the FPD International) T-11 of plate display international symposium 2009 gives a lecture teaching material, Sai Pulasi semiconductor Institute in company (Cypress Semiconductor Corporation) application guide (Application Note) AN2292 etc. The composition of announcement.
<touch screen and its manufacturing method>
Touch screen of the invention is all or part of heat treatment object comprising resin combination of the invention of insulating layer The touch screen of (hardening thing).In addition, touch screen of the invention, which is preferably at least, has transparent substrate, ITO electrode and insulating layer.
Touch panel display device of the invention is preferably the touch panel display device with touch screen of the invention.
In addition, the manufacturing method of touch screen of the invention is the touch screen with transparent substrate, ITO electrode and insulating layer Manufacturing method preferably comprises following step: in a manner of contacting with ITO electrode, this is coated with by ink-jet application mode The step of ink-jet application photosensitive polymer combination of invention；Mounting has opening for regulation shape on above-mentioned resin combination The mask and irradiation active energy ray of mouth pattern are come the step of being exposed；Develop to the resin combination after exposure Step；And the step of resin combination after development is heated to manufacture insulating layer.
As the transparent substrate in touch screen of the invention, it is preferable to enumerate: glass substrate, quartz base plate, transparent tree Aliphatic radical plate etc..
It is above-mentioned in a manner of being contacted with ITO electrode, ink-jet application sense of the invention is coated with by ink-jet application mode Ink-jet application in the step of photosensitive resin composition can be carried out similarly with above-mentioned application step, and preferred form is also identical. In addition, in above-mentioned steps, as long as at least part for the photosensitive polymer combination of the invention being coated with connects with ITO electrode Touching.
The above-mentioned mounting on resin combination has the mask and irradiation active energy ray of the patterns of openings of regulation shape The step of being exposed, and the step of developing to the resin combination after exposure can in the same manner as above-mentioned step of exposure into Row, preferred form are also identical.
The step of above-mentioned resin combination to after development is heated to manufacture insulating layer can be with above-mentioned heat treatment step It is carried out similarly, preferred form is also identical.
In addition, an example as the ITO electrode pattern in touch screen of the invention, it is preferable to enumerate shown in above-mentioned Fig. 5 Pattern.
[embodiment]
Hereinafter, enumerating embodiment to further illustrate the present invention.Without departing from purport of the invention, then reality below Applying material, usage amount shown in example, ratio, process content, processing routine etc. can be suitable for changing.Therefore, the scope of the present invention It is not limited to concrete example as shown below.Furthermore as long as " part ", " % " are quality criteria in advance without special instruction.
Below in an example, symbol below respectively indicates compound below.
MATHF: methacrylic acid tetrahydrofuran -2- base ester (composite)
MAEVE: methacrylic acid 1- ethoxy ethyl ester (and Wako Pure Chemical Industries (share) manufacture)
MACHOE: methacrylic acid 1- (cyclohexyloxy) ethyl ester (composite)
MATHP: methacrylic acid tetrahydro -2H- pyrans -2- base ester (village Xin Zhong chemical industry (share) manufacture)
GMA: glycidyl methacrylate (and Wako Pure Chemical Industries (share) manufacture)
OXE-30: methacrylic acid (3- Ethyloxetane -3- base) methyl esters (Osaka Organic Chemical Industry (share) system It makes)
NBMA: n-butoxy methyl acrylamide (beautiful positive (share) manufacture of Mitsubishi)
MAA: methacrylic acid (and Wako Pure Chemical Industries (share) manufacture)
HEMA: 2-hydroxyethyl methacrylate (and Wako Pure Chemical Industries (share) manufacture)
MAA: methyl methacrylate (and Wako Pure Chemical Industries (share) manufacture)
St: styrene (and Wako Pure Chemical Industries (share) manufacture)
DCPM: two ring pentyl ester of methacrylic acid (Hitachi's chemical conversion industry (share) manufacture)
V-601: 2,2 '-azo of dimethyl-bis- (propionic acid 2- methyl esters) (and Wako Pure Chemical Industries (share) manufacture)
V-65:2,2 '-azos bis- (2,4- methyl pentane nitriles) (and Wako Pure Chemical Industries (share) manufacture)
MEDG: diethylene glycol ethyl methyl ether (eastern nation's chemical industry (share) manufacture, Ha Yisuo (Hisolve) EDM)
PGMEA: acetic acid methoxyl group propyl ester (Showa electrician (share) manufacture)
<synthesis of MATHF>
Methacrylic acid (86g, 1mol) is first cooled to 15 DEG C, then adds camphorsulfonic acid (4.6g, 0.02mol).To 2- dihydrofuran (71g, 1mol, 1.0 equivalent) is added dropwise in the solution.After stirring 1 hour, add saturated sodium bicarbonate (500mL), And extracted using ethyl acetate (500mL), after being dried using magnesium sulfate, insoluble matter is filtered, then 40 DEG C with Under be concentrated under reduced pressure, the yellow oil of residue is evaporated under reduced pressure, and obtain boiling point (bp.) as colorless oil Methacrylic acid tetrahydrofuran -2- base ester (MATHF) 125g (yield 80%) of 54 DEG C~56 DEG C/3.5mmHg fraction.
Furthermore in addition to 2- dihydrofuran is altered to corresponding compound, with method identical with above-mentioned MATHF conjunction At MACHOE.
<measuring method of acid value>
The acid value of polymer is measured by using the titration of potassium hydroxide.
<preparation of dispersion liquid D1>
The dispersion liquid of following compositions is concocted, and mixes it with 17,000 part of zirconium oxide bead (0.3mm φ), then Disperse within 12 hours using coating vibrating machine (Paint Shaker).Leaching zirconium oxide bead (0.3mm φ), and obtain dispersion liquid D1。
Titanium dioxide (stone originates in industry (share) manufacture, trade name: TTO-51 (C), average primary particle diameter: 10nm~ 30nm): 1,875 parts
Dispersing agent (Di Sipabike (DISPERBYK) -111: Japanese Bi Ke chemical (BYK-ChemieJapan) (stock Part) manufacture 30%PGMEA solution): 2,200 parts
Solvent PGMEA (propylene glycol methyl ether acetate): 3,425 parts
<dispersion liquid D2~dispersion liquid D10 preparation>
TTO-51 (C) and Di Sipabike (DISPERBYK) -111 are altered to recorded person in table 1 respectively, except this with Outside, by with dispersion liquid D1 prepare it is identical in a manner of obtain dispersion liquid D2~dispersion liquid D10 respectively.
[table 1]
Dispersion liquid Inorganic particulate Dispersing agent
D1 TTO-51(C) Di Sipabike (DISPERBYK) -111
D2 TTO-51(C) Di Sipabike (DISPERBYK) -2001
D3 TTO-51(C) Suo Sipa (Solsperse) 41000
D4 TTO-51(C) Compound 1
D5 TTO-51(C) Compound 2
D6 TTO-51(A) Di Sipabike (DISPERBYK) -111
D7 TTO-51(A) Di Sipabike (DISPERBYK) -2001
D8 TTO-51(A) Suo Sipa (Solsperse) 41000
D9 TTO-51(A) Compound 1
D10 TTO-51(A) Compound 2
Furthermore contracted notation other than the above used in dispersion liquid recorded in table 1 is as follows.Furthermore compound 1 and " m ", " n " of compound 2 indicate averagely substitution number, and the value of " P1: the P2 " of compound 1 indicates copolymerization ratio (mass ratio), compound 2 " P1 " value indicate monomeric unit repeat number.
In addition, compound 1 and compound 2 are referring to documented side in Japanese Patent Laid-Open 2007-277514 bulletin Method synthesizes.
Titanium oxide (TiO2) particle (2 kinds)-
TTO-51 (C): titanium dioxide, stone originate in industry (share) manufacture, average primary particle diameter: 10nm~30nm
TTO-51 (A): titanium dioxide, stone originate in industry (share) manufacture, average primary particle diameter: 10nm~30nm
Dispersing agent (5 kinds)-
Di Sipabike (DISPERBYK) -111: dispersing agent, Japanese Bi Ke chemical (share) manufacture
Di Sipabike (DISPERBYK) -2001: dispersing agent, Japanese Bi Ke chemical (share) manufacture
Suo Sipa (Solsperse) 41000: dispersing agent, Lubrizol Corp.'s manufacture
Compound 1 (following compounds, Mw=13,800,30%PGMEA solution)
Compound 2: following compounds, Mw=3,200,30%PGMEA solution
Polymer (3 kinds)-
<synthesis of polymer P 1>
Under stream of nitrogen gas, by add up to 100 parts methacrylic acid tetrahydrofuran -2- base ester (0.40 molar equivalent), Methacrylic acid (0.10 molar equivalent), methacrylic acid (3- Ethyloxetane -3- base) methyl esters (0.50 molar equivalent), And the mixed solution of propylene glycol methyl ether acetate (PGMEA) (120 parts) is heated to 70 DEG C.Stir the mixed solution on one side, one Face lasts 3.5 hours dropwise addition radical polymerization initiator V-601, and (2,2 '-azo of dimethyl-is bis- (propionic acid 2- methyl esters), He Guangchun Medicine industry (share) manufacture, 12.0 parts) and PGMEA (80 parts) mixed solution.After completion of dropwise addition, carried out 2 hours at 70 DEG C Reaction, thus to obtain the PGMEA solution of polymer P 1.And then it adds PGMEA and solid component concentration is adjusted to 40 mass %.
The weight average molecular weight (Mw) of polymer P 1 obtained measured by gel permeation chromatography (GPC) is 15, 000.Acid value is 45mgKOH/g.
<synthesis of polymer P 2>
In addition to monomer composition is altered to following monomer composition, by being polymerize with the identical method of polymer P 1 The PGMEA solution of object P2.And then it adds PGMEA and solid component concentration is adjusted to 40 mass %.
Methacrylic acid tetrahydrofuran -2- base ester (0.65 molar equivalent),
Methacrylic acid (0.15 molar equivalent),
Methyl methacrylate (0.20 molar equivalent)
The weight average molecular weight (Mw) of polymer P 2 obtained measured by gel permeation chromatography (GPC) is 15, 000.Acid value is 60mgKOH/g.
<synthesis of polymer P 3>
In addition to monomer composition is altered to following monomer composition, by being polymerize with the identical method of polymer P 1 The PGMEA solution of object P3.And then it adds PGMEA and solid component concentration is adjusted to 40 mass %.
Glycidyl methacrylate (0.70 molar equivalent),
Methacrylic acid (0.10 molar equivalent),
Styrene (0.15 molar equivalent)
Two ring pentyl ester of methacrylic acid (0.05 molar equivalent)
The weight average molecular weight (Mw) of polymer P 3 obtained measured by gel permeation chromatography (GPC) is 12, 000.Acid value is 45mgKOH/g.
<synthesis of polymer P 4>
MEDG (89g) is added into three-necked flask, is warming up to 90 DEG C in a nitrogen environment.2 hours are lasted into the solution MAA (amount as the 9.5mol% in all monomer components), MATHF is added dropwise (as the 43mol%'s in all monomer components Amount), GMA (being equivalent to the 47.5mol% in all monomer components), V-65 is (relative to the total of all monomer components 100mol% is equivalent to 4mol%) and make these dissolutions.It is stirred 2 hours after completion of dropwise addition, then terminates reaction.Thus it obtains Obtain polymer P 4.Furthermore the ratio of the total amount of MEDG and other compositions is set as 70:30.That is, preparing solid component concentration and being 30% polymer solution.
<synthesis of 5~polymer P of polymer P 11>
Type, the polymerization initiator etc. of monomer used in being changed as described in Table 2, and synthesize other polymers.
[table 2]
The numerical value of especially not additional unit in above-mentioned table 2 is using mol% as unit.In addition, the numerical value of polymerization initiator It is mol% when monomer component to be set as to 100mol%.
Solid component concentration can be calculated by formula below.
Solid component concentration: monomer weight/(monomer weight+weight of solvent) × 100 (unit: quality %)
In addition, reaction temperature is set as 90 DEG C when using V-601 as initiator, when use V-65 as initiator When, reaction temperature is set as 70 DEG C.
(embodiment 1)
<preparation of photosensitive polymer combination>
It deployed, mixed after uniform solution is made with following form, use the polyethylene in the aperture with 0.2 μm Filter processed is filtered, and the photosensitive polymer combination of embodiment 1 is made.Use photosensitive resin composition obtained Object carries out aftermentioned various evaluations.It shows the results of the evaluation in aftermentioned table 3.
Propylene glycol methyl ether acetate: 191.1 parts
The 0.2%PGMEA solution of alkali compounds K-1 (Japan's chemical conversion industry (share) manufacture, CMTU): 25.7 parts
The 30%PGMEA solution of polymer P 1: 263.3 parts
Photoacid generator B-1 (following compounds): 5.1 parts
(JER157S65, Mitsubishi Chemical control interest (Mitsubishi Chemical Holdings) (stock crosslinking agent F-1 Part) manufacture, epoxide equivalent: 200g/eq~220g/eq): 17.9 parts
Silane compound J-1 (3- glycidoxypropyltrimewasxysilane, KBM-403, SHIN-ETSU HANTOTAI's chemical industry (share) manufacture): 4.5 parts
Yi Jialesi (Irganox) 1726 (antioxidant, BASF AG's manufacture): 3.0 parts
The 2.0%PGMEA of non-ionic surfactant (F-554, DIC (share) manufacture) containing perfluoroalkyl is molten Liquid: 11.0 parts
D1:478.4 parts of dispersion liquid
Heterocyclic compound AF-5 with 2 or more nitrogen-atoms: 1,000 parts of total amount relative to mentioned component are 5.8 part
<synthesis of B-1>
Above-mentioned B-1 is synthesized according to the following method.
To beta naphthal (10g), chlorobenzene (30mL) suspension solution in add aluminium chloride (10.6g), 2- chlorpromazine chloride (10.1g) reacts 2 hours after mixed liquor is heated to 40 DEG C.Under ice cooling, 4, the HCl/water that 4N is added dropwise into reaction solution is molten Liquid (60mL) then adds ethyl acetate (50mL) and carries out liquid separation.Potassium carbonate (19.2g) is added into organic layer, at 40 DEG C After lower reaction 1 hour, adds the HCL aqueous solution (60mL) of 2N and carry out liquid separation, after organic layer is concentrated, utilize diisopropyl ether (10mL) will crystallize slurried again (reslurry), then be filtered, dry and obtain ketone compound (6.5g).
To ketone compound obtained (3.0g), methanol (30mL) suspension solution in add acetic acid (7.3g), 50 matter It measures % aqueous hydroxylamine solution (8.0g), and is heated to reflux.Place it is cooling after, add water (50mL), to the crystallization being precipitated into Row filtering, after being cleaned using cold methanol, is dried and obtains oxime compound (2.4g).
It is dissolved in oxime compound obtained (1.8g) in acetone (20mL), adds triethylamine under ice cooling, 4 (1.5g), paratoluensulfonyl chloride (2.4g) is warming up to room temperature (25 DEG C) and reacts 1 hour afterwards.Water (50mL) is added into reaction solution, It is slurried again using methanol (20mL) after being filtered to the crystallization being precipitated, it is then filtered, dries and obtain 2.3g's B-1。
Furthermore B-1's1H-NMR spectrum (300MHz, CDCl3) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
Ingredient B (heterocyclic compound with 2 or more nitrogen-atoms)-
Compare compound H-1~compare compound H-3-
(evaluation method)
<residual film ratio in unexposed portion is evaluated>
On the glass substrate (trade name: XG, Corning Incorporated's manufacture) of 100mm × 100mm, using spin coater with film The mode that thickness becomes 1.0 μm is coated with photosensitive polymer combination obtained, and drying in 120 seconds is carried out in 80 DEG C of heating plate (prebake conditions).
Then, at 23 DEG C, by the KOH aqueous solution of 0.5 mass % and develop within 30 seconds using covering liquid method, and then utilize Ultrapure water elute within 10 seconds.Thereafter, and then film thickness is measured, thus finds out and is set as relative to by original film thickness (1.0 μm) Residual film ratio after the development of 100% the case where.Furthermore evaluation criteria is as follows.1 or 2 be usage range.
1: the residual film ratio after development is 90% or more.
2: the residual film ratio after development is 80% or more, less than 90%.
3: the residual film ratio less than 80% after development.
<analyticity evaluation>
In the 100mm for having carried out processing in 3 minutes using hexamethyldisilazane (Hexamethyldisilazane, HMDS) On the glass substrate (trade name: XG, Corning Incorporated's manufacture) of × 100mm, become with film thickness 2.0 μm of side using spin coater Formula is coated with photosensitive polymer combination obtained, and drying (prebake conditions) in 120 seconds is carried out in 90 DEG C of heating plate.
Secondly, using ghi ray high-pressure mercury-vapor lamp exposure machine, with illumination 20mW/cm2、200mJ/cm2Across line and space It is exposed for 1: 1 mask with 1%~60% grayscale (gradation).
Then, at 23 DEG C, by 0.5% KOH aqueous solution and develop within 30 seconds using covering liquid method, and then utilize ultrapure Water elute within 10 seconds.Then, it is heated 45 minutes at 220 DEG C and obtains pattern.The pattern is carried out using optical microscopy Observation.
The operation since the line of mask and 50 μm of the width in space, and make 5 μm of reduced width every time until 10 μm are Only, 10 μm or less when make 1 μm of reduced width every time, by optimum exposure part can the minimum widith of clearly pattern-making set For resolution ratio.1~3 is usage range.
1: resolution ratio is 5 μm or less.
2: resolution ratio is more than 5 μm and is 10 μm or less.
3: resolution ratio is more than 10 μm and is 50 μm or less.
4: pattern can not be formed under the line of mask and 50 μm of width of space.
<evaluation of transmitance>
On the glass substrate (trade name: XG, Corning Incorporated's manufacture) of 100mm × 100mm, using spin coater with film The mode that thickness becomes 1.0 μm is coated with photosensitive polymer combination obtained, and drying in 120 seconds is carried out in 80 DEG C of heating plate (prebake conditions).In turn, heat treatment in 245 minutes (rear baking) is implemented to coated film in 220 DEG C of baking oven, utilizes big tomb electronics Light splitting after being toasted after the MCPD-3000 measurement of (share) manufacture, and evaluate by evaluation criteria below the transmission of 400nm Rate.
The transmitance of 1:400nm is 85% or more.
The transmitance of 2:400nm is 80% or more, less than 85%.
The transmitance of 3:400nm less than 80%.
<evaluation of ITO visibility>
The pattern of ITO is formed in the glass substrate of 100mm × 100mm (trade name: XG, Corning Incorporated's manufacture) in advance, Then photosensitive polymer combination obtained is coated in such a way that film thickness becomes 1.0 μm by spin coater, and at 80 DEG C Heating plate on carry out drying (prebake conditions) in 120 seconds.
Secondly, using ghi ray high-pressure mercury-vapor lamp exposure machine, with illumination 20mW/cm2、200mJ/cm2To substrate entire surface It is exposed.
Then, the desciccator diaphragm of photonasty group resin combination is heated 45 minutes and is arranged on ITO pattern at 220 DEG C. In bright interior, when tilting substrate obtained visually to be observed, and with photonasty is not set on ITO pattern It is compared when resin combination, and carries out the evaluation of visibility.Furthermore evaluation criteria is that the pattern of ITO is more not easy to be seen It is the more preferred.1 or 2 be usage range.
1: being not substantially visible to the pattern of ITO.
2: the pattern of ITO can be seen indistinctly.
3: it may be clearly seen that the pattern of ITO.
<evaluation of mist degree (transparency)>
On the glass substrate (trade name: XG, Corning Incorporated's manufacture) of 100mm × 100mm, using spin coater with dry The mode that dry film thickness becomes 2.0 μm is coated with photosensitive polymer combination obtained, and carries out 120 seconds in 80 DEG C of heating plate Dry (prebake conditions).In turn, heat treatment in 45 minutes (rear baking) is implemented to coated film in 220 DEG C of baking oven, for rear baking Mist degree after roasting keeps film surface upward, and test according to plastic products using the NDH-5000 of Japanese electric color industrial (share) manufacture Method (JIS K7136JIS K7361ASTM D1003) measures turbidity (haze value).
Furthermore so-called haze value refers to by the value represented by spreading the ratio (%) for penetrating light for full light through light. Haze value is smaller, indicates that the transparency is higher.
1: haze value less than 0.5%.
2: haze value is 0.5% or more, less than 0.7%.
3: haze value is 0.7% or more, less than 1.0%.
4: haze value is 1.0% or more, less than 2.0%.
5: haze value is 2.0% or more.
<evaluation of refractive index>
Photosensitive polymer combination obtained is coated on silicon wafer substrate using rotator, and is carried out at 80 DEG C The film with a thickness of 0.5 μm is consequently formed in drying in 120 seconds.Using extra-high-pressure mercury vapour lamp, with 200mJ/cm2It (is carried out using i ray Measurement) substrate is exposed, thereafter, heated 45 minutes at 220 DEG C using baking oven.
Use ellipsograph VUV-VASE (Japanese J.A. fertile blue (J.A.Woollam Japan) (share) is manufactured), measurement The refractive index of cured film under 589nm.
(2~embodiment of embodiment 23 and 1~comparative example of comparative example 4)
In 2~embodiment of embodiment 23 and 1~comparative example of comparative example 4, dispersion liquid, ingredient A and/or ingredient B are distinguished It is altered to recorded person in table 3, in addition to this, prepares photosensitive polymer combination similarly to Example 1, and respectively commented Valence.Evaluation result is shown in Table 3 together.
<preparation of dispersion liquid D11>
The dispersion liquid of following compositions is concocted, and mixes it with 17,000 part of zirconium oxide bead (0.3mm φ), is then made Disperse within 12 hours with coating vibrating machine (Paint Shaker).Leaching zirconium oxide bead (0.3mm φ), and obtain dispersion liquid D11.
Titanium dioxide (stone originates in industry (share) manufacture, trade name: TTO-51 (C), average primary particle diameter: 10nm~ 30nm): 1,875 parts
Dispersing agent (Di Sipabike (DISPERBYK) -111: dispersing agent, Japanese Bi Ke chemical (share) manufacture 30%PGMEA solution): 2,200 parts
AF-5:187.5 parts of heterocyclic compound with 2 or more nitrogen-atoms
Solvent PGMEA (propylene glycol methyl ether acetate): 3237.5 parts
(embodiment 24)
<preparation of photosensitive polymer combination>
It deployed, mixed after uniform solution is made with following form, use the polyethylene in the aperture with 0.2 μm Filter processed is filtered, and the photosensitive polymer combination of embodiment 24 is made.Use photosensitive resin composition obtained Object carries out aftermentioned various evaluations.It shows the results of the evaluation in aftermentioned table 3.
Propylene glycol methyl ether acetate: 191.1 parts
The 0.2%PGMEA solution of alkali compounds K-1 (Japan's chemical conversion industry (share) manufacture, CMTU): 25.7 parts
The 30%PGMEA solution of polymer P 1: 263.3 parts
Photoacid generator B-1 (above compound): 5.1 parts
Crosslinking agent F-1 (JER157S65, Mitsubishi Chemical holding (share) manufacture, epoxide equivalent: 200g/eq~220g/ Eq): 17.9 parts
Silane compound J-1 (3- glycidoxypropyltrimewasxysilane, KBM-403, SHIN-ETSU HANTOTAI's chemical industry (share) manufacture): 4.5 parts
Yi Jialesi (Irganox) 1726 (antioxidant, BASF AG's manufacture): 3.0 parts
The 2.0%PGMEA solution of non-ionic surfactant (F-554, DIC (share) manufacture) containing perfluoroalkyl: 11.0 parts
D11:478.4 parts of dispersion liquid
<preparation of dispersion liquid D12>
The dispersion liquid of following compositions is concocted, and mixes it with 17,000 part of zirconium oxide bead (0.3mm φ), is then made Disperse within 12 hours with coating vibrating machine (Paint Shaker).Leaching zirconium oxide bead (0.3mm φ), and obtain dispersion liquid D12.
Titanium dioxide (stone originates in industry (share) manufacture, trade name: TTO-51 (C), average primary particle diameter: 10nm~ 30nm): 1,875 parts
Dispersing agent (Di Sipabike (DISPERBYK) -111: dispersing agent, Japanese Bi Ke chemical (share) manufacture 30%PGMEA solution): 2,829 parts
Solvent PGMEA (propylene glycol methyl ether acetate): 2,796 parts
(embodiment 25)
<preparation of photosensitive polymer combination>
It deployed, mixed after uniform solution is made with following form, use the polyethylene in the aperture with 0.2 μm Filter processed is filtered, and the photosensitive polymer combination of embodiment 25 is made.Use photosensitive resin composition obtained Object carries out aftermentioned various evaluations.It shows the results of the evaluation in aftermentioned table 3.
Propylene glycol methyl ether acetate: 191.1 parts
The 0.2%PGMEA solution of alkali compounds K-1 (Japan's chemical conversion industry (share) manufacture, CMTU): 25.7 parts
The 30%PGMEA solution of polymer P 1: 263.3 parts
Photoacid generator B-1 (following compounds): 5.1 parts
Crosslinking agent F-1 (JER157S65, Mitsubishi Chemical holding (share) manufacture, epoxide equivalent: 200g/eq~220g/ Eq): 17.9 parts
Silane compound J-1 (3- glycidoxypropyltrimewasxysilane, KBM-403, SHIN-ETSU HANTOTAI's chemical industry (share) manufacture): 4.5 parts
Yi Jialesi (Irganox) 1726 (antioxidant, BASF AG's manufacture): 3.0 parts
The 2.0%PGMEA of non-ionic surfactant (F-554, DIC (share) manufacture) containing perfluoroalkyl is molten Liquid: 11.0 parts
D12:478.4 parts of dispersion liquid
Heterocyclic compound AF-5 with 2 or more nitrogen-atoms: 1,000 parts of total amount relative to mentioned component are 5.8 part
(embodiment 26)
In embodiment 26, AF-5 is altered to AF-11, in addition to this, prepares photoresist similarly to Example 1 Composition, and the photosensitive polymer combination of embodiment 26 is made.Using photosensitive polymer combination obtained, carry out aftermentioned Various evaluations.It shows the results of the evaluation in aftermentioned table 3.
[table 3]
<dispersion liquid D13~dispersion liquid D14 preparation>
TTO-51 (C) and Di Sipabike (DISPERBYK) -111 are altered to recorded person in following table 4 respectively, removed Other than this, by with dispersion liquid D1 prepare it is identical in a manner of obtain dispersion liquid D13 and dispersion liquid D14 respectively.
" n1 ", " n2 ", " m " in the formula of compound 3 indicate averagely substitution number, and the value of " k " indicates the repetition of monomeric unit Number.
Furthermore compound 3 is synthesized referring to documented method in Japanese Patent Laid-Open 2007-277514 bulletin.
[table 4]
Dispersion liquid Inorganic particulate Dispersing agent
D13 TTO-51(C) Compound 3
D14 TTO-51(A) Compound 3
Compound 3: following compounds, Mw=4,300,30%PGMEA solution
(embodiment 27)
<preparation of photosensitive polymer combination>
It deployed, mixed after uniform solution is made with following form, use the polyethylene in the aperture with 0.2 μm Filter processed is filtered, and the photosensitive polymer combination of embodiment 27 is made.Use photosensitive resin composition obtained Object carries out aftermentioned various evaluations.It shows the results of the evaluation in aftermentioned table 7.
Propylene glycol methyl ether acetate: 307.5 parts
Alkali compounds K-2 (following compounds): 0.02 part
7:100.0 parts of polymer P
B-1:1.9 parts of photoacid generator
F-1:6.9 parts of crosslinking agent
J-1:1.7 parts of silane compound
The 2.0%PGMEA of non-ionic surfactant (F-554, DIC (share) manufacture) containing perfluoroalkyl is molten Liquid: 0.08 part
D10:181.7 parts of dispersion liquid
AF-12:0.2 parts of heterocyclic compound with 2 or more nitrogen-atoms
Yi Jialesi (Irganox) 1726 (antioxidant, BASF AG's manufacture): 1.14 parts
(28~embodiment of embodiment 68)
In addition to being altered to polymer, photoacid generator, sensitizer, other compositions shown in following table 5 and table 6, with Embodiment 27 similarly prepares photosensitive polymer combination respectively.Furthermore the additive amount of each component amount in table 5 and table 6 indicates Relative to 100.0 parts of component of polymer of the mass parts containing ingredient A.In addition, each polymer of the ingredient A in table 5 and table 6 Additive amount indicates the quality % in 100 parts of component of polymer containing ingredient A.Using photosensitive polymer combination obtained, Carry out aftermentioned various evaluations.It shows the results of the evaluation in aftermentioned table 7.
[table 7]
As defining such as the result according to shown in above-mentioned table 7, the mist degree of photosensitive polymer combination of the invention is low, is adding Also high transmittance is maintained after heat.In contrast, know that the transmitance of the photosensitive polymer combination of comparative example after the heating is also low, And mist degree is not good enough.
Indicate the details of the contracted notation of each compound used in 27~embodiment of embodiment 68 other than the above such as Shown in lower.
<polymer>
P4~P11: according to polymer synthesized by above-mentioned synthesis example
P12: Zhuan Chen (Joncryl) 67 (acrylic resin of alkali-soluble, weight average molecular weight 12,500, acid value are 213mgKOH/g, BASF AG's manufacture)
<photoacid generator>
B-2: the compound of structure shown in following is (according to the paragraph of Japanese patent special table 2002-528451 bulletin Documented method synthesizes in 0108)
B-3:PAG-103 (trade name, it is following shown in structure, BASF AG manufacture)
B-4:GSID-26-1, triarylsulfonium salt (BASF AG's manufacture)
<crosslinking agent (thermal cross-linking agent)>
F-1:JER157S65 (phenolic resin varnish type epoxy resin, Mitsubishi Chemical holding (share) manufacture)
F-2:JER828 (bisphenol A type epoxy resin, Mitsubishi Chemical holding (share) manufacture)
F-3:JER1007 (bisphenol A type epoxy resin, Mitsubishi Chemical holding (share) manufacture)
<sensitizer>
I-1:DBA (9,10- dibutoxy anthracenes, Kawasaki chemical conversion industry (share) manufacture)
<silane compound>
J-1:3- glycidoxypropyltrimewasxysilane (KBM-403, SHIN-ETSU HANTOTAI's chemical industry (share) manufacture)
J-2: ruthenium trimethoxysilane (KBM-3103 (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture))
<alkali compounds>
K-1:CMTU
K-2:1,5- diazabicyclo [4.3.0] -5- nonene (Tokyo chemical conversion industry (share) manufacture)
(embodiment 69)
In Fig. 1 of No. 3321003 bulletins of Japanese Patent No. in documented active array type LCD, with such as Under type forms cured film 17 and is used as interlayer dielectric, and obtains the liquid crystal display device of embodiment 69.That is, by embodiment 13 Photosensitive polymer combination is spun on substrate, after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, uses high-pressure mercury Lamp irradiates 45mJ/cm from mask2(illumination 20mW/cm2) i ray (365nm), then shown using alkaline aqueous solution Shadow and form pattern, and heat treatment in 30 minutes is carried out at 230 DEG C, and form cured film 17 as interlayer dielectric.
To liquid crystal display device obtained apply driving voltage as a result, know it for show good display characteristic, And the liquid crystal display device of high reliablity.
(embodiment 70)
The organic EL display device using thin film transistor (TFT) (TFT) is made by the following method (referring to Fig. 2).
The TFT1 of bottom gate polar form is formed on glass substrate 6, and being formed in the state of covering the TFT1 includes Si3N4's Insulating film 3.Then, it is formed on the insulating film 3 after the contact hole of diagram is omitted here, via the contact hole in insulating film The wiring 2 (being highly 1.0 μm) for being connected to TFT1 is formed on 3.The wiring 2 be to by between TFT1 or will thereafter the step of in The line that the organic EL element of formation is connect with TFT1.
In turn, in order to planarize the bumps as caused by the formation of wiring 2, in embedment bumps as caused by wiring 2 In the state of, towards insulating film 3 on formed planarization film 4.Formation towards the planarization film 4 on insulating film 3 is by embodiment 13 Photosensitive polymer combination is spun on substrate, after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, uses high-pressure mercury Lamp irradiates 45mJ/cm from mask2(illumination 20mW/cm2) i ray (365nm), then shown using alkaline aqueous solution Shadow and form pattern, and heat treatment in 30 minutes is carried out at 230 DEG C.
Coating when photosensitive resin coating composition is good, the cured film obtained after exposure, development, calcining In, the generation of gauffer or slight crack is not seen.In turn, the average scale of wiring 2 is 500nm, the film thickness of made planarization film 4 For 2,000nm.
Then, the organic EL element of bottom emission type is formed on planarization film 4 obtained.Firstly, making comprising ITO First electrode 5 is connected to wiring 2 via contact hole 7 and is formed on planarization film 4.Thereafter, it is coated with resist, and carries out preliminary drying Roasting, the mask across desired pattern is exposed, and is then developed.Using the resist pattern as mask, by making Pattern processing is carried out with the wet etching of ITO etchant.Thereafter, at 50 DEG C, anticorrosive additive stripping liquid controlling (remover is used (Remover) 100, the manufacture of peace intelligence electronic material (AZ Electronic Materials) company) above-mentioned resist pattern is shelled From.The first electrode 5 obtained in the above described manner is equivalent to the anode of organic EL element.
Then, the insulating film 8 of the shape of the periphery of covering first electrode 5 is formed.By the photoresist group of embodiment 13 It closes object and is used for insulating film 8, form insulating film 8 in the same way as described above.By the way that the insulating film 8 is arranged, the first electricity can be prevented Short circuit between pole 5 and thereafter second electrode the step of formed in.
In turn, it in vacuum deposition apparatus, is successively deposited across desired pattern mask hole is arranged and passes Defeated layer, organic luminous layer, electron transfer layer.Then, the second electrode comprising Al is formed in the entire surface above substrate.From steaming Aforesaid substrate obtained is taken out in plating machine, is bonded by using glass for sealing plate with ultraviolet ray hardening type epoxy resin To seal.
As above, obtain and connected in each organic EL element to active matrix made of the TFT1 that is driven to it The organic EL display device of type.Applied via driving circuit it is alive as a result, know its for show good display characteristic and The organic EL display device of high reliablity.
(embodiment 71)
By method described below, and touch is made using the photosensitive polymer combination of high refractive index of the invention Screen display device.
<formation of first transparent electrode pattern>
[formation of transparent electrode layer]
The front panel of the intensive treatment glass for being previously formed mask layer (300mm × 400mm × 0.7mm) is directed into very In empty room, SnO is used2Containing ratio is the ITO target (indium: tin=95: 5 (molar ratios)) of 10 mass %, passes through direct current (Direct Current, DC) magnetic control sputtering plating (condition: the temperature of substrate is 250 DEG C, and argon pressure is 0.13Pa, and oxygen pressure is 0.01Pa) forms thickness Degree is the ito thin film of 40nm, and obtains the front panel for being formed with transparent electrode layer.The sheet resistance of ito thin film is 80 Ω/.
Then, commercially available etching resist is coated on ITO and is dried, and form etching resist layer.It will expose Photomask (the quartzy exposed mask with transparent electrode pattern) the distance between face and above-mentioned etching resist layer is set as 100 μm, with 50mJ/cm2After the light exposure of (i ray) carries out pattern exposure, developed using dedicated developer solution, Jin Er Rear baking processing in 30 minutes is carried out at 130 DEG C, and is obtained and be formed with transparent electrode layer and etching light-curable resin layer figure The front panel of case.
Make to be formed with transparent electrode layer and etching and is impregnated in addition with the front panel of photocurable resin layer pattern and has ITO erosion Carve agent (hydrochloric acid, potassium chloride solution；Liquid temperature be 30 DEG C) etching groove in, carry out 100 seconds handle, will be not by etching resist layer The transparent electrode layer in the region of covering and exposing dissolves removal, and obtains with the transparent electrode for having etching resist layer pattern The front panel of layer pattern.
Then, make to be impregnated in the front panel of the transparent electrode layer pattern with etching resist layer pattern dedicated anti- It loses in agent stripper, etching is removed with light-curable resin layer, and obtain and be formed with mask layer and first transparent electrode pattern Front panel.
[formation of insulating layer]
The photosensitive polymer combination of embodiment 41 is coated on before being formed with mask layer and first transparent electrode pattern On panel and (film thickness is 1 μm, 90 DEG C, 120 seconds) is dried, and obtains photosensitive polymer combination layer.By exposed mask (tool Having the quartzy exposed mask of insulating layer pattern) the distance between face and above-mentioned photosensitive polymer combination layer be set as 30 μm, With 50mJ/cm2The light exposure of (i ray) carries out pattern exposure.
Then, it at 23 DEG C, is carried out 15 second by the tetramethyl ammonium hydroxide aqueous solution of 2.38 mass % and using covering liquid method Development, and then elute within 10 seconds using ultrapure water.Then, rear baking processing in 45 minutes is carried out at 220 DEG C, and obtains shape At the front panel for having mask layer, first transparent electrode pattern, insulating layer pattern.
<formation of second transparency electrode pattern>
[formation of transparent electrode layer]
Before being formed until insulating layer pattern in such a way that the formation with above-mentioned first transparent electrode pattern is identical Plate carries out DC magnetron sputtering process (condition: the temperature of substrate is 50 DEG C, and argon pressure is 0.13Pa, and oxygen pressure is 0.01Pa), is formed thick Degree is the ito thin film of 80nm, and obtains the front panel for being formed with transparent electrode layer.The sheet resistance of ito thin film is 110 Ω/.
In a manner of identical with the formation of first transparent electrode pattern, the is formed with using the acquisition of commercially available etching resist One transparent electrode pattern is formed by insulating layer pattern, transparent electrode layer, erosion using the photosensitive polymer combination of embodiment 41 Carve front panel (the rear baking processing of resist pattern；130 DEG C, 30 minutes).
In turn, it is etched in a manner of identical with the formation of first transparent electrode pattern, and removes etching resist layer, Thus to obtain being formed with mask layer, first transparent electrode pattern, be formed by using the photosensitive polymer combination of embodiment 41 The front panel of insulating layer pattern, second transparency electrode pattern.
<formation of the key element of electrical conductivity different from first transparent electrode pattern and second transparency electrode pattern>
In a manner of identical with the formation of above-mentioned first transparent electrode pattern and second transparency electrode pattern, to being formed with First transparent electrode pattern is formed by insulating layer pattern, the second transparent electricity using the photosensitive polymer combination of embodiment 41 The front panel of pole figure case carries out DC magnetron sputtering process, and obtains the front panel for being formed with aluminium (Al) film with a thickness of 200nm.
In a manner of identical with the formation of above-mentioned first transparent electrode pattern and second transparency electrode pattern, use is commercially available Etching resist acquisition be formed with first transparent electrode pattern, be formed by using the photosensitive polymer combination of embodiment 41 Insulating layer pattern, second transparency electrode pattern, the front panel for etching resist pattern.(rear baking processing；130 DEG C, 30 minutes).
In turn, it is etched in a manner of identical with the formation of first transparent electrode pattern (30 DEG C, 50 seconds), and will etching Resist layer removes (45 DEG C, 200 seconds), thus to obtain being formed with mask layer, first transparent electrode pattern, utilizing embodiment 41 Photosensitive polymer combination is formed by insulating layer pattern, second transparency electrode pattern and first transparent electrode pattern and second The front panel of the different key element of electrical conductivity of transparent electrode pattern.
<formation of transparent protective layer>
Formed in a manner of identical with the formation of insulating layer to above-mentioned first transparent electrode pattern and the second transparent electricity On front panel until the different key element of electrical conductivity of pole figure case, the photosensitive polymer combination of coating Examples 41 is simultaneously dried (film thickness is 1 μm, 90 DEG C, 120 seconds), and obtain photosensitive polymer combination film.In turn, not across exposed mask with 50mJ/ cm2The light exposure of (i ray) carries out preceding exposure, is then developed, post-exposure (1,000mJ/cm2), rear baking processing, and Acquisition is laminated as follows is formed by insulating layer (transparent protective layer) using the photosensitive polymer combination of embodiment 41 Front panel, which are formed by mask layer, first transparent electrode pattern, using the photosensitive polymer combination of embodiment 41 Insulating layer pattern, second transparency electrode pattern, the conduction different from first transparent electrode pattern and second transparency electrode pattern The mode that property element all covers.
<production of image display device (touch screen)>
On the liquid crystal display element manufactured by the method by being recorded in Japanese Patent Laid-Open 2009-47936 bulletin The front panel manufactured before fitting has figure of the capacitive input device as constituent element using the production of well known method As display device.
<evaluation of front panel and image display device>
First transparent electrode pattern, second transparency electrode pattern and the respective conduction of the key element of electrical conductivity different from the two Property there is no problem, on the other hand, between first transparent electrode pattern and second transparency electrode pattern have insulating properties, as touching Screen is touched, good display characteristic is obtained.In turn, first transparent electrode pattern and second transparency electrode pattern are not easy to be seen, Obtain the excellent image display device of display characteristic.

Claims (20)

1. a kind of photosensitive polymer combination, characterized by comprising:
As ingredient A, have the Component units for the base protected containing acidic group by sour decomposability base polymer,
As ingredient B, heterocyclic compound with 2~6 nitrogen-atoms,
As ingredient C, photoacid generator,
As ingredient D, metal oxide particle and
As ingredient E, solvent, wherein
The ingredient B is that have at least compound of the heterocycle structure containing nitrogen-atoms on 1,3.
2. photosensitive polymer combination according to claim 1, wherein the ingredient B is that have on 1,3 at least The compound of 5 circle heterocyclic ring structures or 6 circle heterocyclic ring structures containing nitrogen-atoms.
3. photosensitive polymer combination according to claim 1 or 2, wherein the ring person of the heterocycle of the ingredient B includes carbon Atom and nitrogen-atoms.
4. photosensitive polymer combination according to claim 1 or 2, wherein the ingredient B be by following formula (1) represented by Compound:
In formula (1), R1And R2Separately indicate the organic group of hydrogen atom, halogen atom or monovalence, R1With R2It can be bonded and be The organic group of divalent, R3And R4Separately indicate the organic group of hydrogen atom or monovalence, L1It indicates to form 5 member rings or 6 member rings The concatenating group of divalent, R3Or R4With L1It can be bonded and form ring, in addition, when there is the nitrogenous double bond as documented by dotted line, dotted line Bond indicate be not present R2And R4, when the nitrogenous double bond as documented by dotted line is not present, the bond of dotted line indicates that there are R2And R4。
5. photosensitive polymer combination according to claim 1 or 2, wherein the ingredient B contains sulfydryl or thioketones base.
6. photosensitive polymer combination according to claim 1 or 2, wherein the ingredient B is by following formula (1-1) or formula Compound represented by (1-2):
In formula (1-1) and formula (1-2), R6~R8Separately indicate the organic group of hydrogen atom or monovalence, L2And L3Independently Ground indicates to form the concatenating group of the divalent of 5 member rings or 6 member rings, R6With L2It can be bonded and form ring, R7Or R8With L3It can be bonded and shape Cyclization.
7. photosensitive polymer combination according to claim 1 or 2, wherein the molecular weight of the ingredient B be 1,000 with Under.
8. photosensitive polymer combination according to claim 1 or 2, wherein the ingredient D is selected from multiple by titanium oxide, titanium Close the metal oxide particle of at least one of oxide, the formed group of zirconium oxide.
9. photosensitive polymer combination according to claim 1 or 2, wherein the total solid content relative to composition, at The content for dividing D is 30 mass % or more.
10. photosensitive polymer combination according to claim 1 or 2 further includes the crosslinking agent as ingredient F.
11. photosensitive polymer combination according to claim 1 or 2 further includes the antioxidant as ingredient G.
12. a kind of manufacturing method of hardening thing at least successively includes step a~step c:
As the application step of step a, photosensitive polymer combination according to any one of claim 1 to 11 is coated with In on substrate；
As the solvent removal step of step b, solvent is removed from the resin combination being coated with；And
As the heat treatment step of step c, the resin combination for eliminating solvent is heat-treated.
13. a kind of resin pattern manufacturing method at least successively includes step 1~step 5:
As the application step of step 1, photosensitive polymer combination according to any one of claim 1 to 11 is coated with In on substrate；
As the solvent removal step of step 2, solvent is removed from the resin combination being coated with；
As the step of exposure of step 3, the resin combination for eliminating solvent is exposed into pattern-like using actinic ray；
As the development step of step 4, developed using aqueous developer to exposed resin combination；And
As the heat treatment step of step 5, developed resin combination is heat-treated.
14. a kind of hardening thing is obtained by the manufacturing method of hardening thing according to claim 12.
15. a kind of hardening thing is obtained by resin pattern manufacturing method according to claim 13.
16. a kind of cured film, be make photosensitive polymer combination according to any one of claim 1 to 11 harden and It is formed.
17. cured film according to claim 16 is interlayer dielectric.
18. a kind of liquid crystal display device comprising cured film according to claim 16 or 17.
19. a kind of organic electroluminescence display device and method of manufacturing same comprising cured film according to claim 16 or 17.
20. a kind of touch panel display device comprising cured film according to claim 16 or 17.
CN201380042751.3A 2012-08-31 2013-08-29 Resin combination, cured film, object and its preparation method and display device with pattern Expired - Fee Related CN104541202B (en)

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