CN104756010A - Photosensitive resin composition, cured product and manufacturing method thereof, resin pattern production method, cured film, organic EL display device, liquid crystal display device, and touch panel display device - Google Patents
Photosensitive resin composition, cured product and manufacturing method thereof, resin pattern production method, cured film, organic EL display device, liquid crystal display device, and touch panel display device Download PDFInfo
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- CN104756010A CN104756010A CN201380055865.1A CN201380055865A CN104756010A CN 104756010 A CN104756010 A CN 104756010A CN 201380055865 A CN201380055865 A CN 201380055865A CN 104756010 A CN104756010 A CN 104756010A
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- YUWFEBAXEOLKSG-UHFFFAOYSA-N Cc1c(C)c(C)c(C)c(C)c1C Chemical compound Cc1c(C)c(C)c(C)c(C)c1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/002—Monoazomethine dyes
- C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
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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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
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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
- G03F7/004—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
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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
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- 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
- G02F1/133357—Planarisation layers
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- 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
- G02F1/13338—Input devices, e.g. touch panels
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
Abstract
The purpose of the present invention is to provide a photosensitive resin composition by which it is possible to obtain a cured product with a high refractive index, little yellowing, and excellent chemical resistance. The photosensitive resin composition is characterized by containing (component A) a polymer which comprises a structural unit having an acid group protected by an acid-decomposable group, (component B) a compound not having an aromatic ether bond and a phenol group and having an epoxy group and/or an oxetanyl group, (component C) metal oxide particles, (component D) a photo acid-generating agent, and (component E) a solvent. Further, the component C is preferably titanium oxide particles or zirconium oxide particles.
Description
Technical field
The present invention relates to a kind of photosensitive polymer combination (following, sometimes referred to as " composition of the present invention ").In addition, the present invention relates to a kind of above-mentioned photosensitive polymer combination is hardened hardening thing and manufacture method, the resin pattern manufacture method of the above-mentioned photosensitive polymer combination of use, the cured film that above-mentioned photosensitive composite is hardened and use the various image display devices of above-mentioned cured film.
More specifically; the present invention relates to one be suitable for the photosensitive polymer combination of the planarization film of the electronic component forming liquid crystal indicator, organic electroluminescent (Electroluminescence, EL) display device, touch panel display device, integrated circuit component, solid photographic element etc., diaphragm or interlayer dielectric and use its manufacture method of cured film.
Background technology
Because of the development of solid photographic element or liquid crystal indicator, and start extensively to carry out utilizing organic material (resin) to make the optical components such as lenticule, optical waveguide, anti-reflective film.
In order to make the refractive index of these optical components uprise, and studying particles (with reference to following patent documentation 1) such as adding titanium dioxide.
In addition, as existing resin combination, there will be a known resin combination described in patent documentation 2 ~ patent documentation 4.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2006-98985 publication
[patent documentation 2] Japanese Patent Laid-Open 2009-258723 publication
[patent documentation 3] Japanese Patent Laid-Open 2011-127096 publication
[patent documentation 4] Japanese Patent Laid-Open 2000-193983 publication
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and a kind ofly obtain that refractive index is high, yellow coloring is few, the photosensitive polymer combination of the hardening thing of good chemical resistance.
The technological means of dealing with problems
Above-mentioned problem of the present invention is solved by means described in following <1>, <8> ~ <11> or <13> ~ <15>.Below <2> ~ the <7> as preferred example and <12> is recorded in the lump.
<1> photosensitive polymer combination, it is characterized in that comprising: (composition A) is containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base, (composition B) does not have aromatic series ehter bond and phenolic group and has the compound of epoxy radicals and/or oxetanylmethoxy, (composition C) metal oxide particle, (components D) light acid producing agent, and (composition E) solvent;
The photosensitive polymer combination of <2> according to above-mentioned <1>, wherein composition C is Titanium particles or Zirconia particles;
The photosensitive polymer combination of <3> according to above-mentioned <1> or <2>, it also comprises (composition F) spreading agent;
The photosensitive polymer combination of <4> according to above-mentioned <3>, wherein composition F contains the spreading agent with at least one acidic group;
The photosensitive polymer combination of <5> according to above-mentioned <4>, wherein composition F contains by following formula (S) expression and has the spreading agent of at least one acidic group;
[changing 1]
(in formula (S), R
3represent the concatenating group of (m+n) valency, R
4and R
5separately represent the concatenating group of singly-bound or divalence, A
2represent the organic group of the monovalence containing the following part-structure of at least one, the group that alkyl, alkoxysilane group, epoxy radicals, isocyanate group and hydroxyl that it is more than 4 that above-mentioned part-structure is 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 form, n A
2, R
4can be identical, also can be different, m represents that 0 ~ 8, n represents that 2 ~ 9, m+n is 3 ~ 10, P
2represent macromolecular scaffold, m P
2, R
5can be identical, also can be different)
The photosensitive polymer combination of <6> according to any one of above-mentioned <1> to <5>, wherein above-mentioned have the Component units of the base that acidic group is protected by sour decomposability base for the Component units represented by following formula;
[changing 2]
(in formula, R
121represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, L
1represent carbonyl or phenylene, R
122~ R
128separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4)
The photosensitive polymer combination of <7> according to any one of above-mentioned <1> to <6>, wherein components D is oxime sulfonate compounds;
The manufacture method of a <8> hardening thing, is characterized in that: comprise step (a) ~ step (c) at least successively;
(a) photosensitive polymer combination according to any one of above-mentioned <1> to <7> is coated application step on substrate,
(b) remove in the resin combination that is coated with solvent solvent removal step and
C heat treatment step that () is heat-treated the resin combination eliminating solvent;
<9> resin pattern manufacture method, is characterized in that: comprise step (1) ~ step (5) at least successively:
(1) photosensitive polymer combination according to any one of above-mentioned <1> to <7> is coated the application step on substrate,
(2) remove in the resin combination that is coated with the solvent removal step of solvent,
(3) utilize actinic ray the resin combination eliminating solvent is exposed into pattern-like step of exposure,
(4) utilize aqueous developer solution to through exposure the resin combination development step of developing and
(5) to the heat treatment step that the resin combination through development is heat-treated;
<10> hardening thing, it utilizes the manufacture method of hardening thing according to above-mentioned <8> or the resin pattern manufacture method according to above-mentioned <9> and obtains;
<11> cured film, it makes the photosensitive polymer combination according to any one of above-mentioned <1> to <7> harden and be formed;
The cured film of <12> according to above-mentioned <11>, it is interlayer dielectric;
<13> liquid crystal indicator, it comprises the cured film according to above-mentioned <11> or <12>;
<14> organic electroluminescence display device and method of manufacturing same, it comprises the cured film according to above-mentioned <11> or <12>;
<15> touch panel display device, it comprises the cured film according to above-mentioned <11> or <12>.
The effect of invention
According to the present invention, can provide a kind of and obtain that refractive index is high, yellow coloring is few, the photosensitive polymer combination of the hardening thing of good chemical resistance.
Accompanying drawing explanation
Fig. 1 represents the formation concept map of an example of liquid crystal indicator.Represent the constructed profile of the active-matrix substrate in liquid crystal indicator, and there is the cured film 17 as interlayer dielectric.
Fig. 2 represents the formation concept map of an example of organic EL display.Represent the constructed profile of the substrate in the organic EL display of bottom emission type, and there is planarization film 4.
Fig. 3 is the sectional view of the formation representing capacitive input device.
Fig. 4 is the key diagram of the example representing front panel.
Fig. 5 is the key diagram of the example representing the first transparent electrode pattern and the second transparent electrode pattern.
Embodiment
Below, content of the present invention is described in detail.The explanation of constitutive requirements described is below carried out based on representative example of the present invention sometimes, but the present invention is not limited thereto kind of an example.
Moreover in the present invention, represent that the record of " lower limit ~ upper limit " of numerical range represents " more than lower limit, below the upper limit ", the record of " upper limit ~ lower limit " represents " below the upper limit, more than lower limit ".That is, the numerical range comprising the upper limit and lower limit is represented.In addition, in the present invention, " quality % " is identical with the implication of " % by weight ", and " mass parts " is identical with the implication of " weight portion ".
In addition; in the present invention; also will " (composition A) is containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base " etc. referred to as " composition A " etc., also by " (a1) has the Component units of the base that acidic group is protected by sour decomposability base " described later etc. referred to as " Component units (a1) " etc.
And then, in the statement of base (atomic group) in this manual, do not record the statement being substituted and being unsubstituted and comprise not there is substituent base (atomic group), and comprise yet there is substituent base (atomic group).Such as, so-called " alkyl ", not only comprises and does not have substituent alkyl (alkyl be unsubstituted), also comprise and have substituent alkyl (alkyl be substituted).
In the following description, the combination of preferred form and preferred form is preferred form.
(photosensitive polymer combination)
Photosensitive polymer combination of the present invention is (following; also referred to as " resin combination ") feature be to comprise: (composition A) is containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base; (composition B) does not have aromatic series ehter bond and phenolic group and has the compound of epoxy radicals and/or oxetanylmethoxy; (composition C) metal oxide particle; (components D) light acid producing agent, and (composition E) solvent.
Photosensitive polymer combination of the present invention can be used as eurymeric anti-corrosion agent composition aptly.
The resin combination of the character that photosensitive polymer combination of the present invention preferably has Yin Re and hardens.
In addition, photosensitive polymer combination of the present invention is preferably positive type photosensitive organic compound, is more preferably the positive type photosensitive organic compound (chemically amplified positive photosensitive polymer combination) of chemical amplification type.
Photosensitive polymer combination of the present invention is preferably and does not contain 1,2-quinone di-azido compound as the photoactinic smooth acid producing agent of induction.1, although 2-quinone di-azido compound generates carboxyl by progressively type photochemical reaction, its quantum yield must be less than 1.
Relative to this; the acid that (components D) light acid producing agent used in the present invention generates because of induction actinic ray plays a role to the deprotection of the acidic group protected in composition A as catalyzer; therefore contribute to multiple deprotection reaction by the acid that the effect of 1 light quantum generates; quantum yield is more than 1; such as become value large as several powers of 10; as the result of so-called chemical amplification, high sensitivity can be obtained.
And then, photosensitive polymer combination of the present invention is preferably lenticule, optical waveguide, anti-reflective film, light emitting diode (LightEmitting Diode, LED) with the optical component resin combination of sealing material and LED chip coating material etc., or the observability reduction resin combination of the distribution electrode used in touch-screen.Moreover, the observability reduction composition of the distribution electrode used in so-called touch-screen, refer to the observability reducing the distribution electrode used in touch-screen, namely, make the component composition that distribution electrode is not easily in sight, include, for example tin indium oxide (Indium Tin Oxide, ITO) interelectrode interlayer dielectric etc., photosensitive polymer combination of the present invention can be suitably used for such use.
Usually, if chemically amplified positive photosensitive polymer combination is exposed, then by the effect with light acid producing agent, the disengaging base that contained polymkeric substance has departs from, and is dissolved in developer solution, and unexposed portion is formed as pattern.
When by containing inorganic particulate, spreading agent and comprise depart from base polymkeric substance resin combination be used as positive type photosensitive organic compound time, the dispersiveness of inorganic particulate is extremely important, if successfully do not disperse, then there is following problem: mean grain size does not diminish and excessive, or generation aggregated particle, or oversize grain is not remained by pulverizing, when final photosensitive resin coating composition, the transparency is not good enough.On the other hand, the compatibility of the bonding agent in dispersion liquid and photosensitive polymer combination is also important, if combination is poor, then can produce muddiness in a liquid.
The present inventor carries out the result studied in great detail, finds the photosensitive polymer combination by being set to containing composition A ~ composition E, and can obtain and a kind ofly obtain that refractive index is high, yellow coloring is few, the photosensitive polymer combination of the hardening thing of good chemical resistance.
Below, photosensitive polymer combination of the present invention is described in detail.
(composition A) is containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base
Photosensitive polymer combination of the present invention comprises (composition A) containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base.
Moreover, in the present invention, also " having the Component units of the base that acidic group is protected by sour decomposability base " is called " Component units that (a1) has the base that acidic group is protected by sour decomposability base ".
Photosensitive polymer combination of the present invention and then can comprise the polymkeric substance beyond the polymkeric substance containing the Component units with the base that acidic group is protected by sour decomposability base.
Photosensitive polymer combination of the present invention is preferably containing the component of polymer comprising the polymkeric substance of at least one meeting following (1) and following (2).
(1) containing (a1), there is the polymkeric substance that the Component units of the base that acidic group is protected by sour decomposability base and (a2) have the Component units of bridging property base
(2) containing (a1), there is the polymkeric substance of the Component units of the base that acidic group is protected by sour decomposability base and there is containing (a2) polymkeric substance of the Component units of bridging property base
The polymkeric substance that photosensitive polymer combination of the present invention can and then contain beyond these.As long as no special instructions, then the composition A in the present invention refers to except above-mentioned (1) and/or (2), contains optionally and the composition of other polymkeric substance of interpolation.
With regard to sclerosis after the transparency (mist degree) and unexposed portion residual film ratio viewpoint with regard to, photosensitive polymer combination of the present invention be preferably containing meeting the composition of above-mentioned (1) as composition A.
On the other hand, with regard to the viewpoint of the degree of freedom of MOLECULE DESIGN, photosensitive polymer combination of the present invention is preferably containing meeting the composition of above-mentioned (2) as composition A.
Moreover; when containing when meeting the composition of above-mentioned (1), also and then can comprise and containing (a1), there is the acryl resin of the Component units of the base that acidic group protect by sour decomposability base and/or contain the acryl resin that (a2) has the Component units of bridging property base.
In addition; when containing when meeting the composition of above-mentioned (2); when at least comprise be equivalent to containing (a1) have the Component units of the base that acidic group is protected by sour decomposability base and (a2) there is the composition of the polymkeric substance of the Component units of bridging property base time, also as situation about being equivalent to containing the composition meeting above-mentioned (1).
Composition A is preferably the resin of addition polymerization type, is more preferably the polymkeric substance containing the Component units being derived from (methyl) acrylic acid and/or its ester.Moreover, also can have the Component units beyond the Component units being derived from (methyl) acrylic acid and/or its ester, such as, be derived from cinnamic Component units or be derived from the Component units etc. of vinyl compound.
Moreover, also " being derived from the Component units of (methyl) acrylic acid and/or its ester " is called " acrylic acid series Component units ".In addition, " (methyl) acrylic acid " refers to " methacrylic acid and/or acrylic acid ".
< Component units (a1) >
Composition A comprises the polymkeric substance at least containing (a1) with the Component units of the base that acidic group is protected by sour decomposability base.Comprise the polymkeric substance containing Component units (a1) by composition A, and can be made into the high photosensitive polymer combination of sensitivity.
" base that acidic group is protected by sour decomposability base " in the present invention can be used as acidic group and the known base of sour decomposability base, is not particularly limited.As concrete acidic group, can preferably enumerate carboxyl and phenolic hydroxyl group.In addition, as sour decomposability base, can use than the base being easier to decompose because of acid acetal system functional groups such as () ester structure of the base such as represented by formula described later (A1), oxinane ester group or tetrahydrofuran ester groups or compare the base (such as carbonic acid three grades of alkyl ester groups such as three grades of alkyl such as tributyl base, carbonic acid tributyl base) being difficult to decompose because of sour.
(a1) Component units with the base that acidic group is protected by sour decomposability base preferably has the Component units of the protection carboxyl that carboxyl is protected by sour decomposability base (also referred to as " having the Component units of the protection carboxyl protected by sour decomposability base ") or has the Component units (also referred to as " having the Component units of the protection phenolic hydroxyl group protected by sour decomposability base ") of the protection phenolic hydroxyl group that phenolic hydroxyl group is protected by sour decomposability base.
Below, successively the Component units (a1-1) with the protection carboxyl protected by sour decomposability base and the Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base are described respectively.
<< (a1-1) has the Component units >> of the protection carboxyl protected by sour decomposability base
The above-mentioned Component units (a1-1) with the protection carboxyl protected by sour decomposability base is the Component units of carboxyl by the following protection carboxyl protected by the sour decomposability base described in detail of the Component units had containing carboxyl.
As can be used for the above-mentioned above-mentioned Component units with carboxyl with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base, known Component units can be used with no particular limitation.Include, for example: be derived from the Component units (a1-1-1) in unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular with the unsaturated carboxylic acid of at least one carboxyl etc., or there is ethene unsaturated group and the Component units (a1-1-2) of structure being derived from acid anhydrides simultaneously.
Below, be derived from molecule the Component units of the unsaturated carboxylic acid with at least one carboxyl etc. and (a1-1-2) to can be used as above-mentioned (a1-1-1) with the Component units of carboxyl there is ethene unsaturated group be simultaneously described respectively with the Component units of the structure being derived from acid anhydrides successively.
<<< (a1-1-1) is derived from molecule the Component units >>> of the unsaturated carboxylic acid with at least one carboxyl etc.
As the above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least one carboxyl etc., the unsaturated carboxylic acid lifted as listed below can be used as the unsaturated carboxylic acid used in the present invention.Namely, as unsaturated monocarboxylic, include, for example: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(methyl) acryloyloxyethylsuccinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid etc.In addition, as unsaturated dicarboxylic, include, for example: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.In addition, the unsaturated polybasic carboxylic acid for obtaining the Component units with carboxyl also can be its acid anhydrides.Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.In addition, unsaturated polybasic carboxylic acid also can be list (2-methacryloxyalkyl) ester of polybasic carboxylic acid, include, for example: succinic acid list (2-acryloyl-oxyethyl) ester, succinic acid list (2-methacryloxyethyl) ester, phthalic acid list (2-acryloyl-oxyethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.And then unsaturated polybasic carboxylic acid also can be list (methyl) acrylate of its two ends dicarboxyl polymkeric substance, include, for example ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc.In addition, as unsaturated carboxylic acid, acrylic acid-2-carboxyethyl, methacrylic acid-2-carboxyethyl, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, 4-carboxyl styrene etc. also can be used.
Wherein, with regard to the viewpoint of developability, in order to form the above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least one carboxyl etc., preferably use the acid anhydride etc. of acrylic acid, methacrylic acid, 2-(methyl) acryloyloxyethylsuccinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid or unsaturated polybasic carboxylic acid, be more preferably and use acrylic acid, methacrylic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid.
The above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least one carboxyl etc. can comprise separately one, also can comprise two or more.
<<< (a1-1-2) has ethene unsaturated group and the Component units >>> of structure being derived from acid anhydrides simultaneously
There is the unit that ethene unsaturated group and the Component units (a1-1-2) of structure being derived from acid anhydrides are preferably derived from the monomer that hydroxyl existing in the Component units making to have ethene unsaturated group and acid anhydrides carry out reacting and obtain simultaneously.
As above-mentioned acid anhydrides, known acid anhydrides can be used, specifically, can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; The acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Among these acid anhydrides, with regard to the viewpoint of developability, be preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.
With regard to the viewpoint of developability, above-mentioned acid anhydrides is preferably 10 % by mole ~ 100 % by mole for the reaction rate of hydroxyl, is more preferably 30 % by mole ~ 100 % by mole.
-can be used for the sour decomposability base of Component units (a1-1)-
As can be used for the above-mentioned above-mentioned sour decomposability base with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base, above-mentioned sour decomposability base can be used.
Among these sour decomposability bases; with regard to the basic physical properties of photosensitive polymer combination; the particularly viewpoint of sensitivity or pattern form, the formative of contact hole, the storage stability of photosensitive polymer combination, being preferably carboxyl is the protection carboxyl protected by the form of acetal.And then, among sour decomposability base, with regard to the viewpoint of sensitivity, be more preferably carboxyl for by the protection carboxyl protected with the form of the acetal represented by following formula (a1-10).Moreover at carboxyl for by the protection carboxyl protected with the form of the acetal represented by following formula (a1-10), the entirety of protection carboxyl becomes-(C=O)-O-CR
101r
102(OR
103) structure.
[changing 3]
(in formula (a1-10), R
101and R
102separately represent hydrogen atom or alkyl, wherein, get rid of R
101with R
102be the situation of hydrogen atom.R
103represent alkyl.R
101or R
102with R
103can link and form cyclic ether).
In above-mentioned formula (a1-10), R
101~ R
103separately represent hydrogen atom or alkyl, abovementioned alkyl can be straight-chain, branched, ring-type any one.Herein, there is not R
101and R
102all represent the situation of hydrogen atom, R
101and R
102at least one represent alkyl.
In above-mentioned formula (a1-10), work as R
101, R
102and R
103when representing alkyl, abovementioned alkyl can be any one of straight-chain, branched or ring-type.
As the alkyl of above-mentioned straight-chain or branched, being preferably carbon number is 1 ~ 12, and being more preferably carbon number is 1 ~ 6, and then to be more preferably carbon number be 1 ~ 4.Specifically, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, tributyl, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.
As above-mentioned cyclic alkyl, being preferably carbon number is 3 ~ 12, and being more preferably carbon number is 4 ~ 8, and then to be more preferably carbon number be 4 ~ 6.As above-mentioned cyclic alkyl, include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc.
Abovementioned alkyl also can have substituting group, alternatively base, can illustrate halogen atom, aryl, alkoxy.When have halogen atom alternatively base time, R
101, R
102, R
103become haloalkyl, when have aryl alternatively base time, R
101, R
102, R
103become aralkyl.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be illustrated, among these halogen atoms, be preferably fluorine atom or chlorine atom.
In addition, as above-mentioned aryl, being preferably carbon number is the aryl of 6 ~ 20, is more preferably the aryl that carbon number is 6 ~ 12.Specifically, can illustrate phenyl, Alpha-Methyl phenyl, naphthyl etc., overall as the alkyl replaced by aryl, i.e. aralkyl, can illustrate benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc.
As above-mentioned alkoxy, being preferably carbon number is the alkoxy of 1 ~ 6, is more preferably the alkoxy that carbon number is 1 ~ 4, and then is more preferably methoxy or ethoxy.
In addition, when abovementioned alkyl is naphthenic base, it is the straight-chain of 1 ~ 10 or the alkyl alternatively base of branched that above-mentioned naphthenic base can have carbon number, when alkyl is the alkyl of straight-chain or branched, can have the naphthenic base alternatively base that carbon number is 3 ~ 12.
These substituting groups also can be replaced by above-mentioned substituting group further.
In above-mentioned formula (a1-10), work as R
101, R
102and R
103when representing aryl, it is 6 ~ 12 that above-mentioned aryl is preferably carbon number, and being more preferably carbon number is 6 ~ 10.Above-mentioned aryl can have substituting group, as above-mentioned substituting group, preferably can illustrate the alkyl that carbon number is 1 ~ 6.As aryl, such as, can illustrate phenyl, tolyl, xylyl, cumenyl, 1-naphthyl etc.
In addition, R
101, R
102and R
103can bond mutually, and together form ring with the carbon atom of these bonds.As R
101with R
102, R
101with R
103or R
102with R
103ring structure during bond, include, for example: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.
Moreover, in above-mentioned formula (a1-10), be preferably R
101and R
102any one be hydrogen atom or methyl.
Free radical polymerization monomer for the formation of the Component units containing the protection carboxyl represented by above-mentioned formula (a1-10) can use commercially available free radical polymerization monomer, also can use the free radical polymerization monomer utilized synthesized by known method.Such as, synthetic method etc. described in the paragraph 0037 ~ paragraph 0040 of Japanese Patent Laid-Open 2011-221494 publication can be utilized to synthesize.
Above-mentioned the first preferred form with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base is the Component units represented by following formula.
[changing 4]
(in formula, R
1and R
2separately represent hydrogen atom, alkyl or aryl, at least R
1and R
2any one be alkyl or aryl, R
3represent alkyl or aryl, R
1or R
2with R
3can link and form cyclic ether, R
4represent hydrogen atom or methyl, X represents singly-bound or arlydene).
Work as R
1and R
2during for alkyl, being preferably carbon number is the alkyl of 1 ~ 10.Work as R
1and R
2during for aryl, be preferably phenyl.R
1and R
2be preferably separately for hydrogen atom or carbon number are the alkyl of 1 ~ 4.
R
3represent alkyl or aryl, being preferably carbon number is the alkyl of 1 ~ 10, is more preferably the alkyl of 1 ~ 6.
X represents singly-bound or arlydene, is preferably singly-bound.
The above-mentioned preferred form of the second with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base is the Component units represented by following formula.
[changing 5]
(in formula, R
121represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, L
1represent carbonyl or phenylene, R
122~ R
128separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4).
R
121be preferably ammonia atom or methyl.
L
1be preferably carbonyl.
R
122~ R
128be preferably hydrogen atom.
As the above-mentioned preferred concrete example with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base, following Component units can be illustrated.Moreover R represents hydrogen atom or methyl.
[changing 6]
<< (a1-2) has the Component units >> of the protection phenolic hydroxyl group protected by sour decomposability base
The above-mentioned Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base is that the Component units with phenolic hydroxyl group has following by the Component units of the protection phenolic hydroxyl group protected by sour decomposability base of detailed description.
<<< (a1-2-1) has the Component units >>> of phenolic hydroxyl group
As the above-mentioned Component units with phenolic hydroxyl group, the Component units in the resin of hydroxy styrenes system Component units or novolaks system can be enumerated, among these Component units, with regard to the viewpoint of sensitivity, be preferably derived from the Component units of hydroxy styrenes or Alpha-Methyl hydroxy styrenes.In addition, as the Component units with phenolic hydroxyl group, with regard to the viewpoint of sensitivity, the Component units represented by following formula (a1-20) is also preferred.
[changing 7]
(in formula (a1-20), R
220represent hydrogen atom or methyl, R
221represent the concatenating group of singly-bound or divalence, R
222represent that halogen atom or carbon number are the alkyl of the straight or branched of 1 ~ 5, a represents the integer of 1 ~ 5, and b represents the integer of 0 ~ 4, and a+b is less than 5.Moreover, as the R of existence more than 2
222time, these R
222mutually can be different, also can be identical).
In above-mentioned formula (a1-20), R
220represent ammonia atom or methyl, be preferably methyl.
In addition, R
221represent the concatenating group of singly-bound or divalence.Work as R
221during for singly-bound, can sensitivity be promoted, and then the transparency of cured film can be promoted, therefore preferably.As R
221the concatenating group of divalence, can alkylidene be illustrated, as R
221for the concrete example of alkylidene, can enumerate: methylene, ethylidene, propylidene, isopropylidene, sub-normal-butyl, isobutylidene, sub-tributyl, pentylidene, isoamylidene, sub-neopentyl, hexylidene etc.Wherein, R
221be preferably singly-bound, methylene or ethylidene.In addition, the concatenating group of above-mentioned divalence can have substituting group, and alternatively base can enumerate halogen atom, hydroxyl, alkoxy etc.In addition, a represents the integer of 1 ~ 5, but with regard to effect of the present invention viewpoint or easily manufacture with regard to this point, being preferably a is 1 or 2, and being more preferably a is 1.
In addition, when will with R
221when the carbon atom carrying out bond is as benchmark (1), the binding site of the hydroxyl in phenyl ring is preferably binding on 4.
R
222separately represent that halogen atom or carbon number are the alkyl of the straight or branched of 1 ~ 5.Specifically, can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, tributyl, amyl group, isopentyl, neopentyl etc.Wherein, just easily manufacture with regard to this point, be preferably chlorine atom, bromine atoms, methyl or ethyl.
In addition, b represents the integer of 0 or 1 ~ 4.
-can be used for the sour decomposability base of Component units (a1-2)-
As can be used for the above-mentioned above-mentioned sour decomposability base with the Component units (a1-2) of the protection phenolic hydroxyl group protected by sour decomposability base; with can be used in the same manner as the above-mentioned above-mentioned sour decomposability base with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base; known sour decomposability base can be used, be not particularly limited.Among acid decomposability base; with regard to the basic physical properties of photosensitive polymer combination; particularly the viewpoint of sensitivity or pattern form, the storage stability of photosensitive polymer combination, the formative of contact hole, preferably has the Component units of the protection phenolic hydroxyl group protected by acetal.And then, among sour decomposability base, with regard to the viewpoint of sensitivity, be more preferably phenolic hydroxyl group for by the protection phenolic hydroxyl group protected with the form of the acetal represented by above-mentioned formula (a1-10).Moreover in phenolic hydroxyl group for by the protection phenolic hydroxyl group protected with the form of the acetal represented by above-mentioned formula (a1-10), the entirety of protection phenolic hydroxyl group becomes-Ar-O-CR
101r
102(OR
103) structure.Moreover Ar represents arlydene.
The preference of the acetal ester structure of phenolic hydroxyl group can illustrate R
101=R
102=R
103the combination of=methyl or R
101=R
102=methyl and R
103the combination of=benzyl.
In addition; as for the formation of the free radical polymerization monomer of Component units with the protection phenolic hydroxyl group that the form of phenolic hydroxyl group by acetal is protected, include, for example free radical polymerization monomer etc. described in the paragraph 0042 of Japanese Patent Laid-Open 2011-215590 publication.
Among these free radical polymerization monomers, with regard to the viewpoint of the transparency, be preferably the 1-alkoxyalkyl protective of methacrylic acid 4-hydroxylphenyl ester, the THP trtrahydropyranyl protective of methacrylic acid 4-hydroxylphenyl ester.
As the concrete example of the acetal protecting group of phenolic hydroxyl group; 1-alkoxyalkyl can be enumerated; include, for example 1-ethoxyethyl group, 1-methoxy ethyl, 1-n-butoxyethyl, 1-isobutoxyethy, 1-(2-chloroethoxy) ethyl, 1-(2-ethyl hexyl oxy) ethyl, 1-positive propoxy ethyl, 1-cyclohexyloxy ethyl, 1-(2-cyclohexylethoxy radical) ethyl, 1-Benzyloxyethyl etc., these bases can be used alone one or be used in combination of two or more.
Commercially available free radical polymerization monomer can be used for the formation of the above-mentioned free radical polymerization monomer with the Component units (a1-2) of the protection phenolic hydroxyl group protected by sour decomposability base, also can use the free radical polymerization monomer utilized synthesized by known method.Such as, compound and vinyl ether by making to have phenolic hydroxyl group in the presence of acid catalyst carry out reacting synthesizing.Above-mentioned synthesis also can make to have the monomer of phenolic hydroxyl group in advance and other monomers carry out copolymerization, then reacts with vinyl ether in the presence of acid catalyst.
As the above-mentioned preferred concrete example with the Component units (a1-2) of the protection phenolic hydroxyl group protected by sour decomposability base, following Component units can be illustrated, but the present invention is not limited to these Component units.In following concrete example, R represents hydrogen atom or methyl.
[changing 8]
-the preferred form of Component units (a1)-
When the polymkeric substance containing above-mentioned Component units (a1) is not in fact containing Component units (a2), in the polymkeric substance containing above-mentioned Component units (a1), the content of Component units (a1) is preferably 20 % by mole ~ 100 % by mole, is more preferably 30 % by mole ~ 90 % by mole.
When the polymkeric substance containing above-mentioned Component units (a1) contains following Component units (a2), with regard to the viewpoint of sensitivity, in the polymkeric substance containing above-mentioned Component units (a1) and Component units (a2), single Component units (a1) is preferably 3 % by mole ~ 70 % by mole, is more preferably 10 % by mole ~ 60 % by mole.In addition, especially when above-mentioned Component units (a1) is the Component units containing the protection carboxyl that carboxyl is protected by the form of acetal, 20 % by mole ~ 50 % by mole are preferably.
Moreover in the present invention, when specifying the content of " Component units " with mol ratio, the implication of above-mentioned " Component units " is identical with " monomeric unit ".In addition, in the present invention, above-mentioned " monomeric unit " is modified after polymerisation by high molecular weight reactive etc.Below like this too.
Compared with the above-mentioned Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base, the above-mentioned Component units (a1-1) with the protection carboxyl protected by sour decomposability base has development this feature fast.Therefore, when for rapid development, preferably there is the Component units (a1-1) of the protection carboxyl protected by sour decomposability base.On the contrary, when making development slack-off, be preferably the Component units (a1-2) using and there is the protection phenolic hydroxyl group protected by sour decomposability base.
Compared with the above-mentioned Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base, the above-mentioned Component units (a1-1) with the protection carboxyl protected by sour decomposability base has development this feature fast.Therefore, when for rapid development, preferably there is the Component units (a1-1) of the protection carboxyl protected by sour decomposability base.On the contrary, when making development slack-off, be preferably the Component units (a1-2) using and there is the protection phenolic hydroxyl group protected by sour decomposability base.
< (a2) has the Component units > of bridging property base
Composition A comprises the polymkeric substance containing Component units (a2), and described Component units (a2) has bridging property base.As long as above-mentioned bridging property base produces the base of sclerous reaction by heating, be then not particularly limited.As the form of Component units preferably with bridging property base, can enumerate containing be selected from by epoxy radicals, oxetanylmethoxy, by-NH-CH
2the Component units of at least one in the group that base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20) and ethene unsaturated group form, is preferably selected from by epoxy radicals, oxetanylmethoxy and by-NH-CH
2at least one in the group that base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20) forms.Wherein, photosensitive polymer combination of the present invention is more preferably mentioned component A and comprises Component units containing at least one in epoxy radicals and oxetanylmethoxy.More specifically, can enumerate following.
<< (a2-1) has the Component units >> of epoxy radicals and/or oxetanylmethoxy
Composition A preferably comprises the polymkeric substance containing Component units (Component units (a2-1)), and described Component units (Component units (a2-1)) has epoxy radicals and/or oxetanylmethoxy.The cyclic ether group of above-mentioned 3 rings is also referred to as epoxy radicals, and the cyclic ether group of 4 rings is also referred to as oxetanylmethoxy.
Above-mentioned have the Component units (a2-1) of epoxy radicals and/or oxetanylmethoxy as long as have at least one epoxy radicals or oxetanylmethoxy in 1 Component units, epoxy radicals and more than 1 oxetanylmethoxy, the epoxy radicals of more than 2 or the oxetanylmethoxy of more than 2 of more than 1 can be had, be not particularly limited, but preferably there is the epoxy radicals and/or oxetanylmethoxy that add up to 1 ~ 3, be more preferably the epoxy radicals and/or oxetanylmethoxy that have and add up to 1 or 2, and then be more preferably there is 1 epoxy radicals or oxetanylmethoxy.
As for the formation of the concrete example of free radical polymerization monomer of Component units with epoxy radicals, include, for example glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3, 4-epoxy radicals butyl ester, methacrylic acid-3, 4-epoxy radicals butyl ester, acrylic acid-3, 4-epoxycyclohexanecarboxylate, methacrylic acid-3, 4-epoxycyclohexanecarboxylate, α-ethylacrylate-3, 4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl ether, between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, the compound etc. containing ester ring type epoxy radicals skeleton described in the paragraph 0031 ~ paragraph 0035 of Jap.P. No. 4168443 publication.
As for the formation of the concrete example of free radical polymerization monomer of Component units with oxetanylmethoxy, include, for example (methyl) acrylate etc. with oxetanylmethoxy described in the paragraph 0011 ~ paragraph 0016 of Japanese Patent Laid-Open 2001-330953 publication.
As for the formation of the above-mentioned concrete example with the free radical polymerization monomer of the Component units (a2-1) of epoxy radicals and/or oxetanylmethoxy, be preferably containing the monomer of metacrylic acid ester structure, the monomer containing acrylate structural.
Among these, be preferably glycidyl methacrylate, acrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate, acrylic acid (3-Ethyloxetane-3-base) methyl esters and methacrylic acid (3-Ethyloxetane-3-base) methyl esters.These Component units can be used alone one or be used in combination of two or more.
As the preferred concrete example of Component units (a2-1) with epoxy radicals and/or oxetanylmethoxy, following Component units can be illustrated.Moreover R represents hydrogen atom or methyl.
[changing 9]
<< (a2-2) has the Component units >> of ethene unsaturated group
As the above-mentioned one with the Component units (a2) of bridging property base, the Component units (a2-2) (hereinafter also referred to as " Component units (a2-2) ") with ethene unsaturated group can be enumerated.As the above-mentioned Component units (a2-2) with ethene unsaturated group, be preferably Component units side chain with ethene unsaturated group, be more preferably end there is ethene unsaturated group and there is the Component units that carbon number is the side chain of 3 ~ 16, and then be more preferably the Component units of the side chain had represented by following formula (a2-2-1).
[changing 10]
(in formula (a2-2-1), R
301represent that carbon number is the concatenating group of the divalence of 1 ~ 13, R
302represent hydrogen atom or methyl, wave-like line part represents and the position that the main chain of the Component units with bridging property base (a2) links).
R
301be the concatenating group of the divalence of 1 ~ 13 for carbon number, the base comprising thiazolinyl, cycloalkenyl group, arlydene or these combined, also can contain the keys such as ester bond, ehter bond, amido link, amino-formate bond.In addition, the concatenating group of divalence can have the substituting group such as hydroxyl, carboxyl on arbitrary position.As R
301concrete example, the concatenating group of following divalence can be enumerated.
[changing 11]
Among side chain represented by above-mentioned formula (a2-2-1), comprise by above-mentioned R
301the concatenating group of represented divalence, is preferably aliphatic side chain.
In addition, there is about (a2-2) Component units of ethene unsaturated group, can with reference to the record of the paragraph 0072 ~ paragraph 0090 of Japanese Patent Laid-Open 2011-215580 publication.
<< (a2-3) has by-NH-CH
2the Component units >> of the base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20)
The multipolymer used in the present invention also preferably has by-NH-CH
2the Component units (a2-3) of the base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20).By containing Component units (a2-3), the heating of mitigation can be utilized to produce sclerous reaction, and the cured film of various excellent can be obtained.Herein, R is preferably the alkyl that carbon number is 1 ~ 20, is more preferably the alkyl that carbon number is 1 ~ 9, and then is more preferably the alkyl that carbon number is 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, but is preferably the alkyl of straight chain or branch.Component units (a2) is more preferably the Component units of the base had represented by following formula (a2-30).
[changing 12]
(in formula (a2-30), R
31represent hydrogen atom or methyl, R
32represent that carbon number is the alkyl of 1 ~ 20).
R
32being preferably carbon number is the alkyl of 1 ~ 9, is more preferably the alkyl that carbon number is 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, but is preferably the alkyl of straight chain or branch.
As R
32concrete example, can enumerate: methyl, ethyl, normal-butyl, isobutyl, cyclohexyl and n-hexyl.Wherein, isobutyl, normal-butyl, methyl is preferably.
-the preferred form of Component units (a2)-
When the polymkeric substance containing above-mentioned Component units (a2) is not in fact containing Component units (a1), in the polymkeric substance containing above-mentioned Component units (a2), the content of Component units (a2) is preferably 5 % by mole ~ 90 % by mole, is more preferably 20 % by mole ~ 80 % by mole.
When the polymkeric substance containing above-mentioned Component units (a2) contains above-mentioned Component units (a1), with regard to the viewpoint of chemical-resistant, in the polymkeric substance containing above-mentioned Component units (a1) and Component units (a2), single Component units (a2) is preferably 3 % by mole ~ 70 % by mole, is more preferably 10 % by mole ~ 60 % by mole.
And then, in the present invention, no matter which kind of form, in all Component units of composition A, be preferably the Component units (a2) containing 3 % by mole ~ 70 % by mole, be more preferably the Component units (a2) containing 10 % by mole ~ 60 % by mole.
If in the scope of above-mentioned numerical value, then the transparency of the cured film obtained by photosensitive polymer combination and chemical-resistant become good.
< (a3) other Component units >
In the present invention, composition A, also can containing other Component units (a3) beyond these except above-mentioned Component units (a1) and/or Component units (a2).Component units (a3) also can containing the component of polymer meeting above-mentioned (1) or above-mentioned (2).In addition, except meeting the component of polymer of above-mentioned (1) or above-mentioned (2), also can comprise the polymkeric substance in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3).When except meeting the component of polymer of above-mentioned (1) or above-mentioned (2), when comprising the component of polymer in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3), in all component of polymer, the allotment amount of above-mentioned component of polymer is preferably below 60 quality %, be more preferably below 40 quality %, and then be more preferably below 20 quality %.In addition, be preferably more than 1 quality %, be more preferably more than 5 quality %.
As the monomer becoming other Component units (a3), there is no particular restriction, include, for example: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, dicyclo unsaturated compound class, maleimide compounds class, unsaturated aromatics, conjugated diolefine based compound, unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.In addition, as described later, also can containing the Component units with acidic group.The monomer becoming other Component units (a3) can be used alone one or be used in combination of two or more.
Below, enumerate the preferred example of component of polymer contained in the composition A in the present invention, but the present invention is not limited to these examples.
-1 example-
Meet the form of the component of polymer of (1) and then other Component units (a3) containing one or more.
-2 example-
Meet the form containing (a1) with the polymkeric substance of the Component units of the base that acidic group is protected by sour decomposability base and then other Component units (a3) containing one or more of the component of polymer of (2).
-3 example-
Meet the form containing (a2) with the polymkeric substance of the Component units of bridging property base and then other Component units (a3) containing one or more of the component of polymer of (2).
-4 example-
In arbitrary example of above-mentioned 1st example ~ the 3rd example, there is in any one polymkeric substance the form of the Component units at least containing acidic group as other Component units (a3).
-5 example-
Except meeting the component of polymer of above-mentioned (1) or above-mentioned (2), and then there is the form of the component of polymer in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3).
-6 example-
Comprise the form of the two or more combination of above-mentioned 1st example ~ the 5th example.
Specifically, Component units (a3) can enumerate the Component units formed by following compound etc.: styrene, 3rd butyl phenyl ether ethene, methyl styrene, hydroxy styrenes, α-methyl styrene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, vinyl benzoic acid ethyl ester, 4-HBA (3-methacryloxypropyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, vinyl cyanide, ethylene glycol single acetyl acetic acid esters list (methyl) acrylate.In addition, compound described in the paragraph 0021 ~ paragraph 0024 of Japanese Patent Laid-Open 2004-264623 publication can be enumerated.
In addition, as other Component units (a3), with regard to the viewpoint of electrical characteristics, be preferably derived from the Component units of the monomer with aliphatics ring type skeleton or aromatic series ring type skeleton, be more preferably the Component units of the monomer being derived from phenylethylene or there is aliphatics ring type skeleton.Specifically, can enumerate: styrene, the 3rd butyl phenyl ether ethene, methyl styrene, hydroxy styrenes, α-methyl styrene, (methyl) acrylic acid two ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate etc.
And then, as other Component units (a3), with regard to the viewpoint of adhesion, be preferably derived from the Component units of (methyl) alkyl acrylate.Specifically, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate etc. can be enumerated, be more preferably (methyl) methyl acrylate.Form in the Component units of polymkeric substance, the containing ratio of above-mentioned Component units (a3) is preferably less than 60 % by mole, is more preferably less than 50 % by mole, and then is more preferably less than 40 % by mole.As lower limit, can be 0 % by mole, but be such as preferably set to more than 1 % by mole, be more preferably and be set to more than 5 % by mole.If in the scope of above-mentioned numerical value, then the various characteristics of the cured film obtained by photosensitive polymer combination become good.
Polymkeric substance contained in composition A is preferably containing having the Component units of acidic group as other Component units (a3).Polymkeric substance by having acidic group, and is easily dissolved in the developer solution of alkalescence, and effect of the present invention is more effectively played.Acidic group in the present invention refers to the proton dissociation base that pKa is less than 10.5.Usually, use the monomer that can form acidic group as the Component units with acidic group, and acidic group is directed in polymkeric substance.There is by comprising this kind in the polymer the Component units of acidic group, and there is the tendency in the developer solution being easily dissolved in alkalescence.
As the acidic group used in the present invention; can illustrate carboxylic acid group, sulfoamido, phosphonate group, sulfonic group, phenolic hydroxyl group, sulfoamido, sulfonyl imide and these acidic groups anhydride group and these acidic groups are neutralized and are formed the base etc. of salt structure, preferably at least there is carboxylic acid group and and/or phenolic hydroxyl group.As above-mentioned salt, there is no particular restriction, can preferably illustrate alkali metal salt, alkali salt and organic ammonium salt.
The Component units with acidic group used in the present invention is more preferably the Component units being derived from distyryl compound or the Component units being derived from vinyl compound, is derived from the Component units of (methyl) acrylic acid and/or its ester.
In the present invention, with regard to the viewpoint of sensitivity, be particularly preferably containing there is the Component units of carboxyl or there is the Component units of phenolic hydroxyl group.
The Component units with acidic group is preferably 1 % by mole ~ 80 % by mole of the Component units of all component of polymer, be more preferably 1 % by mole ~ 50 % by mole, and then be more preferably 5 % by mole ~ 40 % by mole, be particularly preferably 5 % by mole ~ 30 % by mole, most preferably be 5 % by mole ~ 20 % by mole.
In the present invention, except meeting the component of polymer of above-mentioned (1) or above-mentioned (2), also can comprise the polymkeric substance in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3).
As this kind of polymkeric substance, be set to not containing the compound being equivalent to composition B described later, composition F, composition L, be preferably homopolymer or the multipolymer of styrenic or acrylate based compound.
In addition, as this kind of polymkeric substance, be preferably resin side chain with carboxyl.Include, for example as No. 59-44615, Japanese Patent Laid-Open No. Sho, No. 54-34327, Jap.P. examined patent publication, No. 58-12577, Jap.P. examined patent publication, No. 54-25957, Jap.P. examined patent publication, No. 59-53836, Japanese Patent Laid-Open No. Sho, methacrylic acid copolymer described such in each publication of No. 59-71048, Japanese Patent Laid-Open No. Sho, acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, acid/maleic acid copolymers, partial esterification acid/maleic acid copolymers etc., and side chain has the acid cellulose derivant of carboxyl, in the polymkeric substance with hydroxyl addition acid anhydrides etc., and then also can enumerate on side chain there is (methyl) acryloyl group high molecular polymer as preferred polymkeric substance.
Include, for example: (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2-hydroxy propyl ester/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer described in Japanese Patent Laid-Open 7-140654 publication, acrylic acid 2-hydroxyl-3-phenoxy-propyl/polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc.
In addition, known macromolecular compound described in Japanese Patent Laid-Open 7-207211 publication, Japanese Patent Laid-Open 8-259876 publication, Japanese Patent Laid-Open 10-300922 publication, Japanese Patent Laid-Open 11-140144 publication, Japanese Patent Laid-Open 11-174224 publication, Japanese Patent Laid-Open 2000-56118 publication, Japanese Patent Laid-Open 2003-233179 publication, Japanese Patent Laid-Open 2009-52020 publication etc. can also be used.
These polymkeric substance can, only containing a kind of, also can contain two or more.
As these polymkeric substance, also commercially available SMA 1000P can be used, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (more than, Sartomer (Sartomer) company manufactures), A Lufeng (ARUFON) UC-3000, A Lufeng (ARUFON) UC-3510, A Lufeng (ARUFON) UC-3900, A Lufeng (ARUFON) UC-3910, A Lufeng (ARUFON) UC-3920, A Lufeng (ARUFON) UC-3080 (more than, East Asia synthesis (share) manufactures), Zhuan Chen (JONCRYL) 690, Zhuan Chen (JONCRYL) 678, Zhuan Chen (JONCRYL) 67, Zhuan Chen (JONCRYL) 586 (more than, BASF (BASF) company manufactures) etc.
-molecular weight of the polymkeric substance in composition A-
The molecular weight of the polymkeric substance in composition A, with polystyrene conversion weight average molecular weight, is preferably 1,000 ~ 200,000, is more preferably 2,000 ~ 50,000.If in the scope of above-mentioned numerical value, then various characteristic is good.The ratio (dispersion degree, Mw/Mn) of number average molecular weight Mn and weight average molecular weight Mw is preferably 1.0 ~ 5.0, is more preferably 1.5 ~ 3.5.
Moreover the weight average molecular weight in the present invention or the mensuration of number average molecular weight preferably utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) to measure.The mensuration of gel permeation chromatography that utilizes in the present invention preferably uses HLC-8020GPC (eastern Cao (Tosoh) (share) manufactures), and use tsk gel (TSKgel) SuperHZ M-H, tsk gel (TSK gel) Super HZ4000, tsk gel (TSKgel) SuperHZ200 (eastern Cao (share) manufacture, 4.6mmID × 15cm) as tubing string, use tetrahydrofuran (Tetrahydrofuran, THF) as eluent.
-manufacture method of the polymkeric substance in composition A-
In addition, about the synthetic method of the polymkeric substance in composition A, also there will be a known various method, if enumerate an example, then by utilizing radical polymerization initiator, the free radical polymerization monomer potpourri at least containing the free radical polymerization monomer for the formation of above-mentioned Component units (a1) and above-mentioned Component units (a3) is made to carry out being polymerized in organic solvent synthesizing.In addition, also synthesize by so-called high molecular weight reactive.
Relative to the total solid composition of photosensitive polymer combination, the content of the composition A in photosensitive polymer combination of the present invention is preferably 20 quality % ~ 99.9 quality %, be more preferably 50 quality % ~ 98 quality %, and then be more preferably 70 quality % ~ 95 quality %.If content is this scope, then the patternability carried out when developing becomes good, in addition, can obtain the hardening thing that refractive index is higher.Moreover the solid constituent amount of so-called photosensitive polymer combination, refers to the amount desolventized etc. beyond volatile ingredient.
(composition B) does not have aromatic series ehter bond and phenolic group and has the compound of epoxy radicals and/or oxetanylmethoxy
Photosensitive polymer combination of the present invention contains (composition B) and does not have aromatic series ehter bond and phenolic group and the compound with epoxy radicals and/or oxetanylmethoxy.
Composition B only can have 1 epoxy radicals or oxetanylmethoxy, also can have more than 2, in addition, also can have the epoxy radicals of more than 1 and the oxetanylmethoxy of more than 1 simultaneously.
In addition, composition B does not have phenolic group and aromatic series ehter bond, does not namely have ehter bond and is directly binding on structure on aromatic rings.
In photosensitive material, if only expose, then the sclerosis of film is insufficient, therefore adds epoxy resin and carries out thermmohardening.But, the present inventor etc. find when utilizing the photosensitive material of use metal oxide particle to carry out identical operation, compared with when there is not metal oxide particle, there is aromatic series ehter bond and phenolic group and the compound with epoxy radicals and/or oxetanylmethoxy produces yellow coloring consumingly.Infer that its reason is: because of the thermocatalyst effect (identical with photocatalyst effect) of metal oxide particle, and generate quinone body in the residual phenol composition replaced without epoxy radicals.Even if the present inventor etc. find without phenolic group, there is aromatic series ehter bond and have epoxy radicals and and/or the compound of oxetanylmethoxy, also containing the compound with phenolic group as accessory substance or through time the impurity such as analyte, even if above-claimed cpd is trace, also produce yellow coloring consumingly.
Photosensitive polymer combination of the present invention in order to suppress by heating produce painted, and use not there is epoxy compound or the oxetane compound of aromatic series ehter bond and phenolic group, can temper tiniting be prevented thus.
In addition, composition B does not have sour decomposability base, in addition, does not preferably have sour decomposability base and acidic group.
As not there is aromatic series ehter bond and phenolic group and there is the compound of epoxy radicals, alicyclic epoxy thing, aliphatic epoxide etc. can be enumerated.
As alicyclic epoxy thing, can preferably enumerate: by the oxygenant that utilizes hydrogen peroxide, peracid etc. suitable by addition epoxidation and the compound containing cyclohexene oxide or cyclopentene oxide that obtains of the compound with the naphthenic hydrocarbon such as at least one cyclohexene ring or cyclopentene ring ring.
As aliphatic epoxide, such as there are the diglycidyl ether or polyglycidyl ether etc. of aliphatic polyol or its alkylene oxide (alkylene oxide) addition product, as its typical example, can enumerate: the diglycidyl ether of ethylene glycol, the diglycidyl ether of propylene glycol or 1, the diglycidyl ether of the aklylene glycols such as the diglycidyl ether of 6-hexanediol, the polyglycidyl ether of the polyvalent alcohols such as the diglycidyl ether of glycerine or its alkylene oxide addition product or triglycidyl ether, with the diglycidyl ether of polyglycol or its alkylene oxide addition product, the diglycidyl ether of polypropylene glycol or its alkylene oxide addition product is the diglycidyl ether etc. of the poly alkylene glycol of representative.Herein, as alkylene oxide, oxirane and epoxypropane etc. can be enumerated.
Illustrate in detail and used in the present inventionly not there is aromatic series ehter bond and phenolic group and be simple function and polyfunctional epoxy compound.
As monofunctional epoxy compound, include, for example: butyl glycidyl ether, 2-hexyl glycidyl ether, allyl glycidyl ether, 1,2-epoxy butane, 1,3-butadiene monoxide, 1,2-Epoxydodecane, chloropropylene oxide, 1,2-decamethylene, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide etc.
In addition, as multi-functional epoxy compound, include, for example: 3,4-epoxycyclohexyl-methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3,4-epoxy radicals) cyclohexane-Jian diox, two (3,4-epoxycyclohexyl-methyl) adipate, two (3,4-epoxy radicals-6-methylcyclohexylmethyl) adipate, 3,4-epoxy radicals-6-methylcyclohexyl-3 ', 4 '-epoxy radicals-6 '-methylcyclohexanecarboxylic acid ester, di-2-ethylhexylphosphine oxide (3,4-7-oxa-bicyclo[4.1.0), bicyclopentadiene diepoxide, two (3,4-epoxycyclohexyl-methyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexane carboxylate), epoxy radicals di-2-ethylhexyl hexahydrophthalate, epoxy radicals di-2-ethylhexyl hexahydrophthalate, BDDE, 1,6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether class, 1,1,3-tetradecadiene dioxide, citrene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxy cyclooctane etc.
Among these epoxy compounds, be particularly preferably alicyclic epoxy thing.
In addition, in photoresist product of the present invention, also can use and not there is aromatic series ehter bond and phenolic group and the polymkeric substance of monomer for simple function and polyfunctional epoxy compound.
As the example of this kind of monomer, include, for example: glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3,4-epoxy radicals butyl ester, methacrylic acid-3,4-epoxy radicals butyl ester, acrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate, α-ethylacrylate 3,4-epoxycyclohexanecarboxylate etc.
Wherein, glycidyl methacrylate, acrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate is preferably.
In addition, the polymkeric substance of these monomers and other monomers can also be used.
As the example of other monomers of this kind, can enumerate: acrylic acid, methacrylic acid, acrylate, methacrylate.
Among these polymkeric substance, be preferably homopolymer or the multipolymer of (methyl) glycidyl acrylate, be more preferably poly-(methyl) glycidyl acrylate.
In the case of the copolymer, not there is aromatic series ehter bond and phenolic group and be preferably 99 % by mole ~ 20 % by mole for the containing ratio of the monomer of simple function and polyfunctional epoxy compound, be more preferably 99 % by mole ~ 40 % by mole, and then be more preferably 99 % by mole ~ 60 % by mole.
Not there is aromatic series ehter bond and phenolic group and be simple function and polyfunctional epoxy compound, or the molecular weight of its homopolymer or multipolymer or weight average molecular weight (Mw) are preferably 100 ~ 30,000, be more preferably 300 ~ 20,000, and then be more preferably 500 ~ 10,000.
Not there is aromatic series ehter bond and phenolic group as used in the present invention and there is the compound of oxetanylmethoxy, being preferably the compound in its structure with 1 ~ 4 oxetanylmethoxy.
As the compound in molecule with 1 ~ 2 oxetanylmethoxy, include, for example the compound etc. represented by following formula (1) ~ formula (3).
[changing 13]
R
a1fluoroalkyl, allyl, aryl, furyl or thiophene that the alkyl that expression hydrogen atom, carbon number are 1 ~ 6, carbon number are 1 ~ 6 expect base.When molecular memory is at 2 R
a1time, these R
a1can be identical, also can be different.
As alkyl, can enumerate methyl, ethyl, propyl group, butyl etc., as fluoroalkyl, any one hydrogen preferably can enumerating these alkyl is replaced by fluorine atom.
R
a2represent hydrogen atom, carbon number is the alkyl of 1 ~ 6, and carbon number is the thiazolinyl of 2 ~ 6; not there is aromatic series ehter bond and phenolic group and there is the base of aromatic rings; carbon number is the alkyl-carbonyl of 2 ~ 6, and carbon number is the alkoxy carbonyl of 2 ~ 6, and carbon number is the N-alkylcarbamoyl group of 2 ~ 6.As alkyl, methyl, ethyl, propyl group, butyl etc. can be enumerated, as thiazolinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propylene base, 2-methyl-2-propenyl, 1-butenyl group, 2-butenyl group, 3-butenyl group etc. can be enumerated.As not there is aromatic series ehter bond and phenolic group and there is the base of aromatic rings, benzyl, luorobenzyl etc. can be enumerated.As alkyl-carbonyl; ethylcarbonyl group, propyl group carbonyl, butyl carbonyl etc. can be enumerated; as alkoxy carbonyl; ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl etc. can be enumerated; as N-alkylcarbamoyl group, ethyl carbamyl, propyl group carbamyl, butylcarbamoyl, pentylcarbamoyl etc. can be enumerated.In addition, R
a2can substituting group be had, alternatively base, the alkyl of 1 ~ 6, fluorine atom can be enumerated.
R
a3represent wire alkylidene or branch-like alkylidene, poly-(alkylene oxide group) base of wire or branch-like poly-(alkylene oxide group) base, wire unsaturated alkyl or branch-like unsaturated alkyl, carbonyl or the alkylidene containing carbonyl, the alkylidene containing carboxyl, the alkylidene containing carbamyl or base shown below.As alkylidene, include, for example ethylidene, propylidene, butylidene, as poly-(alkylene oxide group) base, poly-(inferior ethoxyl) base, poly-(sub-propoxyl group) base etc. can be enumerated.As unsaturated alkyl, allylidene, methylpropenylene, butenylidene etc. can be enumerated.
[changing 14]
Work as R
a3during for above-mentioned polyad, R
a4alkoxy, halogen atom, nitro, cyano group, sulfydryl, lower alkylcarboxyl, carboxyl or carbamyl that the alkyl that expression hydrogen atom, carbon number are 1 ~ 4, carbon number are 1 ~ 4.
R
a5represent oxygen atom, sulphur atom, methylene, NH, SO, SO
2, C (CF
3)
2, or C (CH
3)
2.
R
a6represent that carbon number is alkyl or the aryl of 1 ~ 4, n is the integer of 0 ~ 2,000.R
a7represent that carbon number is alkyl, the aryl of 1 ~ 4 or has the base of monovalence of following structure.In following formula, R
a8for alkyl or aryl that carbon number is 1 ~ 4, m is the integer of 0 ~ 100.
[changing 15]
As the compound represented by formula (1), include, for example: 3-ethyl-3-hydroxymethyl oxetane (OXT-101: East Asia synthesis (share) manufactures), 3-ethyl-3-(2-Ethylhexoxymethyl) oxetanes (OXT-212: East Asia synthesis (share) manufactures), 3-ethyl-3-phenoxymethyloxetane (OXT-211: East Asia synthesis (share) manufactures).As the compound represented by formula (2), include, for example Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy methoxyl) methyl] benzene (OXT-121: East Asia synthesis (share).In addition, as the compound represented by formula (3), two (3-ethyl-3-oxetanyl methyl) ether (OXT-221: East Asia synthesis (share)) can be enumerated.
As the compound with 3 ~ 4 oxetanes rings, include, for example the compound represented by following formula (4).
[changing 16]
In formula (4), R
a1implication and above-mentioned formula (1) in R
a1identical.In addition, as the R of multivalence concatenating group
a9include, for example: the poly-branch-like polysilane such as (alkylene oxide group) base or the base represented by the following E oxygen base of the branch-like such as the branch-like alkylidene that the carbon numbers such as the base represented by following A ~ following C are 1 ~ 12, the base represented by following D etc.J is 3 or 4.
[changing 17]
In above-mentioned A, R
a10represent methyl, ethyl or propyl group.In addition, in above-mentioned D, p is the integer of 1 ~ 10.
In addition, as other forms that can be suitably used for oxetane compound of the present invention, the compound represented by following formula (5) side chain with oxetanes ring can be enumerated.
[changing 18]
In formula (5), R
a1and R
a8implication and above-mentioned formula in R
a1and R
a8identical.R
a11for alkyl or trialkylsilanyl that the carbon numbers such as methyl, ethyl, propyl group or butyl are 1 ~ 4, r is 1 ~ 4.
Among these, composition B preferably can illustrate following shown compound.Moreover in following, n represents the integer of more than 1, be preferably the integer of 1 ~ 4, be more preferably 1.
[changing 19]
Composition B can be used alone one, also can and with two or more.
Relative to total solid composition 100 mass parts of photosensitive polymer combination, the content of the composition B in photosensitive polymer combination of the present invention is preferably 0.01 mass parts ~ 30 mass parts, be more preferably 0.1 mass parts ~ 20 mass parts, and then be more preferably 1 mass parts ~ 10 mass parts.By adding within the scope of this, and can obtain that yellow coloring is few, the hardening thing of good chemical resistance.
(composition C) metal oxide particle
Resin combination of the present invention to regulate for the purpose of refractive index or light transmission, and contains metal oxide particle.Metal oxide particle because the transparency is high, have light transmission, therefore can obtain the positive type photosensitive organic compound that refractive index is high, the transparency is excellent.
Composition C is preferably the refractive index of refractive index higher than the resin combination of the material comprised except above-mentioned particle, specifically, the refractive index be more preferably in the light of the wavelength with 400nm ~ 750nm is the particle of more than 1.50, and then be more preferably the particle that refractive index is more than 1.70, be particularly preferably the particle that refractive index is more than 1.90.In addition, the upper limit of refractive index is not particularly limited, but with regard to the viewpoint obtaining easiness, being preferably refractive index is the particle of less than 2.80.
Herein, the what is called refractive index had in the light of the wavelength of 400nm ~ 750nm is more than 1.50, refer to that the mean refractive index in the light of the wavelength with above-mentioned scope is more than 1.50, and be more than 1.50 without the need to the refractive index in all light of the wavelength with above-mentioned scope.In addition, mean refractive index is by for having the summation of measured value of refractive index of each light of wavelength of above-mentioned scope divided by the value of the quantity gained of measuring point.
Moreover the metal of the metal oxide particle in the present invention also comprises the semimetals such as B, Si, Ge, As, Sb, Te.
As light transmission, metal oxide particle that refractive index is high, preferably comprise the equiatomic oxide particle of Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, be more preferably titanium dioxide, titanium composite oxide, zinc paste, zirconia, indium/tin-oxide, antimony/tin-oxide, and then be more preferably titanium dioxide, titanium composite oxide, zirconia, be particularly preferably titanium dioxide, zirconia, most preferably be titanium dioxide.As titanium dioxide, be preferably the extra high rutile-type of refractive index.In order to give dispersion stabilization, the surface of organic material to these metal oxide particles also can be utilized to process.
With regard to the viewpoint of the transparency of resin combination, the average primary particle diameter of composition C is preferably 1nm ~ 200nm, is particularly preferably 3nm ~ 80nm.Herein, utilize the particle diameter of arbitrary 200 particles of determination of electron microscopy, and its arithmetic mean is called the average primary particle diameter of particle.In addition, when the shape of particle and aspherical time, obtain the projected area of metal oxide particle, and using correspond to it area diameter projected as particle diameter.
In addition, the specific surface area of metal oxide particle is preferably 10m
2/ g ~ 400m
2/ g, is more preferably 20m
2/ g ~ 200m
2/ g, most preferably is 30m
2/ g ~ 150m
2/ g.
There is no particular restriction for the shape of metal oxide particle.Such as can be grain of rice shape, spherical, cubic, fusiform or indefinite shape.
In addition, composition C can be used alone one, also can and with two or more.
As long as the content of the composition C in resin combination of the present invention is considered the refractive index required by the optical component obtained by resin combination or light transmission etc., and be suitable for determining, but relative to the total solid composition of resin combination of the present invention, preferably be set to 5 quality % ~ 80 quality %, be more preferably and be set to 10 quality % ~ 70 quality %.
In the present invention, metal oxide particle also can be used as following dispersion liquid come in, above-mentioned dispersion liquid is by (composition F) spreading agent described later and solvent, uses the mixing arrangement such as bowl mill, rod mill to carry out mixing the dispersion liquid prepared by dispersion.
The solvent used in preparation as above-mentioned dispersion liquid, such as except (composition E) described later solvent, the alcohols etc. such as 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl-2-propanol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 3-methyl-1-butanol, 2-methyl-2-butanols, neopentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol can be enumerated.
These solvents can be used alone one or be use mixing two or more.
As the preparation method of above-mentioned dispersion liquid, there is no particular restriction, can use known method, is preferably to utilize to use the wet type dispersion machine of medium to carry out the method for disperseing.
As wet type process for dispersing, ball mill, bowl mill, sand mill etc. can be illustrated.Wherein, ball mill is preferably.
As the mean grain size of above-mentioned medium, be preferably less than 0.1mm, be more preferably more than 0.01mm, less than 0.1mm, and then be more preferably more than 0.015mm, below 0.07mm, be particularly preferably more than 0.03mm, below 0.05mm.If above-mentioned scope, then when for photosensitive polymer combination, the mist degree of the hardening thing obtained is little, analyticity is excellent, can suppress the generation of residue when developing, when patterning, edge shape becomes good.In addition, above-mentioned effect as resin combination of the present invention containing the positive type photosensitive organic compound of metal oxide particle in significantly.
(components D) light acid producing agent
Photosensitive polymer combination of the present invention contains (components D) light acid producing agent.
As the light acid producing agent used in the present invention, being preferably induction wavelength is more than 300nm, is preferably actinic ray and acidic compound that wavelength is 300nm ~ 450nm, but does not limit by its chemical constitution.In addition, be the photoactinic smooth acid producing agent of more than 300nm about directly not responding to wavelength, if by being used for responding to sensitizer the actinic ray and acidic compound that wavelength is more than 300nm, then preferably use after also can combining with sensitizer.As the light acid producing agent used in the present invention, be preferably and produce the light acid producing agent that pKa is the acid of less than 4, be more preferably and produce the light acid producing agent that pKa is the acid of less than 3, most preferably be and produce the light acid producing agent that pKa is the acid of less than 2.In addition, the lower limit of pKa is not particularly limited, but with regard to the viewpoint obtaining easiness, is preferably more than-15.
As the example of light acid producing agent, 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 light acid producing agents, with regard to the viewpoint of insulativity, sensitivity, preferably use oxime sulfonate compounds.These light acid producing agents can be used alone one or be used in combination of two or more.As the concrete example of trichloromethyl-s-triazine, two fragrant base Iodonium salts, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative, compound described in the paragraph 0083 ~ paragraph 0088 of Japanese Patent Laid-Open 2011-221494 publication can be illustrated.
As oxime sulfonate compounds, namely there is the compound of oxime sulfonates structure, preferably can illustrate the compound containing the oxime sulfonates structure represented by following formula (D1).
[changing 20]
(in formula (D1), R
21represent alkyl or aryl, wave-like line part represents the bond position with other bases).
Any base all can be substituted, R
21in alkyl can be straight-chain, also can be branch-like, also can be ring-type.The substituting group of allowing below is described.
As R
21alkyl, be preferably carbon number be 1 ~ 10 straight-chain alkyl or branch-like alkyl.R
21alkyl can be 6 ~ 11 by carbon number aryl, carbon number be 1 ~ 10 alkoxy or naphthenic base (comprise the endocyclic alicyclic groups such as 7,7-dimethyl-2-oxo norborny, be preferably bicyclic alkyl etc.) replace.
As R
21aryl, be preferably carbon number be the aryl of 6 ~ 11, be more preferably phenyl or naphthyl.R
21aryl can be 1 ~ 10 by carbon number alkyl, carbon number be 1 ~ 10 alkoxy or halogen atom replace.
Above-claimed cpd containing oxime sulfonates structure represented by above-mentioned formula (D1) for the oxime sulfonate compounds represented by following formula (D2) also preferred.
[changing 21]
(in formula (D2), R
42represent alkyl or aryl, X represents alkyl, alkoxy or halogen atom, and m4 represents the integer of 0 ~ 3, and when m4 is 2 or 3, multiple X can be identical, also can be different).
Alkyl as X is preferably straight-chain alkyl or the branch-like alkyl that carbon number is 1 ~ 4.
Alkoxy as X is preferably straight-chain alkoxy or the 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 (D2), to be particularly preferably m4 be 1, X is methyl, and the position of substitution of X is ortho position, R
42for straight-chain alkyl, 7,7-dimethyl-2-oxo norborny methyl or the compounds to toluyl groups that carbon number is 1 ~ 10.
Compound containing oxime sulfonates structure represented by above-mentioned formula (D1) for the oxime sulfonate compounds represented by following formula (D3) also preferred.
[changing 22]
(in formula (D3), R
43implication and formula (D2) in R
42identical, X
1alkoxy, cyano group or nitro that the alkyl that expression halogen atom, hydroxyl, carbon number are 1 ~ 4, carbon number are 1 ~ 4, n4 represents the integer of 0 ~ 5).
As the R in above-mentioned formula (D3)
43, be preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor-n-pro-pyl, perfluor-normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, be particularly preferably n-octyl.
X
1being preferably carbon number is the alkoxy of 1 ~ 5, is more preferably methoxyl.
N4 is preferably the integer of 0 ~ 2, is particularly preferably 0 or 1.
As the concrete example of the compound represented by above-mentioned formula (D3), can enumerate: α-(methylsulfonyloxyimino) benzyl cyanide, α-(ethylsulfonyloxy imino group) benzyl cyanide, α-(n-pro-pyl 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-pro-pyl sulfonyloxyimino)-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, can enumerate following compound (i) ~ compound (viii) etc., these compounds can be used alone one or and with two or more.Compound (i) ~ compound (viii) can be used as commercially available product and obtains.In addition, also can combinationally use with (components D) light acid producing agent of other kinds.
[changing 23]
As the compound containing the oxime sulfonates structure represented by above-mentioned formula (D1), the compound represented by following formula (OS-1) is also preferred.
[changing 24]
In above-mentioned formula (OS-1), R
101represent hydrogen atom, alkyl, thiazolinyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl, sulfamoyl, sulfo group, cyano group, aryl or heteroaryl.R
102represent alkyl or aryl.
X
101represent-O-,-S-,-NH-,-NR
105-,-CH
2-,-CR
106h-or-CR
105r
107-, R
105~ R
107represent alkyl or aryl.
R
121~ R
124separately represent hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxy, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide group, sulfo group, cyano group or aryl.R
121~ R
124in 2 can mutual bond and form ring respectively.
As R
121~ R
124, be preferably separately hydrogen atom, halogen atom or alkyl, in addition, also preferably can enumerate R
121~ R
124in at least two mutual bonds and form the form of aryl.Wherein, with regard to the viewpoint of sensitivity, be preferably R
121~ R
124be the form of hydrogen atom.
Already described functional group all can have substituting group further.
Compound represented by above-mentioned formula (OS-1) is more preferably the compound represented by following formula (OS-2).
[changing 25]
In above-mentioned formula (OS-2), R
101, R
102, R
121~ R
124implication respectively with the R in formula (OS-1)
101, R
102, R
121~ R
124identical, in addition, preference is also identical.
Among these, be more preferably the R in above-mentioned formula (OS-1) and above-mentioned formula (OS-2)
101for the form of cyano group or aryl, most preferably be and represented by above-mentioned formula (OS-2), and R
101for the form of cyano group, phenyl or naphthyl.
In addition, in oxime sulfonate compounds in the present invention, about the spatial structure (E, Z etc.) of oxime or benzothiazole ring, can be any one spatial structure respectively, also can be potpourri.
As the concrete example that can be suitably used for the compound represented by above-mentioned formula (OS-1) of the present invention, can enumerate compound (exemplary compounds b-1 ~ exemplary compounds b-34) described in the paragraph 0128 ~ paragraph 0132 of Japanese Patent Laid-Open 2011-221494 publication, but the present invention is not limited thereto.
In the present invention, as the compound containing the oxime sulfonates structure represented by above-mentioned formula (D1), be preferably the oxime sulfonate compounds represented by following formula (OS-3), following formula (OS-4) or following formula (OS-5).
[changing 26]
(in formula (OS-3) ~ formula (OS-5), R
22, R
25and R
28separately represent alkyl, aryl or heteroaryl, R
23, R
26and R
29separately represent hydrogen atom, alkyl, aryl or halogen atom, R
24, R
27and R
30separately represent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X
1~ X
3separately represent oxygen atom or sulphur atom, n
1~ n
3separately represent 1 or 2, m
1~ m
3separately represent the integer of 0 ~ 6).
In above-mentioned formula (OS-3) ~ formula (OS-5), R
22, R
25and R
28in alkyl, aryl or heteroaryl can have substituting group.
In above-mentioned formula (OS-3) ~ formula (OS-5), as R
22, R
25and R
28in alkyl, preferably can have substituent total carbon number is the alkyl of 1 ~ 30.
In addition, in above-mentioned formula (OS-3) ~ formula (OS-5), as R
22, R
25and R
28in aryl, preferably can have substituent total carbon number is the aryl of 6 ~ 30.
In addition, in above-mentioned formula (OS-3) ~ formula (OS-5), as R
22, R
25and R
28in heteroaryl, preferably can have substituent total carbon number is the heteroaryl of 4 ~ 30.
In above-mentioned formula (OS-3) ~ formula (OS-5), R
22, R
25and R
28as long as at least one ring of heteroaryl be assorted aromatic rings, such as mix aromatic rings and phenyl ring also can carry out contracting ring.
In above-mentioned formula (OS-3) ~ formula (OS-5), R
23, R
26and R
29be preferably hydrogen atom, alkyl or aryl, be more preferably hydrogen atom or alkyl.
In above-mentioned formula (OS-3) ~ formula (OS-5), be preferably the R of existence more than 2 in compound
23, R
26and R
29in 1 or 2 be alkyl, aryl or halogen atom, be more preferably 1 for alkyl, aryl or halogen atom, be particularly preferably 1 for alkyl and remaining as hydrogen atom.
As R
23, R
26and R
29in alkyl, preferably can have substituent total carbon number is the alkyl of 1 ~ 12, is more preferably that can to have substituent total carbon number be the alkyl of 1 ~ 6.
As R
23, R
26and R
29in aryl, preferably can have substituent total carbon number is the aryl of 6 ~ 30.
In above-mentioned formula (OS-3) ~ formula (OS-5), X
1~ X
3separately represent O or S, be preferably O.
In above-mentioned formula (OS-3) ~ formula (OS-5), containing X
1~ X
3ring as ring element is 5 rings or 6 rings.
In above-mentioned formula (OS-3) ~ formula (OS-5), n
1~ n
3separately represent 1 or 2, work as X
1~ X
3during for O, n
1~ n
3being preferably is separately 1, in addition, works as X
1~ X
3during for S, n
1~ n
3be preferably separately 2.
In above-mentioned formula (OS-3) ~ formula (OS-5), R
24, R
27and R
30separately represent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.Wherein, R is preferably
24, R
27and R
30be separately alkyl or alkoxy.
R
24, R
27and R
30in alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl can have substituting group.
In above-mentioned formula (OS-3) ~ formula (OS-5), as R
24, R
27and R
30in alkyl, preferably can have substituent total carbon number is the alkyl of 1 ~ 30.
In above-mentioned formula (OS-3) ~ formula (OS-5), as R
24, R
27and R
30in alkoxy, preferably can have substituent total carbon number is the alkoxy of 1 ~ 30.
In addition, in above-mentioned formula (OS-3) ~ formula (OS-5), m
1~ m
3separately represent the integer of 0 ~ 6, be preferably the integer of 0 ~ 2, be more preferably 0 or 1, be particularly preferably 0.
In addition, about each substituting group of above-mentioned formula (OS-3) ~ formula (OS-5), the substituent preferred scope of (OS-3) ~ (OS-5) described in the paragraph 0092 ~ paragraph 0109 of Japanese Patent Laid-Open 2011-221494 publication is preferred too.
In addition, the compound containing oxime sulfonates structure represented by above-mentioned formula (D1) particularly preferably for by following formula (OS-6) ~ formula (OS-11) any one represented by oxime sulfonate compounds.
[changing 27]
(in formula (OS-6) ~ formula (OS-11), R
301~ R
306represent alkyl, aryl or heteroaryl, R
307represent hydrogen atom or bromine atoms, R
308~ R
310, R
313, R
316and R
318separately represent hydrogen atom, carbon number be 1 ~ 8 alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, R
311and R
314separately represent hydrogen atom, halogen atom, methyl or methoxy, R
312, R
315, R
317and R
319separately represent hydrogen atom or methyl).
Preferred scope in above-mentioned formula (OS-6) ~ formula (OS-11) is identical with the preferred scope of (OS-6) ~ (OS-11) described in the paragraph 0110 ~ paragraph 0112 of Japanese Patent Laid-Open 2011-221494 publication.
As the concrete example of the oxime sulfonate compounds represented by above-mentioned formula (OS-3) ~ above-mentioned formula (OS-5), can enumerate compound described in the paragraph 0114 ~ paragraph 0120 of Japanese Patent Laid-Open 2011-221494 publication, but the present invention is not limited to these compounds.
In photosensitive polymer combination of the present invention, relative to composition A 100 mass parts in photosensitive polymer combination, (components D) light acid producing agent is preferably use 0.1 mass parts ~ 10 mass parts, is more preferably use 0.5 mass parts ~ 10 mass parts.
In addition, components D can be used alone one, also can and with two or more.
(composition E) solvent
Photosensitive polymer combination of the present invention contains (composition E) solvent.Photosensitive polymer combination of the present invention is preferably as making of the present invention must composition and the solution of arbitrary component dissolves described later in (composition E) solvent preparation.
As the solvent used in photosensitive polymer combination of the present invention, known solvent can be used, can illustrate: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol 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, ester class, ketone, amide-type, lactone etc.In addition, as the concrete example of the solvent used in photosensitive polymer combination of the present invention, solvent described in the paragraph 0174 ~ paragraph 0178 of Japanese Patent Laid-Open 2011-221494 publication also can be enumerated.
In addition, optionally also in these solvents, benzyl ether, two hexyl ethers, ethyleneglycol monophenylether acetic acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, anisole, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, carbonic allyl ester equal solvent can be added further.
These solvents can be used alone one or be use mixing two or more.Solvent used in the present invention be preferably used alone one or and with two kinds.
In addition, as composition E, be preferably that boiling point is more than 130 DEG C, solvent less than 160 DEG C, boiling point is the solvent of more than 160 DEG C, or these potpourri.
As boiling point be more than 130 DEG C, solvent less than 160 DEG C, can illustrate: propylene glycol methyl ether acetate (boiling point is 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).
As the solvent that boiling point is more than 160 DEG C, can illustrate: 3-ethoxyl ethyl propionate (boiling point is 170 DEG C), diethylene glycol 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 butyl ether acetic acid esters (boiling point is 171 DEG C), diethylene glycol diethyl ether (boiling point is 189 DEG C), diethylene 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 is 220 DEG C), dimethyl ether (boiling point is 175 DEG C), 1, 3-butylene glycol diacetate esters (boiling point is 232 DEG C).
Among these, as solvent, be preferably propylene-glycol monoalky lether acetate esters, be particularly preferably propylene glycol methyl ether acetate.
Relative to composition A 100 mass parts in photosensitive polymer combination, the content of (composition E) solvent in photosensitive polymer combination of the present invention is preferably 50 mass parts ~ 95 mass parts, is more preferably 60 mass parts ~ 90 mass parts.
(composition F) spreading agent
Photosensitive polymer combination of the present invention is preferably containing (composition F) spreading agent.By containing spreading agent, and the dispersiveness of composition C in resin combination can be promoted further.
As spreading agent, known spreading agent can be used, such as, can be suitable for selecting known pigment dispersing agent to use.
In addition, as spreading agent, preferably macromolecule dispersing agent can be used.Moreover so-called macromolecule dispersing agent, refers to that molecular weight (weight average molecular weight) is the spreading agent of 1, more than 000.
As spreading agent, multiple compounds can be used, specifically, include, for example: organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), (methyl) acrylic acid series (being total to) polymkeric substance Po Lifuluo (Polyflow) No.75, No.90, No.95 (common prosperity society chemistry (share) manufacture), the kation system surfactants such as W001 (abundant business (share) manufacture), the nonionic system surfactants such as polyoxyethylene laurel ether, polyoxyethylene stearyl ether, polyoxyl 10 oleyl ether, polyoxethylene octylphenyl phenylate, ethylene nonyl phenylate, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid esters, the negative ion system surfactants such as W004, W005, W017 (abundant business (share) manufacture), EFKA (EFKA)-46, EFKA (EFKA)-47, EFKA (EFKA)-47EA, EFKA polymkeric substance (EFKA Polymer) 100, EFKA polymkeric substance (EFKA Polymer) 400, EFKA polymkeric substance (EFKA Polymer) 401, EFKA polymkeric substance (EFKAPolymer) 450 (being Ciba (Ciba Specialty Chemicals) company to manufacture), this Paasche of enlightening Ai De (DisperseAid) 6, this Paasche of enlightening Ai De (Disperse Aid) 8, this Paasche of enlightening Ai De (Disperse Aid) 15, the macromolecule dispersing agents such as this Paasche of enlightening Ai De (Disperse Aid) 9100 (being Sheng Nuopuke (San Nopco) (share) to manufacture), various Suo Sipa (Solsperse) spreading agents such as Suo Sipa (Solsperse) 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (AstraZeneca (AstraZeneca) (share) manufactures), Ai Dike pluronic (AdekaPluronic) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Ai Dike (ADEKA) (share) manufactures) and her Nat difficult to understand (IONET) S-20 (Sanyo changes into industry (share) manufacture), Di Sipabike (DISPERBYK) 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 (manufactures of Bi Ke chemistry (BYK-Chemie) company).In addition, oligomer or the polymkeric substance that acrylic acid series copolymer etc. has polar group in molecular end or side chain can be enumerated.
As spreading agent, preferably there is the spreading agent of at least one acidic group, particularly preferably for being represented by following formula (S) and there is the spreading agent (hereinafter also referred to as " composition S ") of at least one acidic group.Resin combination of the present invention passes through containing the spreading agent with at least one acidic group, when the dispersion of metal oxide particle, oversize grain is less, cohesion when being mixed with component of polymer by dispersion liquid is also less, therefore can form the hardening thing that refractive index is high, the transparency is excellent.
[changing 28]
(in formula (S), R
3represent the concatenating group of (m+n) valency, R
4and R
5separately represent the concatenating group of singly-bound or divalence, A
2represent the organic group of the monovalence containing the following part-structure of at least one, the group that alkyl, alkoxysilane group, epoxy radicals, isocyanate group and hydroxyl that it is more than 4 that above-mentioned part-structure is 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 form, n A
2, R
4can be identical, also can be different, m represents that 0 ~ 8, n represents that 2 ~ 9, m+n is 3 ~ 10, P
2represent macromolecular scaffold, m P
2, R
5can be identical, also can be different).
When use there is at least one acidic group spreading agent as spreading agent time, infer, by spreading agent, there is acidic group, and as absorption base, metal oxide particle played a role, the excellent dispersion of metal oxide particle.
As acidic group, carboxylic acid group's (carboxyl), sulfonic group, phosphate, phenolic hydroxyl group etc. can be enumerated, with regard to regard to the absorption affinity of metal oxide particle and the viewpoint of dispersiveness, preferably be selected from least one in the group be made up of carboxylic acid group, sulfonic group and phosphate, be particularly preferably carboxylic acid group.Acidic group in above-mentioned spreading agent can separately containing a kind of in these acidic groups or containing two or more combinations.
Acidic group in composition S can have any one structure of formula (S).Specifically, such as acidic group can be contained in the A in above-mentioned formula (S)
2in, in addition, can be contained in by P
2in represented macromolecular scaffold, also A can be contained in
2and P
2in two, but with regard to the viewpoint of effect, be preferably contained in A
2in.
In above-mentioned formula (S), A
2represent the organic group of the monovalence containing the following part-structure of at least one, the group that alkyl, alkoxysilane group, epoxy radicals, isocyanate group and hydroxyl that it is more than 4 that above-mentioned part-structure is 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 form.In addition, in formula (S), there is the A of n
2respectively can be identical, also can be different.
That is, above-mentioned A
2represent the organic group of the monovalence containing the following structure of at least one or functional group, said structure is the structure with the adsorptive power for metal oxide particle as organic pigmentary structures, heterocycle structure, above-mentioned functional group be as acidic group, the base with basic nitrogen atom, urea groups, carbamate groups, the base with coordinating oxygen atom, carbon number be more than 4 alkyl, alkoxysilane group, epoxy radicals, there is isocyanate group and hydroxyl the functional group of the adsorptive power for metal oxide particle.
Moreover below, the part-structure (said structure and functional group) this with the adsorptive power for metal oxide particle is suitable for being generically and collectively referred to as " adsorption site " to be described.
As long as at 1 A
2in containing the above-mentioned adsorption site of at least one, also can contain two or more.
In addition, in the present invention, " organic group of the monovalence containing at least one adsorption site " is above-mentioned adsorption site and the organic group of the monovalence of the concatenating group bond be made up of the sulphur atom of the carbon atom of 1 ~ 200, the nitrogen-atoms of 0 ~ 20, the oxygen atom of 0 ~ 100, the hydrogen atom of 1 ~ 400 and 0 ~ 40.Moreover when adsorption site itself can form the organic group of monovalence, adsorption site itself can be by A
2the organic group of represented monovalence.
First, below to the above-mentioned A of formation
2adsorption site be described.
As above-mentioned " organic pigment structure ", include, for example phthalocyanine system, insoluble azo system, azo lake system, anthraquinone system, quinacridone, dioxazine system, diketopyrrolo-pyrrole system, anthracene pyridine system, anthanthrone system, indanthrene (indanthrone) is, yellow scholar's ketone system, purple cyclic ketones (perinone) is, perylene system, the pigmentary structures of thioindigo system is as preference, be more preferably phthalocyanine system, azo lake system, anthraquinone system, dioxazine system, the pigmentary structures of diketopyrrolo-pyrrole system, be particularly preferably phthalocyanine system, anthraquinone system, the pigmentary structures of diketopyrrolo-pyrrole system.
In addition, as above-mentioned " heterocycle structure ", as long as have the base of at least more than one heterocycle.As the heteroatoms in above-mentioned " heterocycle structure ", preferably contain at least one of O (oxygen atom), N (nitrogen-atoms) or S (sulphur atom), be more preferably containing at least one nitrogen-atoms.As the heterocycle in above-mentioned " heterocycle structure ", include, for example and be selected from by thiophene, furans, xanthene, pyrroles, pyrrolin, pyrrolidine, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles, oxazole, thiazole, oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines, diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, indoles, quinoline, carbazole, acridine, and the heterocycle in the group that forms of acridone is as preference, is more preferably and is selected from by pyrrolin, pyrrolidine, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, carbazole, acridine, and the heterocycle in the group that forms of acridone.
Moreover, above-mentioned " organic pigment structure " or " heterocycle structure " and then can have substituting group, as above-mentioned substituting group, include, for example: methyl, the carbon numbers such as ethyl are the alkyl of 1 ~ 20, phenyl, the carbon numbers such as naphthyl are the aryl of 6 ~ 16, hydroxyl, amino, carboxyl, sulfoamido, N-sulfonyl amide group, the carbon numbers such as acetoxyl group are the acyloxy of 1 ~ 6, methoxyl, the carbon numbers such as ethoxy are the alkoxy of 1 ~ 20, chlorine atom, the halogen atoms such as bromine atoms, methoxycarbonyl, ethoxy carbonyl, the carbon numbers such as cyclohexyloxy carbonyl are the alkoxy carbonyl of 2 ~ 7, cyano group, the carbonate groups etc. such as carbonic acid tributyl base.Herein, these substituting groups can via following structural unit or the concatenating group that said structure unit combination is formed with organic pigment structure or heterocycle structure bond.
[changing 29]
As above-mentioned " acidic group ", include, for example carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group, boronate as preference, be more preferably carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, monophosphate ester group, and then be more preferably carboxylic acid group, sulfonic group, phosphate, be particularly preferably carboxylic acid group.
In addition, as above-mentioned " there is the base of basic nitrogen atom ", include, for example amino (-NH
2), substituted imido (-NHR
8,-NR
9r
10, herein, R
8, R
9and R
10separately represent carbon number be 1 ~ 20 alkyl, carbon number be the aryl of more than 6, carbon number is the aralkyl of more than 7, the aryl that to be preferably carbon number be 1 ~ 20 alkyl, carbon number are 6 ~ 20 or the aralkyl that carbon number is 7 ~ 20), the guanidine radicals represented by following formula (a1), the amidino groups represented by following formula (a2) etc. are as preference.
[changing 30]
In formula (a1), R
11and R
12separately represent carbon number be 1 ~ 20 alkyl, carbon number be more than 6 aryl, carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 20 alkyl, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20.
In formula (a2), R
13and R
14separately represent carbon number be 1 ~ 20 alkyl, carbon number be more than 6 aryl, carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 20 alkyl, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20.
Among these, be more preferably amino (-NH
2), substituted imido (-NHR
8,-NR
9r
10, herein, R
8, R
9and R
10separately represent carbon number be 1 ~ 10 alkyl, phenyl, benzyl), guanidine radicals represented by above-mentioned formula (a1) (in formula (a1), R
11and R
12separately represent carbon number be 1 ~ 10 alkyl, phenyl, benzyl), amidino groups represented by above-mentioned formula (a2) (in formula (a2), R
13and R
14separately represent that carbon number is alkyl, phenyl, the benzyl of 1 ~ 10) etc.
Especially, amino (-NH can preferably be used
2), substituted imido (-NHR
8,-NR
9r
10, herein, R
8, R
9and R
10separately represent carbon number be 1 ~ 5 alkyl, phenyl, benzyl), guanidine radicals represented by above-mentioned formula (a1) (in formula (a1), R
11and R
12separately represent carbon number be 1 ~ 5 alkyl, phenyl, benzyl), amidino groups represented by above-mentioned formula (a2) (in formula (a2), R
13and R
14separately represent that carbon number is alkyl, phenyl, the benzyl of 1 ~ 5) etc.
As above-mentioned " urea groups ", include, for example-NR
15cONR
16r
17(herein, R
15, R
16and R
17separately represent hydrogen atom, carbon number be 1 ~ 20 alkyl, carbon number be more than 6 aryl or carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 20 alkyl, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20) as preference, be more preferably-NR
15cONHR
17(herein, R
15and R
17separately represent hydrogen atom, carbon number be 1 ~ 10 alkyl, carbon number be more than 6 aryl or carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 10 alkyl, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20), be particularly preferably-NHCONHR
17(herein, R
17represent hydrogen atom, carbon number be 1 ~ 10 alkyl, carbon number be more than 6 aryl or carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 10 alkyl, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20).
As above-mentioned " carbamate groups ", include, for example-NHCOOR
18,-NR
19cOOR
20,-OCONHR
21,-OCONR
22r
23(herein, R
18, R
19, R
20, R
21, R
22and R
23separately represent carbon number be 1 ~ 20 alkyl, carbon number be more than 6 aryl or carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 20 alkyl, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20) etc. as preference, be more preferably-NHCOOR
18,-OCONHR
21(herein, R
18and R
21separately represent carbon number be 1 ~ 20 alkyl, carbon number be more than 6 aryl or carbon number be the aralkyl of more than 7) etc., be particularly preferably-NHCOOR
18,-OCONHR
21(herein, R
18and R
21separately represent carbon number be 1 ~ 10 alkyl, carbon number be more than 6 aryl or carbon number be the aralkyl of more than 7, be preferably carbon number be 1 ~ 10 alkyl, carbon number be 6 ~ 12 aryl or carbon number be the aralkyl of 7 ~ 13) etc.
As above-mentioned " there is the base of coordinating oxygen atom ", include, for example: the base etc. acetylacetone based, there is crown ether structures.
As above-mentioned " carbon number is the alkyl of more than 4 ", can enumerate carbon number be more than 4 alkyl, carbon number be more than 6 aryl, carbon number be that aralkyl of more than 7 etc. is as preference, be more preferably carbon number be 4 ~ 20 alkyl, carbon number be 6 ~ 20 aryl, carbon number be the aralkyl etc. of 7 ~ 20, be particularly preferably alkyl (such as octyl group, dodecyl etc.), the carbon number aryl (such as phenyl, naphthyl etc.) that is 6 ~ 15, the carbon number aralkyl (such as benzyl etc.) etc. that is 7 ~ 15 that carbon number is 4 ~ 15.
As above-mentioned " alkoxysilane group ", include, for example: trimethoxy silane base, triethoxysilicane alkyl etc.
As the concatenating group with above-mentioned adsorption site bond, be preferably singly-bound, or the concatenating group to be made up of the sulphur atom of the carbon atom of 1 ~ 100, the nitrogen-atoms of 0 ~ 10, the oxygen atom of 0 ~ 50, the hydrogen atom of 1 ~ 200 and 0 ~ 20, this concatenating group can be unsubstituted, and also and then can have substituting group.As the concrete example of this concatenating group, the base following structural unit can enumerated or said structure unit combination is formed.
[changing 31]
When above-mentioned concatenating group has substituting group; as above-mentioned substituting group; include, for example: the carbon number such as methyl, ethyl is the alkyl of 1 ~ 20; the carbon number such as phenyl, naphthyl is the aryl of 6 ~ 16; hydroxyl; amino; carboxyl, sulfoamido, N-sulfonyl amide group; the carbon numbers such as acetoxyl group are the acyloxy of 1 ~ 6; the carbon number such as methoxyl, ethoxy is the halogen atoms such as the alkoxy of 1 ~ 6, chlorine atom, bromine atoms, and the carbon numbers such as methoxycarbonyl, ethoxy carbonyl, cyclohexyloxy carbonyl are the alkoxy carbonyl of 2 ~ 7; cyano group, the carbonate groups etc. such as carbonic acid tributyl base.
Among above-mentioned, as above-mentioned A
2be preferably the organic group of the monovalence of the part-structure in the group formed containing at least one alkyl that to be selected from by organic pigment structure, heterocycle structure, acidic group, the base with basic nitrogen atom, urea groups and carbon number be more than 4, be particularly preferably the organic group of the monovalence containing at least one acidic group.
As above-mentioned A
2, be more preferably the organic group of the monovalence represented by following formula (4).
[changing 32]
In above-mentioned formula (4), B
1represent above-mentioned adsorption site (namely, part-structure in the group that alkyl, alkoxysilane group, epoxy radicals, isocyanate group and hydroxyl that to 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 be more than 4 form), R
24represent the concatenating group of singly-bound or (a+1) valency.A represents the integer of 1 ~ 10, there is the B of a in formula (4)
1respectively can be identical, also can be different.
As by above-mentioned B
1represented adsorption site, can enumerate and the A forming above-mentioned formula (S)
2adsorption site identical, preference is also identical.
Wherein, the part-structure in the group that the alkyl that to be preferably selected from by organic pigment structure, heterocycle structure, acidic group, the base with basic nitrogen atom, urea groups and carbon number be more than 4 forms, is particularly preferably acidic group.
R
24represent the concatenating group of singly-bound or (a+1) valency, a represents the integer of 1 ~ 10, is preferably the integer of 1 ~ 7, is more preferably the integer of 1 ~ 5, is particularly preferably the integer of 1 ~ 3.
As the concatenating group of (a+1) valency, comprise the base be made up of the sulphur atom of the carbon atom of 1 ~ 100, the nitrogen-atoms of 0 ~ 10, the oxygen atom of 0 ~ 50, the hydrogen atom of 1 ~ 200 and 0 ~ 20, can be unsubstituted, also and then can there is substituting group.
As the concrete example of the concatenating group of above-mentioned (a+1) valency, the base following structural unit can enumerated or said structure unit combination is formed (can ring structure be formed).
[changing 33]
As R
24, be preferably singly-bound, or by the carbon atom of 1 ~ 50, the nitrogen-atoms of 0 ~ 8, the oxygen atom of 0 ~ 25, the hydrogen atom of 1 ~ 100, and the concatenating group of (a+1) valency of the sulphur atom formation of 0 ~ 10, be more preferably singly-bound, or by the carbon atom of 1 ~ 30, the nitrogen-atoms of 0 ~ 6, the oxygen atom of 0 ~ 15, the hydrogen atom of 1 ~ 50, and the concatenating group of (a+1) valency of the sulphur atom formation of 0 ~ 7, be particularly preferably singly-bound, or by the carbon atom of 1 ~ 10, the nitrogen-atoms of 0 ~ 5, the oxygen atom of 0 ~ 10, the hydrogen atom of 1 ~ 30, and the concatenating group of (a+1) valency of the sulphur atom formation of 0 ~ 5.
Among above-mentioned, when the concatenating group of (a+1) valency has substituting group, as above-mentioned substituting group, include, for example: methyl, the carbon numbers such as ethyl are the alkyl of 1 ~ 20, phenyl, the carbon numbers such as naphthyl are the aryl of 6 ~ 16, hydroxyl, amino, carboxyl, sulfoamido, N-sulfonyl amide group, the carbon numbers such as acetoxyl group are the acyloxy of 1 ~ 6, methoxyl, the carbon numbers such as ethoxy are the alkoxy of 1 ~ 6, chlorine atom, the halogen atoms such as bromine atoms, methoxycarbonyl, ethoxy carbonyl, the carbon numbers such as cyclohexyloxy carbonyl are the alkoxy carbonyl of 2 ~ 7, cyano group, the carbonate groups etc. such as carbonic acid tributyl base.
In above-mentioned formula (S), R
4and R
5separately represent the concatenating group of singly-bound or divalence.There is the R of n
4respectively can be identical, also can be different.In addition, there is the R of m
5respectively can be identical, also can be different.
As R
4and R
5in the concatenating group of divalence, comprise the base be made up of the sulphur atom of the carbon atom of 1 ~ 100, the nitrogen-atoms of 0 ~ 10, the oxygen atom of 0 ~ 50, the hydrogen atom of 1 ~ 200 and 0 ~ 20, can be unsubstituted, also and then can there is substituting group.
As the concrete example of the concatenating group of above-mentioned divalence, the base following structural unit can enumerated or said structure unit combination is formed.
[changing 34]
R
4and R
5be preferably separately singly-bound, or by the carbon atom of 1 ~ 50, the nitrogen-atoms of 0 ~ 8, the oxygen atom of 0 ~ 25, the hydrogen atom of 1 ~ 100, and the concatenating group of the divalence of the sulphur atom formation of 0 ~ 10, be more preferably singly-bound, or by the carbon atom of 1 ~ 30, the nitrogen-atoms of 0 ~ 6, the oxygen atom of 0 ~ 15, the hydrogen atom of 1 ~ 50, and the concatenating group of the divalence of the sulphur atom formation of 0 ~ 7, be particularly preferably singly-bound, or by the carbon atom of 1 ~ 10, the nitrogen-atoms of 0 ~ 5, the oxygen atom of 0 ~ 10, the hydrogen atom of 1 ~ 30, and the concatenating group of the divalence of the sulphur atom formation of 0 ~ 5.
Among above-mentioned, when the concatenating group of divalence has substituting group, as above-mentioned substituting group, include, for example: methyl, the carbon numbers such as ethyl are the alkyl of 1 ~ 20, phenyl, the carbon numbers such as naphthyl are the aryl of 6 ~ 16, hydroxyl, amino, carboxyl, sulfoamido, N-sulfonyl amide group, the carbon numbers such as acetoxyl group are the acyloxy of 1 ~ 6, methoxyl, the carbon numbers such as ethoxy are the alkoxy of 1 ~ 6, chlorine atom, the halogen atoms such as bromine atoms, methoxycarbonyl, ethoxy carbonyl, the carbon numbers such as cyclohexyloxy carbonyl are the alkoxy carbonyl of 2 ~ 7, cyano group, the carbonate groups etc. such as carbonic acid tributyl base.
In above-mentioned formula (S), R
3represent the concatenating group of (m+n) valency.M+n meets 3 ~ 10.
As by above-mentioned R
3the concatenating group of represented (m+n) valency, comprise the base be made up of the sulphur atom of the carbon atom of 1 ~ 60, the nitrogen-atoms of 0 ~ 10, the oxygen atom of 0 ~ 50, the hydrogen atom of 1 ~ 100 and 0 ~ 20, can be unsubstituted, also and then can there is substituting group.
As the concrete example of the concatenating group of above-mentioned (m+n) valency, the base following structural unit can enumerated or said structure unit combination is formed (can ring structure be formed).
[changing 35]
As the concatenating group of (m+n) valency, be preferably by the carbon atom of 1 ~ 60, the nitrogen-atoms of 0 ~ 10, the oxygen atom of 0 ~ 40, the hydrogen atom of 1 ~ 120, and the base that the sulphur atom of 0 ~ 10 is formed, be more preferably by the carbon atom of 1 ~ 50, the nitrogen-atoms of 0 ~ 10, the oxygen atom of 0 ~ 30, the hydrogen atom of 1 ~ 100, and the base that the sulphur atom of 0 ~ 7 is formed, be particularly preferably by the carbon atom of 1 ~ 40, the nitrogen-atoms of 0 ~ 8, the oxygen atom of 0 ~ 20, the hydrogen atom of 1 ~ 80, and the base that the sulphur atom of 0 ~ 5 is formed.
Among above-mentioned, when the concatenating group of (m+n) valency has substituting group, as above-mentioned substituting group, include, for example: methyl, the carbon numbers such as ethyl are the alkyl of 1 ~ 20, phenyl, the carbon numbers such as naphthyl are the aryl of 6 ~ 16, hydroxyl, amino, carboxyl, sulfoamido, N-sulfonyl amide group, the carbon numbers such as acetoxyl group are the acyloxy of 1 ~ 6, methoxyl, the carbon numbers such as ethoxy are the alkoxy of 1 ~ 6, chlorine atom, the halogen atoms such as bromine atoms, methoxycarbonyl, ethoxy carbonyl, the carbon numbers such as cyclohexyloxy carbonyl are the alkoxy carbonyl of 2 ~ 7, cyano group, the carbonate groups etc. such as carbonic acid tributyl base.
Below represent by above-mentioned R
3the concrete example [concrete example (1) ~ concrete example (17)] of the concatenating group of represented (m+n) valency.But, in the present invention, do not limit by these concrete examples.
[changing 36]
[changing 37]
Among above-mentioned concrete example, with regard to raw material acquired, synthesis easiness, for various solvent deliquescent viewpoint with regard to, the concatenating group of most preferred (m+n) valency is following base.
[changing 38]
In above-mentioned formula (S), m represents 0 ~ 8.As m, be preferably 0.5 ~ 5, be more preferably 0.5 ~ 4, be particularly preferably 0.5 ~ 3.
In addition, in above-mentioned formula (S), n represents 2 ~ 9.As n, be preferably 2 ~ 8, be more preferably 2 ~ 7, be particularly preferably 3 ~ 6.
In addition, the P in formula (S)
2represent macromolecular scaffold, can select in known polymkeric substance etc. according to object etc.The P of m is there is in formula (S)
2respectively can be identical, also can be different.In addition, P
2be preferably the macromolecular scaffold of monovalence.
As the polymer chain forming macromolecular scaffold, preferably be selected from by the polymkeric substance of vinyl monomer or multipolymer, ester based polymer, ether based polymer, carbamate based polymer, acid amides based polymer, epoxy polymkeric substance, silicone-based polymer, and these modifier or multipolymer [such as comprise polyethers/polyurethane co-polymer, the multipolymer etc. of the polymkeric substance of polyethers/vinyl monomer (can be random copolymers, segmented copolymer, any one of graft copolymer, be more preferably random copolymers)] at least one in the group that forms, be more preferably and be selected from by the polymkeric substance of vinyl monomer or multipolymer, ester based polymer, ether based polymer, carbamate based polymer, and at least one in the group that forms of these modifier or multipolymer, and then be more preferably polymkeric substance or the multipolymer of vinyl monomer, be particularly preferably acryl resin (polymkeric substance of (methyl) acrylic monomers or multipolymer).
And then above-mentioned polymkeric substance preferably dissolves in organic solvent.In addition, composition S preferably dissolves in organic solvent.If high with the compatibility of organic solvent, then sometimes such as abundant with the compatibility of dispersion medium, the adsorbed layer being formed at metal oxide particle surface by composition S being enough to realize decentralized stabilization can be guaranteed.
In the present invention, above-mentioned P
2in macromolecular scaffold can have more than one acidic group, also can not have acidic group.
As the polymkeric substance with the acidic group forming above-mentioned macromolecular scaffold, include, for example: daiamid and its salt, polycarboxylic acid and its salt, high molecular unsaturated acid ester, modification polycarbamate, modified poly ester, the modification with acidic group gather (methyl) acrylate, (methyl) acrylic acid series copolymer, naphthalene sulfonic acid-formaldehyde condensation product) and polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.Among these, be preferably (methyl) acrylic copolymer.
In macromolecular scaffold, importing the method for acidic group, there is no particular restriction, the method that can adopt the vinyl monomer by having acidic group to import, method etc. by utilizing bridging property side chain to make acidic group addition to import, as described later, with regard to easily control the import volume of acidic group viewpoint, synthesis cost viewpoint with regard to, contain preferably by macromolecular scaffold the Component units being derived from the vinyl monomer with acidic group and form the form importing acidic group.
Herein, " acidic group " can similarly enumerate above-mentioned A
2explanation in as cited by " acidic group ", be preferably carboxyl.
As above-mentioned vinyl monomer, there is no particular restriction, such as, be preferably: (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid ester class, fumaric acid two are drunk class, itaconic acid diester class, (methyl) acrylic amide, phenylethylene, vinyl ethers, vinyl ketones, olefines, maleimide class, (methyl) vinyl cyanide, had the vinyl monomer etc. of acidic group.
Below, the preference of these vinyl monomers is described.
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) acrylic acid tributyl, (methyl) amyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tributyl cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid the 3rd monooctyl ester, (methyl) dodecyl acrylate, (methyl) octadecyl acrylate, (methyl) acrylic acid acetoxyethyl, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 34 hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-methoxy acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) acrylic acid 2-chloroethene ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, (methyl) vinyl acrylate, (methyl) acrylic acid 2-phenylethylene ester, (methyl) acrylic acid 1-propylene, (methyl) allyl acrylate, (methyl) acrylic acid 2-allyloxy ethyl ester, (methyl) propargylacrylate, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether, (methyl) acrylic 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 ethyl, (methyl) nonylphenol acrylate phenoxy group polyglycol, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) perfluoroethyl octyl group ethyl ester, (methyl) acrylic acid two ring pentyl ester, (methyl) tribromophenyl acrylate, (methyl) acrylic acid tribromophenoxy ethyl ester, (methyl) acrylic acid gamma-butyrolacton-2-base ester etc.
As the example of crotonates class, can enumerate: butyl crotonate and the own ester of crotonic acid etc.
As the example of vinyl ester, can enumerate: vinyl acetate, vinyl chloroacetate, propionate, vinyl butyrate, 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 fumaric acid diester class, can enumerate: dimethyl fumarate, diethyl fumarate and dibutyl fumarate etc.
As the example of itaconic acid diester class, can enumerate: dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide, can enumerate: (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-n-butyl acryloyloxy ethyl acyl group (methyl) acid amides, N-tributyl (methyl) acrylamide, N-cyclohexyl (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-nitrophenylacrylamide, N-ethyl, N-phenyl acrylamide, N-benzyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinyl (methyl) acrylamide, N, N-diallyl (methyl) acrylamide, N-allyl (methyl) acrylamide etc.
As the example of phenylethylene, can enumerate: styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, hydroxy styrenes, vinylbenzoate and the α-methyl styrene etc. protected by the base (such as the 3rd butoxy carbonyl (t-Boc) etc.) of the deprotection by acidic materials.
As the example of vinyl ethers, can enumerate: methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinylethers, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxy-ethylvinyl ether and Vinyl phenyl ether etc.
As the example of vinyl ketones, can enumerate: methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone etc.
As the example of olefines, can enumerate: ethene, propylene, isobutylene, butadiene, isoprene etc.
As the example of maleimide class, can enumerate: maleimide, butyl maleimide, cyclohexylmaleimide, phenylmaleimide etc.
Also can use (methyl) vinyl cyanide, replace the hetero ring type base (such as vinylpyridine, NVP, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactam etc. that there are vinyl.
Except above-claimed cpd, also can use the vinyl monomer such as with functional groups such as carbamate groups, urea groups, sulfoamido, phenolic group, imides.There is as this kind the monomer of carbamate groups or urea groups, such as, can utilize the addition reaction of isocyanate group and hydroxyl or amino and be suitable for synthesizing.Specifically, by the monomer containing isocyanate group and the compound containing 1 hydroxyl or addition reaction that is amino containing 1 one-level or compound that secondary is amino, or the addition reaction of monomer containing hydroxyl or or monomer that secondary amino amino containing one-level and monoisocyanates etc. and be suitable for synthesizing.
Secondly, to for macromolecular scaffold P
2the vinyl monomer with acidic group of middle importing acidic group is described.
As the above-mentioned example with the vinyl monomer of acidic group, the vinyl monomer with carboxyl can be enumerated or there is sulfonic vinyl monomer.
As the vinyl monomer with carboxyl, can enumerate: (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer etc.In addition, (methyl) acrylic acid 2-hydroxy methacrylate etc. also can be utilized to have the addition reaction of the monomer of hydroxyl and maleic anhydride or phthalic anhydride, cyclic anhydride as cyclohexane dicarboxylic acid acid anhydride, ω-carboxy-polycaprolactone list (methyl) acrylate etc.In addition, as the precursor of carboxyl, the monomer containing acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride also can be used.Moreover, among these, with regard to the viewpoint of copolymerizable or cost, dissolubility etc., be particularly preferably (methyl) acrylic acid.
In addition, as having sulfonic vinyl monomer, 2-acrylamide-2-methyl propane sulfonic etc. can be enumerated, as the vinyl monomer with phosphate, mono phosphoric acid ester (2-acryloyloxyethyl ester), mono phosphoric acid ester (1-methyl-2-acryloyloxyethyl ester) etc. can be enumerated.
And then, as the vinyl monomer with acidic group, the vinyl monomer containing phenolic hydroxyl group or the vinyl monomer etc. containing sulfoamido also can be utilized.
As macromolecular scaffold P
2when comprising the monomeric unit of the vinyl monomer be derived from containing acidic group, the content of the monomeric unit being derived from the vinyl monomer containing acidic group in macromolecular scaffold is in mass conversion, relative to the entirety of macromolecular scaffold, be preferably 3 quality % ~ 40 quality %, be more preferably the scope of 5 quality % ~ 20 quality %.
Represented by above-mentioned formula (S) and have among the spreading agent of at least one acidic group, most preferably being and meeting R shown below simultaneously
3, R
4, R
5, P
2, m and n.
R
3: above-mentioned concrete example (1), concrete example (2), concrete example (10), concrete example (11), concrete example (16) or concrete example (17)
R
4: singly-bound, or by following structural unit or the " carbon atom of 1 ~ 10 that said structure unit combination is formed, the nitrogen-atoms of 0 ~ 5, the oxygen atom of 0 ~ 10, the hydrogen atom of 1 ~ 30, and the sulphur atom of 0 ~ 5 " concatenating group of divalence that forms (can have substituting group, as above-mentioned substituting group, include, for example: methyl, the carbon numbers such as ethyl are the alkyl of 1 ~ 20, phenyl, the carbon numbers such as naphthyl are the aryl of 6 ~ 16, hydroxyl, amino, carboxyl, sulfoamido, N-sulfonyl amide group, the carbon numbers such as acetoxyl group are the acyloxy of 1 ~ 6, methoxyl, the carbon numbers such as ethoxy are the alkoxy of 1 ~ 6, chlorine atom, the halogen atoms such as bromine atoms, methoxycarbonyl, ethoxy carbonyl, the carbon numbers such as cyclohexyloxy carbonyl are the alkoxy carbonyl of 2 ~ 7, cyano group, the carbonate groups etc. such as carbonic acid tributyl base)
[changing 39]
R
5: singly-bound, ethylidene, propylidene, following base (a) or following base (b)
Moreover, in following base, R
12represent hydrogen atom or methyl, L represents 1 or 2.
[changing 40]
P
2: there is the vinyl monomer of carboxyl and the multipolymer of other vinyl monomers; Not there is polymkeric substance or the multipolymer of the vinyl monomer of acidic group; Be selected from the group be made up of ester based polymer, ether based polymer and carbamate based polymer and these modifier, and the polymkeric substance of at least one acidic group can be contained
m：0.5～3
n：3～6
The content of the acidic group in composition S is that the acid number had by composition S is suitable for determining.As the acid number of composition S, be preferably 20 ~ 300 (mgKOH/g), be more preferably 50 ~ 250 (mgKOH/g), be particularly preferably 50 ~ 210 (mgKOH/g).If acid number is more than 20 (mgKOH/g), then fully can obtain the alkali-developable of photosensitive polymer combination, if acid number be 300 (mgKOH/g) below, then the dispersiveness of metal oxide particle and dispersion stabilization excellent.
As the molecular weight of composition S, with weight average molecular weight, be preferably 2,000 ~ 200,000, be more preferably 2,000 ~ 15,000, be particularly preferably 2,500 ~ 10,000.If weight average molecular weight is in above-mentioned scope, then the effect being directed into the multiple above-mentioned adsorption site of the end of polymkeric substance is played fully, and plays the adsorbability for solid surface.Composition S contained by resin combination of the present invention can be only one, also can be two or more.When two or more, are preferably it and add up to above-mentioned scope.
Below, enumerate the exemplary compounds of composition S, but the present invention is not limited thereto, as long as in the formula of being contained in (S), then arbitrary structure can be adopted.In addition, in following exemplary compounds, in mass conversion, P1 and P2 can adopt arbitrary value respectively.In addition, in following exemplary compounds, with the sulphur atom of polymer chain bond can with any one monomeric unit bond.In addition, there is no particular restriction for the end structure of following polymer chain, such as, can illustrate: hydrogen atom, alkyl, hydroxyl, alkoxy etc.
[changing 41]
[changing 42]
[changing 43]
[changing 44]
[changing 45]
[changing 46]
[changing 47]
In the exemplary compounds of mentioned component S, in mass conversion, the monomeric unit with carboxylate in macromolecular scaffold with have carboxyl monomeric unit containing than (P1: P2) be preferably 100: 0 ~ 80: 20 scope.
Composition S such as can refer to method described in Japanese Patent Laid-Open 2006-278118 publication and synthesizes.
Spreading agent can be used alone one, also can and with two or more.
Relative to the total solid composition of photosensitive polymer combination, the content of the spreading agent in photosensitive polymer combination of the present invention is preferably the scope of 5 quality % ~ 70 quality %, is more preferably the scope of 10 quality % ~ 50 quality %.
(composition G) thermal cross-linking agent
Optionally, photosensitive polymer combination of the present invention is preferably containing the thermal cross-linking agent beyond composition A and composition B.By adding thermal cross-linking agent, the film that the cured film obtained by photosensitive polymer combination of the present invention becomes harder can be made.
As thermal cross-linking agent, as long as Yin Re and produce cross-linking reaction, then and unrestricted (but, except composition A and composition B).Such as, can add the following stated containing the crosslinking chemical of alkoxy methyl or blocked isocyanate compound etc.
Relative to total solid composition 100 mass parts of photosensitive polymer combination, the addition of the composition A in photosensitive polymer combination of the present invention and the thermal cross-linking agent beyond composition B is preferably 0.01 mass parts ~ 50 mass parts, be more preferably 0.1 mass parts ~ 30 mass parts, and then be more preferably 0.5 mass parts ~ 20 mass parts.By adding within the scope of this, the cured film of physical strength and excellent solvent resistance can be obtained.Thermal cross-linking agent beyond composition A and composition B can and with multiple, in the case, all thermal cross-linking agents added up to and are calculated content.In addition, the addition of the thermal cross-linking agent beyond composition A and composition B is preferably less than the addition of composition A, in addition, is preferably less than the addition of composition B.
As thermal cross-linking agent, described containing the crosslinking chemical of alkoxy methyl and there is the compound etc. of at least one ethene unsaturated double-bond in the paragraph 0107 ~ paragraph 0108 of Japanese Patent Laid-Open 2012-8223 publication also preferably can be used.As the crosslinking chemical containing alkoxy methyl, be preferably aikoxymethytated glycolurils.
< blocked isocyanate compound >
In photosensitive polymer combination of the present invention, also can preferably adopt blocked isocyanate compound as thermal cross-linking agent.As long as blocked isocyanate compound has the compound of blocked isocyanate base, then there is no particular restriction, but with regard to indurative viewpoint, be preferably the compound in 1 molecule with the blocked isocyanate base of more than 2.
Such as, moreover the blocked isocyanate base in the present invention refers to the base that can generate isocyanate group because of heat, preferably can illustrate the base making sealer and isocyanate group carry out reacting to protect isocyanate group.In addition, above-mentioned blocked isocyanate base preferably can because of 90 DEG C ~ 250 DEG C heat and generate the base of isocyanate group.
In addition, as blocked isocyanate compound, its skeleton is not particularly limited, as long as have the compound of 2 isocyanate group in 1 molecule, then can be any compound, can be aliphatics, alicyclic or aromatic polyisocyanate, such as, can use aptly: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-nine methylene diisocyanate, 1,10-decamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-diethyl ether diisocyanate, diphenyl methane-4,4 '-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate, P-xylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, 3,3 '-xylene-4,4 '-diisocyanate, 4,4 '-diphenyl ether diisocyanate, tetrachloro phenylene vulcabond, norbornene alkyl diisocyanate, hydrogenation 1,3-eylylene diisocyanate, the isocyanate compounds such as hydrogenation Isosorbide-5-Nitrae-eylylene diisocyanate and the compound of the skeleton of prepolymer type gone out from these compound derivings.Among these, be particularly preferably toluene diisocyanate (Tolylene Diisocyanate, or methyl diphenylene diisocyanate (Diphenyl MethaneDiisocyanate TDI), MDI), hexamethylene diisocyanate (Hexamethylene Diisocyanate, HDI), isophorone diisocyanate (Isophorone Diisocyanate, IPDI).
As the parent structure of the blocked isocyanate compound in photosensitive polymer combination of the present invention, can enumerate: biuret form, isocyanuric acid ester type, adduct type, two functional prepolymer types etc.
As the sealer of the enclosed construction of the above-mentioned blocked isocyanate compound of formation, can enumerate: oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazole compound, imide series compound etc.Among these, be particularly preferably the sealer be selected from oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound.
As above-mentioned oxime compound, aldoxime and ketoxime can be enumerated, specifically, can illustrate: acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone-oxime, diphenyl-ketoxime, acetoxime etc.
As above-mentioned lactam compound, can illustrate: epsilon-caprolactams, butyrolactam etc.
As above-mentioned phenolic compounds, can illustrate: phenol, naphthols, cresols, xylenol, halogen substiuted phenol etc.
As above-mentioned alcoholic compound, can illustrate: methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, lactic acid alkyl ester etc.
As above-mentioned amines, primary amine and secondary amine can be enumerated, can be aromatic amine, fatty amine, cycloaliphatic amines any one, can illustrate: aniline, diphenylamine, aziridine, polyethyleneimine etc.
As above-mentioned activity methene compound, can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, methyl acetoacetate etc.
As above-mentioned pyrazole compound, can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc.,
As above-mentioned mercaptan compound, can illustrate: alkyl sulfhydryl, aryl mercaptan etc.
The blocked isocyanate compound of photosensitive polymer combination used in the present invention can be used as commercially available product and obtains, such as, can 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, rice Leo resistance to moral (Millionate) MS-50 (more than, Japanese polyurethane industry (NipponPolyurethane Industry) (share) manufactures), 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) manufactures), how resistance to moral (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) manufactures), De Shimo is (Desmodur) BL1100, BL1265MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Soviet Union rice all (Sumidur) BL3175 (more than, live change Baeyer polyurethane (Sumika Bayer Urethane) (share) manufacture) etc.
(composition H) antioxidant
Photosensitive polymer combination of the present invention is preferably containing antioxidant.
Can containing known antioxidant as antioxidant.By adding antioxidant, there is following advantage: can prevent cured film painted, maybe the thickness that can reduce caused by decomposing reduce, in addition, heat resistant transparent is excellent.
As this kind of antioxidant, include, for example: phosphorous antioxidant, amide-type, hydrazides class, hindered amine system antioxidant, sulphur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxylamine derivative etc.Among these antioxidants, with regard to the viewpoint that painted, the thickness of cured film reduces, be particularly preferably phenol system antioxidant, acid amides system antioxidant, hydrazides system antioxidant, sulphur system antioxidant.These antioxidants can be used alone one, also can be use mixing two or more.
As the commercially available product of phenol system antioxidant, include, for example: Ai Di Coase tower ripple (Adekastab) AO-15, Ai Di Coase tower ripple (Adekastab) AO-18, Ai Di Coase tower ripple (Adekastab) AO-20, Ai Di Coase tower ripple (Adekastab) AO-23, Ai Di Coase tower ripple (Adekastab) AO-30, Ai Di Coase tower ripple (Adekastab) AO-37, Ai Di Coase tower ripple (Adekastab) AO-40, Ai Di Coase tower ripple (Adekastab) AO-50, Ai Di Coase tower ripple (Adekastab) AO-51, Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-70, Ai Di Coase tower ripple (Adekastab) AO-80, Ai Di Coase tower ripple (Adekastab) AO-330, Ai Di Coase tower ripple (Adekastab) AO-412S, Ai Di Coase tower ripple (Adekastab) AO-503, Ai Di Coase tower ripple (Adekastab) A-611, Ai Di Coase tower ripple (Adekastab) A-612, Ai Di Coase tower ripple (Adekastab) A-613, Ai Di Coase tower ripple (Adekastab) PEP-4C, Ai Di Coase tower ripple (Adekastab) PEP-8, Ai Di Coase tower ripple (Adekastab) PEP-8W, Ai Di Coase tower ripple (Adekastab) PEP-24G, Ai Di Coase tower ripple (Adekastab) PEP-36, Ai Di Coase tower ripple (Adekastab) PEP-36Z, Ai Di Coase tower ripple (Adekastab) HP-10, Ai Di Coase tower ripple (Adekastab) 2112, Ai Di Coase tower ripple (Adekastab) 260, Ai Di Coase tower ripple (Adekastab) 522A, Ai Di Coase tower ripple (Adekastab) 1178, Ai Di Coase tower ripple (Adekastab) 1500, Ai Di Coase tower ripple (Adekastab) C, Ai Di Coase tower ripple (Adekastab) 135A, Ai Di Coase tower ripple (Adekastab) 3010, Ai Di Coase tower ripple (Adekastab) TPP, Ai Di Coase tower ripple (Adekastab) CDA-1, Ai Di Coase tower ripple (Adekastab) CDA-6, Ai Di Coase tower ripple (Adekastab) ZS-27, Ai Di Coase tower ripple (Adekastab) ZS-90, Ai Di Coase tower ripple (Adekastab) ZS-91 (more than, Ai Dike (share) manufactures), 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 add Floex (Irgafos) 168, Yi Jiamode (Irgamod) 295 (BASF AG's manufacture), ground slave refined (Tinuvin) 405 (BASF AG's manufacture) etc.Wherein, can use aptly Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (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 composition of photosensitive polymer combination, the content of antioxidant is preferably 0.1 quality % ~ 10 quality %, is more preferably 0.2 quality % ~ 5 quality %, is particularly preferably 0.5 quality % ~ 4 quality %.By being set within the scope of this, the film formed can obtain the sufficient transparency and pattern formed time sensitivity also become good.
In addition, also using various ultraviolet light absorber described in " new development (Nikkan Kogyo Shimbun (share)) of polymeric additive " or metal passivator etc. as the adjuvant beyond antioxidant, can be added in photosensitive polymer combination of the present invention.
Other compositions of < >
In photosensitive polymer combination of the present invention, except mentioned component, optionally preferably can add (composition I) sensitizer, (composition J) touch modifying agent, (composition K) alkali compounds, (composition L) surfactant.And then, in photosensitive polymer combination of the present invention, above-mentioned ultraviolet light absorber, metal passivator or acid proliferation generator can be added, development accelerant, plasticiser, hot radical produce agent, thermal acid generator, tackifier and organic or inorganic the known adjuvant such as antisettling agent.
(composition I) sensitizer
Photosensitive polymer combination of the present invention be preferably with the combination of (components D) light acid producing agent in containing sensitizer, to promote the decomposition of light acid producing agent.Sensitizer absorbs actinic ray or radioactive ray and becomes electron excitation state.The sensitizer becoming electron excitation state contacts with light acid producing agent, and produces the effects such as electronics moves, energy moves, heating.Thus, light acid producing agent produces chemical change and decomposes, and generates acid.As the example of preferred sensitizer, can enumerate belong to following compounds and the wavelength region may of 350nm ~ 450nm any one in there is the compound of absorbing wavelength.
The polynuclear aromatic same clan (such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxy anthracene, 9,10-diethoxy anthracene, 3,7-dimethoxy anthracene, 9,10-dipropoxy anthracene), xanthene (xanthene) class (such as fluorescein (fluorescein), eosin, red algae red (erythrosine), rhodamine B (Rhodamine B), rose bengal (Rose Bengal)), xanthone (such as xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class (such as thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (such as merocyanine, carbonyl merocyanine), if red cyanines class, oxonols class, thiazide (such as give repeated exhortations by thiophene, 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), salt (such as the sour inner salt in side) in side's acid, styrene base class, basicity styrene base class (such as 2-{2-[4-(dimethylamino) phenyl] vinyl } benzoxazole), Coumarins (such as 7-lignocaine-4-methylcoumarin, Hymecromone, 2,3,6,7-tetrahydrochysene-9-methyl isophthalic acid H, 5H, 11H [1] chromene is [6,7,8-ij] quinolizine-11-ketone also).
Among these sensitizers, be preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, Coumarins, be more preferably the polynuclear aromatic same clan.
Relative to light acid producing agent 100 mass parts of photosensitive polymer combination, the addition of the sensitizer in photosensitive polymer combination of the present invention is preferably 0 mass parts ~ 1,000 mass parts, is more preferably 10 mass parts ~ 500 mass parts, and then is more preferably 50 mass parts ~ 200 mass parts.
In addition, sensitizer can be used alone one, also can and with two or more.
(composition J) touches modifying agent
Photosensitive polymer combination of the present invention can containing contiguity modifying agent.
The contiguity modifying agent of photosensitive polymer combination used in the present invention is the compound of the adhesion promoting inorganics silicon compounds such as (, the metals such as gold, copper, aluminium) such as silicon, monox, silicon nitrides and the dielectric film becoming base material.Specifically, silane coupling agent, mercaptan based compound etc. can be enumerated.Among these, be preferably silane coupling agent.
Silane coupling agent as the contiguity modifying agent used in the present invention is modified as object with interface, is not particularly limited, can uses known silane coupling agent.
As preferred silane coupling agent, include, for example: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane.
Among these, be more preferably γ-glycidyloxypropyl silane or γ-methacryloxypropyl trialkoxy silane, and then be more preferably γ-glycidyloxypropyl silane.
These compounds can be used alone a section or be used in combination of two or more.These compounds are effective for promoting with the adhesion of substrate, and also effective with the cone angle of substrate for adjustment.
Relative to components D 100 weight portion, the content of the contiguity modifying agent in photosensitive polymer combination of the present invention is preferably 0.1 mass parts ~ 20 mass parts, is more preferably 0.5 mass parts ~ 10 mass parts.
(composition K) alkali compounds
Photosensitive polymer combination of the present invention can contain alkali compounds.
As alkali compounds, at random select in the alkali compounds that can use in Chemical amplification resist to use.Include, for example: the quarternary ammonium salt etc. of fatty amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic acid.As these concrete example, compound described in the paragraph 0204 ~ paragraph 0207 of Japanese Patent Laid-Open 2011-221494 publication can be enumerated.
Specifically, as fatty amine, include, for example: trimethylamine, diethylamine, triethylamine, two-n-propylamine, three-n-propylamine, two-n-amylamine, three-n-amylamine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexylmethylamine etc.
As aromatic amine, include, for example: aniline, benzyl amine, DMA, diphenylamine etc.
As hetero ring type amine, include, for example: pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, DMAP, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenylimidazolyl, nicotine, nicotinic acid, niacinamide, quinoline, oxine, pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, 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, include, for example: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide four-normal-butyl ammonium, hydroxide four-n-hexyl ammonium etc.
As the quarternary ammonium salt of carboxylic acid, include, for example: acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid four-normal-butyl ammonium, benzoic acid four-normal-butyl ammonium etc.
Among these, be preferably hetero ring type amine, be particularly preferably N-cyclohexyl-N '-[2-(4-morpholinyl) ethyl] thiocarbamide.
Alkali compounds used in the present invention can be used alone one, also can and with two or more.
Relative to total solid composition 100 mass parts in photosensitive polymer combination, the content of the alkali compounds in photosensitive polymer combination of the present invention is preferably 0.001 mass parts ~ 3 mass parts, is more preferably 0.005 mass parts ~ 1 mass parts.
(composition L) surfactant
Photosensitive polymer combination of the present invention can contain surfactant.
As surfactant, can use negative ion system, kation system, nonionic system or both sexes any one, but preferred surfactant is nonionic system surfactant.
As the example of nonionic system surfactant, can enumerate: the higher aliphatic acid diesters class of polyoxyethylene higher alkyl ether, polyoxyethylene higher alkyl phenyl ethers, polyoxyethylene glycol, silicone-based, fluorine system surfactant.As fluorine system surfactant, the example of silicone-based surfactant, specifically, No. 62-36663, Japanese Patent Laid-Open No. Sho can be enumerated, No. 61-226746, Japanese Patent Laid-Open No. Sho, No. 61-226745, Japanese Patent Laid-Open No. Sho, No. 62-170950, Japanese Patent Laid-Open No. Sho, No. 63-34540, Japanese Patent Laid-Open No. Sho, No. 7-230165, Japanese Patent Laid-Open, No. 8-62834, Japanese Patent Laid-Open, No. 9-54432, Japanese Patent Laid-Open, No. 9-5988, Japanese Patent Laid-Open, the surfactant recorded in each publication of Japanese Patent Laid-Open 2001-330953 etc., also commercially available surfactant can be used.In addition, following trade name can be enumerated: KP (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), Po Lifuluo (Polyflow) (common prosperity society chemistry (share) manufacture), Ai Futuo (Eftop) (Mitsubishi General Materials electronics changes into (share) and manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (share) manufactures), not rad (Fluorad) (Sumitomo 3M (share) manufacture), A Sajia (Asahi Guard) (Asahi Glass (share) manufacture), Sha Fulong (Surflon) (AGC beautifies clearly (AGC SEIMI CHEMICAL) (share) manufacture), Pohle Floex (PolyFox) (manufacture of Ou Nuofa (OMNOVA) company), each series such as SH-8400 (eastern beautiful DOW CORNING silicone (Dow CorningToray Silicone) (share) manufacture).
Among these, be preferably fluorine system surfactant or silicone-based surfactant, be more preferably fluorine system surfactant, and then be more preferably fluorine system non-ionic surfactant, be particularly preferably the non-ionic surfactant containing perfluor base.
In addition, as surfactant, the multipolymer that can be listed below is as preference, this multipolymer contains Component units A represented by following formula (L-1) and Component units B, and be 1 using tetrahydrofuran (THF) as the weight average molecular weight (Mw) of the polystyrene conversion measured by gel permeation chromatography during solvent, more than 000,10, less than 000.
[changing 48]
(in formula (L-1), R
401and R
403separately represent hydrogen atom or methyl, R
402represent that carbon number is the straight-chain alkyl-sub-of more than 1, less than 4, R
404represent that hydrogen atom or carbon number are the alkyl of more than 1, less than 4, L represents that carbon number is the alkylidene of more than 3, less than 6, p and q is the quality percentage representing polymerization ratio, p represents the numerical value of more than 10 quality %, below 80 quality %, q represents the numerical value of more than 20 quality %, below 90 quality %, r represents the integer of more than 1, less than 18, and s represents the integer of more than 1, less than 10).
Above-mentioned L is preferably the branched alkylene groups represented by following formula (L-2).R in formula (L-2)
405represent that carbon number is the alkyl of more than 1, less than 4, with regard to compatibility and the viewpoint for the wetting state of applied, be preferably the alkyl that carbon number is more than 1, less than 3, be more preferably the alkyl that carbon number is 2 or 3.P and q is preferably p+q=100 with (p+q), is 100 quality %.
[changing 49]
The weight average molecular weight (Mw) of above-mentioned multipolymer is more preferably 1, more than 500,5, less than 000.
These surfactants can be used alone one or be use mixing two or more.
Relative to total solid composition 100 mass parts in photosensitive polymer combination, the addition of the surfactant in photosensitive polymer combination of the present invention is preferably below 10 mass parts, be more preferably 0.001 mass parts ~ 10 mass parts, and then be more preferably 0.01 mass parts ~ 3 mass parts.
(composition M) acid proliferation generator
In order to promote sensitivity, photosensitive polymer combination of the present invention can contain acid proliferation generator.
Acid proliferation generator used in the present invention produces acid further by acid catalyst reaction and make the compound that the acid concentration in reactive system rises, and the compound for stably existing under the state that there is not acid.This kind of compound increases more than one acid by 1 secondary response, therefore with the progress of reacting, reacts and carry out post, but the acid produced itself can bring out selfdecomposition, therefore the intensity of the acid of this place generation is in acid ionization constant, pKa, is preferably less than 3, is more preferably less than 2.In addition, the lower limit of pKa is not particularly limited, but with regard to the viewpoint obtaining easiness, is preferably more than-15, is more preferably more than-10.
As the concrete example of acid proliferation generator, can enumerate: compound described in page the 2nd row of the paragraph 0203 ~ paragraph 0223 of Japanese Patent Laid-Open 10-1508 publication, the paragraph 0016 ~ paragraph 0055 of Japanese Patent Laid-Open 10-282642 publication and Jap.P. JP-A 9-512498 publication the 39th page of the 12nd row ~ 47.
As acid proliferation generator used in the present invention, the acid because producing from acid producing agent can be enumerated and decompose, and producing the compound that the pKa such as dichloroacetic acid, trichloroacetic acid, methane-sulforic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid are the acid of less than 3.
Specifically, following compound etc. can be enumerated.
[changing 50]
With regard to the viewpoint of the dissolving contrast in exposure portion and unexposed portion, relative to light acid producing agent 100 weight portion, the content of acid proliferation generator in photosensitive polymer combination is preferably set to 10 mass parts ~ 1,000 mass parts, is more preferably and is set to 20 mass parts ~ 500 mass parts.
(composition N) development accelerant
Photosensitive polymer combination of the present invention can contain development accelerant.
As development accelerant, the arbitrary compound with development accelaration effect can be used, but preferably there is the compound of at least one structure in the group selecting free carboxyl group and alkylene oxide group to form, most preferably be the compound with carboxyl.
As development accelerant, can with reference to the record of the paragraph 0171 ~ paragraph 0172 of Japanese Patent Laid-Open 2012-042837 publication, its content can be incorporated into in present specification.
In addition, the molecular weight of development accelerant is preferably 100 ~ 2, and 000, be more preferably 150 ~ 1,500, and then be more preferably 150 ~ 1,000.
Development accelerant can be used alone one, also can and with two or more.
With regard to the viewpoint of sensitivity and residual film ratio, relative to total solid composition 100 mass parts of photosensitive composite, the addition of the development accelerant in photosensitive polymer combination of the present invention is preferably 0 mass parts ~ 30 mass parts, be more preferably 0.1 mass parts ~ 20 mass parts, most preferably be 0.5 mass parts ~ 10 mass parts.
(composition O) plasticiser
Resin combination of the present invention can contain plasticiser.
As plasticiser, include, for example: dibutyl phthalate, dioctyl phthalate, phthalic acid two-ten diester, polyglycol, glycerine, dimethyl glyceryl phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerine etc.
Relative to content 100 mass parts of composition A, the content of the plasticiser in resin combination of the present invention is preferably 0.1 mass parts ~ 30 mass parts, is more preferably 1 mass parts ~ 10 mass parts.
In addition, in the hot radical generation agent described in also can using in the paragraph 0120 ~ paragraph 0121 of Japanese Patent Laid-Open 2012-8223 publication, No. 2011/136074th, International Publication, described nitrogen-containing compound and thermal acid generator are as other adjuvants.
(manufacture method of resin pattern)
Secondly, the manufacture method of resin pattern of the present invention is described.
The manufacture method of resin pattern of the present invention preferably comprises the step of following (1) ~ (5).
(1) photosensitive polymer combination of the present invention is coated the application step on substrate;
(2) in the resin combination be coated with, remove the solvent removal step of solvent;
(3) utilize actinic ray that the resin combination eliminating solvent is exposed into the step of exposure of pattern-like;
(4) development step that aqueous developer solution is developed to the resin combination through exposure is utilized; And
(5) to the heat treatment step that the resin combination through development is heat-treated.
Next coming in order are described each step.
In the application step of (1), be preferably the moistening film coated by photosensitive polymer combination of the present invention and substrate makes containing solvent.Be preferably and coat the cleaning that substrate goes forward to carry out the substrates such as alkali cleaning or plasma clean photonasty being set resin combination, be more preferably after base-plate cleaning and then utilize hexamethyldisilazane to process substrate surface.By carrying out this process, photosensitive polymer combination promotes for the adhesion of substrate.As the method utilizing hexamethyldisilazane to process substrate surface, be not particularly limited, include, for example and make substrate be exposed to method etc. in hexamethyldisilazane steam in advance.
As aforesaid substrate, can enumerate: inorganic substrate, resin, resin composite materials, ITO, Cu substrate, the plastic base of polyethylene terephthalate, cellulose triacetate (Cellulose Triacetate, TAC) etc.
As inorganic substrate, include, for example: glass, quartz, silicone, silicon nitride, and on the substrate as these the composite base plate of evaporation molybdenum, titanium, aluminium, copper etc.
As resin, the substrate comprising following resin can be enumerated: polybutylene terephthalate, polyethylene terephthalate, Polyethylene Naphthalate, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyethersulfone, polyarylate, allyl diglycol carbonates, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, polycyclic alkene, norbornene resin, the fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acryl resin, epoxy resin, silicone resin, ionomeric resins, cyanate ester resin, crosslinked fumaric acid diester resin, cyclic polyolefin, aromatic ether resin, maleimide-olefin resin, cellulose, the substrate of the synthetic resin such as episulfide resin (episulfide resin).
The situation that these substrates directly use with above-mentioned form is few, usually according to the form of end article, such as, is formed with multilayer laminated structure as such in thin film transistor (TFT) (Thin Film Transistor, TFT) element.
The method be coated with on substrate is not particularly limited, such as, can use: the methods such as slot coated method, spraying rubbing method, rolling method, method of spin coating, cast coating method, slit and rotation (slit and spin) method.And then, also can apply as so-called (prewet) method of prewetting described in Japanese Patent Laid-Open 2009-145395 publication.
Coating film thickness is not particularly limited, and can be coated with, but preferably use in the scope of 0.5 μm ~ 10 μm with the thickness corresponding to purposes.
In the solvent removal step of (2), in the above-mentioned film applied, remove solvent by decompression (vacuum) and/or heating, thus form dry coating on substrate.The heating condition of solvent removal step is preferably and heats 30 seconds ~ about 300 seconds at 70 DEG C ~ 130 DEG C.When temperature and time is above-mentioned scope, the adhesion of pattern is good and also can reduce residue.
In the step of exposure of (3), the mask across the pattern with regulation irradiates actinic ray to the substrate being provided with film.In this step, light acid producing agent decomposes and produces acid.Be coated with the catalyst action of the acid that sour decomposability gene contained in film component produces and be hydrolyzed, thus generating acidic group (such as carboxyl or phenolic hydroxyl group).
As utilizing photoactinic exposure light source, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light emitting diode (Light Emitting Diode can be used, LED) light source, excimer laser generation device etc., can preferably use g ray (436nm), i ray (365nm), h ray (405nm) etc. to have the actinic ray of wavelength of more than wavelength 300nm, below 450nm.In addition, optionally also irradiation light is adjusted by point optical filter as long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter.
As exposure device, mirror surface projection can be used to aim at exposer (mirror projection aligner), stepper, scanner, the exposure machine of the various modes such as close induction type, contact, microlens array formula, laser explosure formula.
Having in the region of acid catalyst in generation, in order to accelerate said hydrolyzed reaction, can carry out exposing rear heating: postexposure bake (Post Exposure Bake) (hereinafter also referred to as " PEB ").By PEB, can promote from the sour carboxyl of decomposability base or the generation of phenolic hydroxyl group.Temperature when carrying out PEB is preferably more than 30 DEG C, less than 130 DEG C, is more preferably more than 40 DEG C, less than 110 DEG C, is particularly preferably more than 50 DEG C, less than 100 DEG C.
But, the energy of activation that sour decomposability base in the present invention decomposes due to acid is low, easy reason exposes the acid being derived from acid producing agent that produces and decomposes, and produce acidic group (such as carboxyl or phenolic hydroxyl group), therefore not must carry out PEB, also form erect image (positive image) by development.
In the development step of (4), alkaline-based developer is used to develop to the multipolymer with free acidic group (such as carboxyl or phenolic hydroxyl group).The region, exposure portion comprising the resin combination with the acidic group (such as carboxyl or phenolic hydroxyl group) be easily dissolved in alkaline-based developer is removed, forms erect image thus.
Containing alkali compounds in the developer solution preferably used in development step.As alkali compounds, such as, can use: the alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide; The alkali carbonate classes such as sodium carbonate, sal tartari, cesium carbonate; The alkaline metal bicarbonate such as sodium bicarbonate, potassium bicarbonate class; The tetraalkylammonium hydroxide classes such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, diethyldimethylammonhydroxide hydroxide: the hydroxides such as choline (hydroxyalkyl) trialkyl ammonium class; The silicates such as sodium silicate, sodium metasilicate; The alkyl amines such as ethamine, propylamine, diethylamine, triethylamine; The alcamines such as dimethylethanolamine, triethanolamine; The ester ring type amines such as 1,8-diazabicyclo [5.4.0]-7-hendecene, 1,5-diazabicyclo [4.3.0]-5-nonene.
Among these, be preferably NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, choline (hydroxide 2-hydroxyethyl trimethyl ammonium).
In addition, also the aqueous solution of adding the water-miscible organic solvents such as appropriate methyl alcohol or ethanol or surfactant in the aqueous solution to above-mentioned alkali compounds can be used as developer solution.
As preferred developer solution, can enumerate: 0.4 quality % aqueous solution of tetraethyl ammonium hydroxide, 0.5 quality % aqueous solution, 0.7 quality % aqueous solution or 2.38 quality % aqueous solution.
The pH of developer solution is preferably 9.0 ~ 14, is more preferably 10.0 ~ 14.0.The concentration of developer solution is preferably 0.1 quality % ~ 20 quality %, is more preferably 0.1 quality % ~ 5.0 quality %.
Development time is preferably 30 seconds ~ 500 seconds, is more preferably 30 seconds ~ 180 seconds.In addition, the method for development can be any one methods such as covering liquid method, infusion process, spray process.After development, can flowing water cleaning be carried out, and the pattern desired by being formed.The time of flowing water cleaning is preferably 30 seconds ~ 300 seconds, is more preferably 30 seconds ~ 90 seconds.
After development, also rinsing step can be carried out.In rinsing step, utilize the substrate after the cleaning developments such as pure water, thus accompanying developer solution is removed, and the residue that will develop is removed.ELUTION METHOD can use known method.Include, for example spray drip washing or dipping drip washing etc.
In the heat treatment step (toasting afterwards) of (5), by heating obtained erect image, sour decomposability base can be made to carry out thermal decomposition and generate acidic group (such as carboxyl or phenolic hydroxyl group), and be cross-linked with bridging property base, crosslinking chemical etc., form resin pattern thus.This heating is preferably and uses the heating arrangement such as heating plate or baking oven, in the temperature of regulation, such as, at 180 DEG C ~ 250 DEG C, with official hour, if on such as heating plate, then carry out the heating of 5 minutes ~ 90 minutes, if baking oven, then carry out the heating of 30 minutes ~ 120 minutes.By making cross-linking reaction carry out, and the excellent diaphragm such as thermotolerance, hardness or interlayer dielectric can be formed.In addition, when heating, also can carry out in a nitrogen environment, promoting the transparency thus.When using plastic base, at 80 DEG C ~ 140 DEG C, preferably carry out the heating of 5 minutes ~ 120 minutes.
Also can front at heat treatment step (afterwards toast), toast with lower temperature after carry out heat treatment step (adding of middle baking procedure).When carrying out centre baking, being preferably and heating after 1 minute ~ 60 minutes at 90 DEG C ~ 150 DEG C, toasting after carrying out under the high temperature more than 200 DEG C.In addition, also centre can be toasted, rear baking is divided into the multistage in more than 3 stages and heats.By the design of baking, rear baking in the middle of this kind, the cone angle of adjustable pattern.These heating can use the known heating means such as heating plate, baking oven, infrared heater.
Moreover, can before rear baking, utilize actinic ray to carry out exposing again (post-exposure) to the figuratum substrate of formation comprehensively, then rear baking is carried out, acid is produced thus from the light acid producing agent existed in unexposed portion, and make it as promoting that the catalyzer of cross-linking step plays function, thus the sclerous reaction of film can be promoted.As preferred exposure when comprising post-exposure step, be preferably 100mJ/cm
2~ 3,000mJ/cm
2, be particularly preferably 100mJ/cm
2~ 500mJ/cm
2.
And then the cured film obtained from photosensitive polymer combination of the present invention also can be used as dry-etching resist (dryetching resist).When the cured film obtained carrying out thermmohardening by heat treatment step is used as dry-etching resist, the dry-etching process such as ashing, plasma etching, ozone etching can be carried out as etch processes.
(cured film and resin pattern)
Cured film of the present invention is cured film photosensitive polymer combination of the present invention being hardened and obtains.
Resin pattern of the present invention is formed figuratum cured film of the present invention.
Cured film of the present invention can be used as interlayer dielectric aptly.In addition, cured film of the present invention preferably utilizes the resin pattern that the formation method of resin pattern of the present invention obtains.
According to photosensitive polymer combination of the present invention, insulativity excellence can be obtained, also there is when at high temperature toasting the interlayer dielectric of high transparent.The interlayer dielectric of photosensitive polymer combination of the present invention is used to have high transparent, and cured film physical properties excellent, the purposes therefore for organic EL display or liquid crystal indicator is useful.
(hardening thing and manufacture method thereof)
Hardening thing of the present invention is hardening thing photosensitive polymer combination of the present invention being hardened and obtains, and as mentioned above, its shape can not be film, as long as arbitrary shape.
There is no particular restriction for the manufacture method of hardening thing of the present invention, but preferably comprise the following steps (a) ~ step (c) at least successively.
A photosensitive polymer combination of the present invention is coated the application step on substrate by ();
B () removes the solvent removal step of solvent in the resin combination be coated with; And
C heat treatment step that () is heat-treated the resin combination eliminating solvent.
The implication of step (a) and step (b) is identical with above-mentioned application step and above-mentioned solvent removal step respectively, and preferred form is also identical.
Except the object of heat-treating is for except the resin combination eliminating solvent that obtained by step (b), step (c) is the step identical with above-mentioned heat treatment step, and the preferred form of the heating-up temperature in above-mentioned heat treatment step, heat time, heating means etc. is preferred too.
Hardening thing of the present invention or cured film can be used as the optical components such as lenticule, optical waveguide, anti-reflective film, LED sealing material and LED chip coating material aptly, or the observability reduction hardening thing of the distribution electrode used in touch-screen.
In addition; hardening thing of the present invention or cured film such as can be suitably used for planarization film in liquid crystal indicator or organic el device etc. as described later or interlayer dielectric, colored filter diaphragm, in order to the thickness of the liquid crystal layer in liquid crystal indicator to be remained the structure component etc. of fixing distance piece, MEMS (micro electro mechanical system) (Micro Electro Mechanical System, MEMS) element.
(liquid crystal indicator)
The feature of liquid crystal indicator of the present invention is to possess cured film of the present invention.
As liquid crystal indicator of the present invention, use except the planarization film that formed of photosensitive polymer combination of the present invention or interlayer dielectric except having, there is no particular restriction, can enumerate the known liquid crystal indicator adopting various structure.
Such as, as the concrete example of the TFT (Thin-Film Transistor) that liquid crystal indicator of the present invention possesses, can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to electrical characteristics excellence, preferably uses after therefore can combining with these TFT.
In addition, as the adoptable liquid crystal drive mode of liquid crystal indicator of the present invention, can enumerate: twisted nematic (TwistedNematic, TN) mode, vertical orientated (VirticalAlignment, VA) mode, coplanar switching (In-PlaceSwitching, IPS) mode, fringing field switch (FringsField Switching, FFS) mode, optical compensation curved (Optically CompensatedBend, OCB) mode etc.
In panel is formed, even if colorful optical filter array (Color Filter on Allay [Array], COA) liquid crystal indicator of mode, also can use cured film of the present invention, such as, can be used as organic insulating film (212) described in organic insulating film (115) described in Japanese Patent Laid-Open 2005-284291 publication or Japanese Patent Laid-Open 2005-346054 publication.
In addition, concrete aligned as the adoptable liquid crystal orientation film of liquid crystal indicator of the present invention, can enumerate friction orientation method, light orientation side etc.In addition, also can utilize polymer stabilizing orientation (Polymer Sustained Alignment, PSA) technology described in Japanese Patent Laid-Open 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication and obtain polymer orientation support.
In addition, photosensitive polymer combination of the present invention and cured film of the present invention are not limited to such use, can be used for various uses.Such as; except planarization film or interlayer dielectric, also can be suitably used for colored filter diaphragm or in order to the thickness of the liquid crystal layer in liquid crystal indicator to be remained in fixing distance piece or solid photographic element the lenticule etc. be arranged on colored filter.
Fig. 1 is the concept sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.This color liquid crystal display arrangement 10 has the liquid crystal panel of back light unit 12 for the back side, and liquid crystal panel is configured with the element of the TFT16 corresponding with being configured in the 2 sheet glass substrates 14, all pixels between glass substrate 15 that are pasted with light polarizing film.Be formed in each element on glass substrate, by being formed at contact hole 18 in cured film 17 and the ito transparent electrode 19 of the tangible pixel electrode of distribution.The layer that ito transparent electrode 19 is provided with liquid crystal 20 and the RGB colored filter 22 being configured with black matrix".
As the light source of backlight, be not particularly limited, known light source can be used.Include, for example: multi-colored led, fluorescent light (cold-cathode tube), organic EL etc. of White LED, blue red green etc.
In addition, liquid crystal indicator also can be made into the device of 3D (stereopsis) type or the device of touch screen type.And then, also can be set to flexible type, and can be used as phase insulation film (520) described in the 2nd phase insulation film (48) described in Japanese Patent Laid-Open 2011-145686 publication or Japanese Patent Laid-Open 2009-258758 publication.
(organic EL display)
The feature of organic EL display of the present invention is to possess cured film of the present invention.
As organic EL display of the present invention, use except the planarization film that formed of photosensitive polymer combination of the present invention or interlayer dielectric except having, there is no particular restriction, can enumerate the known various organic EL display or liquid crystal indicator that adopt various structure.
Such as, as the concrete example of the TFT (Thin-Film Transistor) that organic EL display of the present invention possesses, can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to electrical characteristics excellence, preferably uses after therefore can combining with these TFT.
Fig. 2 is the formation concept map of an example of organic EL display.Represent the constructed profile of the substrate in the organic EL display of bottom emission type, and there is planarization film 4.
Glass substrate 6 is formed the TFT1 of bottom gate polar form, and under the state covering this TFT1, forms the dielectric film 3 comprising Si3N4.Formed on the insulating film 3 after explanations are omitted hering illustrated contact hole, form via this contact hole the distribution 2 (being highly 1.0 μm) being connected to TFT1 on the insulating film 3.Distribution 2 is the lines in order to will be connected with TFT1 between TFT1 or by the organic EL formed in step thereafter.
And then, in order to make to form produced concavo-convex planarization by distribution 2, imbedding under the concavo-convex state produced by distribution 2, forming planarization film 4 on the insulating film 3.
Planarization film 4 is formed the organic EL of bottom emission type.That is, the first electrode 5 comprising ITO is made to be connected to distribution 2 via contact hole 7 and to be formed on planarization film 4.In addition, the first electrode 5 is equivalent to the anode of organic EL.
Forming the dielectric film 8 of the shape of the periphery of covering first electrode 5, by arranging this dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and step thereafter can be prevented.
And then, although not shown in Fig. 2, but carry out evaporation successively to arrange hole transmission layer, organic luminous layer, electron transfer layer across desired pattern mask, then, whole of surface is formed the second electrode comprising Al, then carry out fitting sealing with glass for sealing plate by using ultraviolet ray hardening type epoxy resin, and obtain the organic EL display connecting the active array type in order to the TFT1 driven it on each organic EL.
The Resist patterns using photosensitive polymer combination of the present invention to be formed, due to hardening and cured film excellent, is therefore made dividing wall and is used as the structure component of MEMS element or is assembled rear use as a part for Mechanical Driven part by photosensitive polymer combination of the present invention.As this kind of MEMS element, include, for example: the parts such as surface acoustic wave (surfaceacoustic wave) wave filter, bulk acoustic wave (bulk acoustic wave) wave filter, gyro sensor (gyro sensor), the micro-shutter of display, imageing sensor, Electronic Paper, ink gun, biochip, sealant.Example has illustration in Jap.P. spy table 2007-522531 publication, Japanese Patent Laid-Open 2008-250200 publication, Japanese Patent Laid-Open 2009-263544 publication etc. more specifically.
Photosensitive polymer combination of the present invention is due to flatness or transparency excellence, therefore also can be used for being formed accumulation horizon (16) described in Fig. 2 of such as Japanese Patent Laid-Open 2011-107476 publication and planarization film (57), dividing wall (12) described in Fig. 4 (a) of Japanese Patent Laid-Open 2010-9793 publication and planarization film (102), accumulation horizon (221) described in Figure 10 of Japanese Patent Laid-Open 2010-27591 publication and the 3rd interlayer dielectric (216b), the 2nd interlayer dielectric (125) described in Fig. 4 (a) of Japanese Patent Laid-Open 2009-128577 publication and the 3rd interlayer dielectric (126), planarization film (12) described in Fig. 3 of Japanese Patent Laid-Open 2010-182638 publication and pixel separation dielectric film (14) etc.
(touch panel display device)
Touch panel display device of the present invention possesses the capacitive input device with cured film of the present invention.In addition, capacitive input device of the present invention has cured film of the present invention.
Capacitive input device of the present invention preferably has front panel, and at least has the key element of following (1) ~ following (5) in the noncontact side of above-mentioned front panel, and above-mentioned (4) are hardening thing of the present invention.
(1) mask layer
(2) multiple pad part above extends at first direction (X) multiple first transparent electrode patterns formed via coupling part
(3) be electrically insulated with above-mentioned first transparent electrode pattern and be included in multiple second transparent electrode patterns direction that intersects with above-mentioned first direction (X) extending formed multiple pad parts
(4) by insulation course that above-mentioned first transparent electrode pattern and above-mentioned second transparent electrode pattern are electrically insulated
(5) be electrically connected from least one of above-mentioned first transparent electrode pattern and above-mentioned second transparent electrode pattern and with above-mentioned first transparent electrode pattern and the different electric conductivity key element (conductive element) of above-mentioned second transparent electrode pattern
Capacitive input device of the present invention is preferably all or part of mode of the key element to cover above-mentioned (1) ~ above-mentioned (5) and then arranges protective clear layer, and being more preferably above-mentioned protective clear layer is cured film of the present invention.
First, the formation of capacitive input device is described.Fig. 3 is the sectional view of the formation representing capacitive input device.In figure 3, capacitive input device 30 comprises: front panel 31, mask layer 32, first transparent electrode pattern 33, second transparent electrode pattern 34, insulation course 35, electric conductivity key element 36 and protective clear layer 37.
Front panel 31 is made up of light-transmitting substrates such as glass substrates, the tempered glass etc. that can to use with the gorilla glass of healthy and free from worry (Corning) company (Gorilla Glass) be representative.In addition, in figure 3, the side being provided with each key element of front panel 31 is called noncontact face.In capacitive input device 30 of the present invention, finger etc. is contacted with the surface of contact (opposing face in noncontact face) of front panel 31 etc. and input.Below, sometimes front panel is called " base material ".
In addition, the noncontact face of front panel 31 is provided with mask layer 32.Mask layer 32 is patterns of the frame shape around the viewing area of the noncontact side being formed at touch-screen front panel, and it is in order to make lead-in wire etc. not in sight and be formed.
In capacitive input device of the present invention, as shown in Figure 4, the mode in the region (region in Fig. 4 beyond input face) covering a part for front panel 31 is provided with mask layer 32.And then, in front panel 31, as shown in Figure 2, can peristome 38 be set in a part.In peristome 38, the mechanical switch utilizing pressing can be set.
As shown in Figure 5, the surface of contact of front panel 31 is formed multiple first transparent electrode pattern 33, multiple second transparent electrode pattern 34, and insulation course 35, above-mentioned multiple first transparent electrode pattern 33 is that multiple pad part formed upper extension of first direction (X) via coupling part, above-mentioned multiple second transparent electrode pattern 34 is electrically insulated with the first transparent electrode pattern 33, and be included in and the direction that intersects with first direction (X) extend formed multiple pad parts, above-mentioned insulation course 35 makes the first transparent electrode pattern 33 and the second transparent electrode pattern 34 be electrically insulated.Above-mentioned first transparent electrode pattern 33, second transparent electrode pattern 34 and electric conductivity key element 36 described later such as can utilize the conductive metal oxide film of the light transmission such as ITO (Indium Tin Oxide) or indium zinc oxide (Indium Zinc Oxide, IZO) to make.As this kind of metal film, can enumerate: ito film; The metal film of Al, Zn, Cu, Fe, Ni, Cr, Mo etc.; SiO
2deng metal oxide film etc.Now, the thickness of each key element can be set to 10nm ~ 200nm.In addition, because making the ito film of amorphous become the ito film of polycrystalline by calcining, therefore also resistance can be reduced.In addition, above-mentioned first transparent electrode pattern 33, second transparent electrode pattern 34 and electric conductivity key element 36 described later also can use photosensitive transfer printing material to manufacture, and this photosensitive transfer printing material has the photosensitive polymer combination using above-mentioned conducting fibre.In addition, when utilizing ITO etc. to form first conductive pattern etc., can with reference to the paragraph 0014 ~ paragraph 0016 etc. of Jap.P. No. 4506785 publication.
In addition, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 can be opposition side with front panel 31 these two regions, face are arranged across the noncontact face of front panel 31 and mask layer 32.In figure 3, the figure that with front panel 31 be opposition side face this two region arrange of the second transparent electrode pattern across the noncontact face of front panel 31 and mask layer 32 is represented.
Fig. 5 is used to be described the first transparent electrode pattern 33 and the second transparent electrode pattern 34.Fig. 5 is the key diagram of the example representing the first transparent electrode pattern in the present invention and the second transparent electrode pattern.As shown in Figure 5, the first transparent electrode pattern 33 is that pad part 33a is formed in the upper extension of first direction (X) via coupling part 33b.In addition, the second transparent electrode pattern 34 is electrically insulated with the first transparent electrode pattern 33 by insulation course 35 and is included in the direction (second direction (Y) in Fig. 5) intersected with first direction (X) and above extends the multiple pad parts formed.Herein, when formation the first transparent electrode pattern 33, using above-mentioned pad part 33a and coupling part 33b as integrally making, also can only make coupling part 33b, and using pad part 33a and the second transparent electrode pattern 34 as integrally making (patterning).When using pad part 33a and the second transparent electrode pattern 34 as when integrally making (patterning), as shown in Figure 5, each layer is formed as follows: a part and a part of pad part 33a of coupling part 33b are connected and the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by insulation course 35.
In figure 3, be opposition side with front panel 31 side, face is provided with electric conductivity key element 36 at mask layer 32.Electric conductivity key element 36 be electrically connected from least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 and with the first transparent electrode pattern 33 and the different key element of the second transparent electrode pattern 34.In figure 3, the figure that electric conductivity key element 36 is connected with the second transparent electrode pattern 34 is represented.
In addition, in figure 3, the mode each inscape all covered is provided with protective clear layer 37.Protective clear layer 37 can be formed in the mode of the part only covering each inscape.Insulation course 35 can be identical material with protective clear layer 37, also can be different materials.
< capacitive input device and possess the touch panel display device > of capacitive input device
Utilize the capacitive input device that manufacture method of the present invention obtains, and possess above-mentioned capacitive input device as the touch panel display device of inscape can apply " up-to-date touch screen technology " (on July 6th, 2009 issue, Age of Technology (Techno Times) (share)), male two supervisions of three paddy, " technology of touch-screen and exploitation ", CMC publishes (2004, 12), flat-panel monitor international symposium 2009 (FPD International 2009 Forum) T-11 gives a lecture teaching material, the formation disclosed in Cypress Semiconductor Co., Ltd (Cypress Semiconductor Corporation) application guide (Application Note) AN2292 etc.
[embodiment]
Below, embodiment is enumerated to further illustrate the present invention.Only otherwise depart from purport of the present invention, then following the material shown in embodiment, use amount, ratio, contents processing, handling procedure etc. can be suitable for changing.Therefore, scope of the present invention is not limited to concrete example shown below.Moreover as long as in advance without special instruction, then " part ", " % " are quality criteria.
Below in an example, following symbol represents following compound respectively.
MATHF: methacrylic acid 2-tetrahydrofuran ester (composite)
OXE-30: methacrylic acid (3-Ethyloxetane-3-base) methyl esters (Osaka Organic Chemical Industry (share) manufacture)
HEMA: 2-hydroxyethyl methacrylate (manufacturing with the pure pharmaceutical worker's industry (share) of light)
GMA: glycidyl methacrylate (manufacturing with the pure pharmaceutical worker's industry (share) of light)
MAA: methacrylic acid (manufacturing with the pure pharmaceutical worker's industry (share) of light)
MMA: methyl methacrylate (manufacturing with the pure pharmaceutical worker's industry (share) of light)
St: styrene (manufacturing with the pure pharmaceutical worker's industry (share) of light)
V-601: dimethyl 2,2 '-azo two (propionic acid 2-methyl esters) (manufacturing with the pure pharmaceutical worker's industry (share) of light)
PGMEA: propylene glycol methyl ether acetate
The synthesis > of <MATHF
First methacrylic acid (86g, 1mol) is cooled to 15 DEG C, then adds camphorsulfonic acid (4.6g, 0.02mol).2-dihydrofuran (71g, 1mol, 1.0 equivalents) is dripped in this solution.Stir after 1 hour, add saturated sodium bicarbonate (500mL), and utilize ethyl acetate (500mL) to extract, after utilizing magnesium sulfate to carry out drying, insolubles is filtered, then below 40 DEG C, reduced pressure concentration is carried out, decompression distillation is carried out to the yellow oil of residue, and obtains methacrylic acid tetrahydrofuran-2-base ester (MATHF) 125g (productive rate is 80%) as boiling point (bp.) 54 DEG C ~ 56 DEG C/3.5mmHg cut of colorless oil.
The preparation > of < dispersion liquid D1
The dispersion liquid of following composition is concocted, and make itself and zirconium oxide bead (0.05mm φ: YTZ ball, Ni Kate (Nikkato) (share) manufactures) 1,700 parts of mixing, use super Ah's Orion Pax grinding machine (Ultra Apex Mill) UMA-0.15 (longevity industry (share) manufacture), carry out dispersion in 3 hours with the peripheral speed of 12m/min.Leaching zirconium oxide bead (0.05mm φ), and obtain dispersion liquid D1.
Titania (stone originates in industry (share) manufacture, trade name: TTO-51 (C), average primary particle diameter: 10nm ~ 30nm): 187.5 parts
Spreading agent (Di Sipabike (DISPERBYK)-111 (spreading agent, the 30%PGMEA solution that Japanese Bi Ke chemistry (share) manufactures): 220.0 parts
Solvent PGMEA (propylene glycol methyl ether acetate): 342.5 parts
The preparation > of < dispersion liquid D2 and dispersion liquid D3
Described in Titanium particles and spreading agent being replaced to respectively in table 1, in addition, prepare in the mode identical with dispersion liquid D1, and obtain dispersion liquid D2 and dispersion liquid D3 respectively.
The preparation > of < dispersion liquid D4
Zirconium oxide bead is replaced to the zirconium oxide bead of 0.1mm φ, in addition, disperse in the mode identical with dispersion liquid D3, and obtain dispersion liquid D4.
[table 1]
| Dispersion liquid | Inorganic particulate | Spreading agent | Pearl diameter |
| D1 | TTO-51(C) | The 30%PGMEA solution of Di Sipabike (DISPERBYK)-111 | 0.05mm |
| D2 | TTO-51(C) | The 30%PGMEA solution of compound 1 | 0.05mm |
| D3 | TTO-51(A) | The 30%PGMEA solution of compound 1 | 0.05mm |
| D4 | TTO-51(A) | The 30%PGMEA solution of compound 1 | 0.1mm |
Moreover the contracted notation other than the above used in the dispersion liquid recorded in table 1 is as follows.
Compound 1 described in table 1 is following compound, Mw=3,300." l in the formula of compound 1
1", " l
2", " m
1" and " m
2" represent respectively and on average replace number.In addition, compound 1 synthesizes with reference to method described in Japanese Patent Laid-Open 2007-277514 publication.
TTO-51 (A): titania, stone originates in industry (share) manufacture, average primary particle diameter: 10nm ~ 30nm
[changing 51]
The synthesis > of < polymer P 1
Under stream of nitrogen gas, methacrylic acid tetrahydrofuran-2-base ester (0.405 molar equivalent), 2-hydroxyethyl methacrylate (0.125 molar equivalent), methacrylic acid (0.095 molar equivalent), methacrylic acid (3-Ethyloxetane-3-base) methyl esters (0.375 molar equivalent) of 100 parts will be added up to, and the mixed solution of propylene glycol methyl ether acetate (PGMEA) (120 parts) is heated to 70 DEG C.One side stirs this mixed solution, one side is lasted 3.5 hours and is dripped radical polymerization initiator V-601 (dimethyl 2,2 '-azo two (propionic acid 2-methyl esters)), manufacture with the pure pharmaceutical worker's industry (share) of light, 12.0 parts) and the mixed solution of PGMEA (80 parts).After dropping terminates, at 70 DEG C, carry out reaction in 2 hours, obtain the PGMEA solution of polymer P 1 thus.And then solid component concentration is adjusted to 40 quality % by interpolation PGMEA.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polymer P 1 obtained is 15,000.
The synthesis > of < polymer P 2 and polymer P 3
Be altered to except following monomer composition except by monomer composition, utilize the method identical with polymer P 1 to obtain the PGMEA solution of polymer P 2, polymer P 3 respectively.And then solid component concentration is adjusted to 40 quality % by interpolation PGMEA.
The Mw measured by GPC of the polymer P 2 obtained is 15,000, and the weight average molecular weight Mw measured by GPC of the polymer P 3 obtained is 15,000.
[table 2]
(embodiment 1)
The preparation > of < photosensitive polymer combination
Carry out allocating with following composition, mix and after making uniform solution, use the tygon filtrator with the aperture of 0.2 μm to filter, and make the photosensitive polymer combination of embodiment 1.
Propylene glycol methyl ether acetate (PGMEA): 127.7 parts
The 0.2%PGMEA solution of following compound (Japan changes into industry (share) manufacture, CMTU): 30.0 parts
The 30%PGMEA solution of polymer P 1: 191.3 parts
Light acid producing agent B-1 (following compound): 6.0 parts
Following EP-1:15.0 part
Non-ionic surfactant (F-554, Di Aisheng (share) manufacture, 2.0%PGMEA solution) containing perfluoroalkyl: 30.0 parts
Dispersion liquid D1:600.0 part
[changing 52]
[changing 53]
(embodiment 2 ~ embodiment 11 and comparative example 1 ~ comparative example 4)
The preparation > of < photosensitive polymer combination
Described in dispersion liquid, polymkeric substance and/or composition B being replaced to respectively in table 3, in addition, prepare in the same manner as example 1, and obtain the photosensitive polymer combination of embodiment 2 ~ embodiment 11 and comparative example 1 ~ comparative example 4 respectively.
(embodiment 12)
The preparation > of < photosensitive polymer combination
Carry out allocating with following composition, mix and after making uniform solution, use the tygon filtrator with the aperture of 0.2 μm to filter, and make the photosensitive polymer combination of embodiment 12.
Propylene glycol methyl ether acetate (PGMEA): 105.3 parts
The 0.2%PGMEA solution of following compound (Japan changes into industry (share) manufacture, CMTU): 30.0 parts
The 30%PGMEA solution of polymer P 1: 191.3 parts
Light acid producing agent B-1 (following compound): 6.0 parts
EP-8 (diethylene glycol ethyl methyl ether 40% solution): 37.5 parts
Non-ionic surfactant (F-554, Di Aisheng (share) manufacture, 2.0%PGMEA solution) containing perfluoroalkyl: 30.0 parts
Dispersion liquid D1:600.0 part
-evaluate-
Method shown below is utilized to carry out the photosensitive polymer combination obtained in Evaluation operation example 1 ~ embodiment 12 and comparative example 1 ~ comparative example 4 respectively.Evaluation result is gathered and is shown in Table 3.
The evaluation > of < refractive index
Use spinner to be coated on silicon wafer substrate by obtained photosensitive polymer combination, and at 80 DEG C, carry out drying in 120 seconds, form the film that thickness is 0.5 μm thus.Use extra-high-pressure mercury vapour lamp, with 200mJ/cm
2(utilizing i ray to measure), to this base board to explosure, thereafter, utilizes baking oven to heat 60 minutes at 230 DEG C.
Use ellipsometer VUV-VASE (Japanese J.A. fertile blue (J.A.Woollam Japan) (share) manufactures), measure the refractive index of the cured film under 589nm.Refractive index is more high more preferred, is more preferably more than 1.70.
The evaluation > of < yellow coloring
Use spinner to be coated on silicon wafer substrate by obtained photosensitive polymer combination, and at 80 DEG C, carry out drying in 120 seconds, form the film that thickness is 2 μm thus.Use extra-high-pressure mercury vapour lamp, with 200mJ/cm
2(utilizing i ray to measure), to this base board to explosure, thereafter, utilizes baking oven to heat 60 minutes at 230 DEG C.
Sense evaluation is carried out with the visual coloring case to obtained substrate.Metewand is as follows.
1: non-coloring or almost can't see painted.
2: slightly can see the painted of yellow.
3: the painted of yellow can be seen.
The evaluation > of < mist degree (transparency)
Utilize spin coater to be coated by obtained photosensitive polymer combination on the glass substrate (trade name: XG, Corning Incorporated manufactures) of 100mm × 100mm, and carry out on the heating plate of 80 DEG C 120 seconds dry (prebake conditions).Secondly, ghi ray high-pressure mercury-vapor lamp exposure machine is used, with energy intensity 20mW/cm
2, accumulative light quantity 200mJ/cm
2carry out blanket exposure.And then, implement within 45 minutes, to heat (toasting afterwards) to coated film in the baking oven of 220 DEG C.Thickness adjusts initial coating film thickness in the mode becoming 1 μm after rear baking.For the mist degree of the sample after rear baking, utilize the NDH-5000 that Japanese electric look industry (share) manufactures, make face upwards, and measure mist degree (haze value) according to plastic products test method (JIS K7136JIS K7361ASTM D1003).
Moreover, so-called haze value, refer to by diffuse transmission light for full light therethrough light ratio (%) represented by value.Haze value is less, represents that the transparency is higher.
1: haze value is less than 0.5%.
2: haze value is more than 0.5%, less than 1.0%.
3: haze value is more than 1.0%, less than 3.0%.
4: haze value is more than 3.0%, less than 5.0%.
5: haze value is more than 5.0%.
The evaluation > of < chemical-resistant
Use spinner to be coated on silicon wafer substrate by obtained photosensitive polymer combination, and at 80 DEG C, carry out drying in 120 seconds, form the film that thickness is 2 μm thus.Use extra-high-pressure mercury vapour lamp, with 200mJ/cm
2(utilizing i ray to measure), to this base board to explosure, thereafter, utilizes baking oven to heat 60 minutes at 230 DEG C.
Obtained substrate is flooded 8 minutes in the PGMEA of 24 DEG C, and measures the Thickness Variation before and after dipping.
1: Thickness Variation is less than 1%.
2: Thickness Variation is more than 1%, less than 3%.
3: Thickness Variation is more than 3%.
The evaluation > of <ITO pattern observability
In advance in the glass substrate (trade name: XG of 100mm × 100mm, Corning Incorporated manufactures) the upper pattern forming ITO, then the mode utilizing spin coater to become 1.0 μm with thickness is coated with obtained photosensitive polymer combination, and carries out on the heating plate of 80 DEG C 120 seconds dry (prebake conditions).
Secondly, ghi ray high-pressure mercury-vapor lamp exposure machine is used, with energy intensity 20mW/cm
2, accumulative light quantity 200mJ/cm
2the whole face of substrate is exposed.
Then, heat 60 minutes at 230 DEG C and the desciccator diaphragm of photonasty group resin combination is set on ITO pattern.In bright indoor, one side makes obtained substrate inclination one side observe with naked eyes, and compares with when not arranging photosensitive polymer combination on ITO pattern, and carries out the evaluation of observability.Moreover metewand is that the pattern of ITO is more in sight better.1 or 2 is usage range.
1: the pattern that roughly can't see ITO.
2: the pattern indistinctly can seeing ITO.
3: the pattern that can be clear that ITO.
[table 3]
As shown in table 3, the refractive index of photosensitive polymer combination of the present invention is high, painted less, chemical-resistant is also good, and in addition, the observability of ITO pattern is also good.
Moreover EP-1 ~ EP-8 described in table 3 is compound shown below.
EP-1: above-mentioned EP-1, long rapids Dai Nake (Denacol) EX-216L changing into (Nagase chemteX) (share) and manufacture
EP-2: above-mentioned EP-2, long rapids Dai Nake (Denacol) EX-411L changing into (share) and manufacture
EP-3: above-mentioned EP-3, Sai Luo West Germany (Celloxide) 2021P that Daicel (Daicel) chemical industry (share) manufactures
EP-4: above-mentioned EP-4, the OXT-221 that East Asia synthesis (share) manufactures
EP-5: above-mentioned EP-5, Yin Tenake (ETERNACOLL) OXBP that space portion emerging product (share) manufactures
EP-6: above-mentioned EP-6, long rapids Dai Nake (Denacol) EX-214L changing into (share) and manufacture
EP-7: the potpourri of above-mentioned EP-7-1 and above-mentioned EP-7-2, long rapids Dai Nake (Denacol) EX-321L changing into (share) and manufacture
EP-8: 40 quality % diethylene glycol ethyl methyl ether (MEDG) solution of poly (glycidyl methacrylate), utilizes the composite of following shown method gained
EP-9: following compound, the jER-157 that Mitsubishi Chemical's (share) manufactures
EP-10: following compound, the jER-1007 that Mitsubishi Chemical's (share) manufactures
The HP-4032D that EP-11: following compound, Di Aisheng (share) manufacture
The synthesis > of <EP-8
Under stream of nitrogen gas, the mixed solution of 100 parts, methyl propenoic acid glycidyl ether and diethylene glycol ethyl methyl ether (MEDG) 120 parts is heated to 70 DEG C.One side stirs this mixed solution, one side is lasted 3.5 hours and is dripped radical polymerization initiator V-601 (dimethyl 2,2 '-azo two (propionic acid 2-methyl esters)), manufacture with the pure pharmaceutical worker's industry (share) of light, 20.0 parts) and the mixed solution of MEDG (80 parts).After dropping terminates, at 60 DEG C, carry out reaction in 2 hours, obtain the MEDG solution of EP-8 thus.And then solid component concentration is adjusted to 40 quality % by interpolation PGMEA.The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the EP-8 obtained is 5,000.
[changing 54]
[changing 55]
(embodiment 13)
In active array type LCD described in Fig. 1 of Jap.P. No. 3321003 publication, form cured film 17 as follows as interlayer dielectric, and obtain the liquid crystal indicator of embodiment 13.That is, the photosensitive polymer combination of embodiment 1 is spun on substrate, after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, uses high-pressure mercury-vapor lamp to irradiate 45mJ/cm on mask
2(energy illumination is 20mW/cm
2) i ray (365nm), then utilize alkaline aqueous solution to carry out developing and forming pattern, and carry out the heating of 30 minutes at 230 DEG C, and form cured film 17 as interlayer dielectric.
Apply the result of driving voltage to obtained liquid crystal indicator, known its be show good display characteristic and the high liquid crystal indicator of reliability.
(embodiment 14)
Utilize following method to make the organic EL display (with reference to Fig. 2) using thin film transistor (TFT) (TFT).
Glass substrate 6 is formed the TFT1 of bottom gate polar form, and formation comprises Si under the state covering this TFT1
3n
4dielectric film 3.Then, this dielectric film 3 is formed after explanations are omitted hering illustrated contact hole, form the distribution 2 (being highly 1.0 μm) being connected to TFT1 via this contact hole face on the insulating film 3.This distribution 2 is the lines in order to will be connected with TFT1 between TFT1 or by the organic EL formed in step thereafter.
And then, in order to make to form produced concavo-convex planarization by distribution 2, imbedding under the concavo-convex state produced by distribution 2, on dielectric film 3, form planarization film 4.Formation towards the planarization film 4 on dielectric film 3 is spun on substrate by the photosensitive polymer combination of embodiment 1, after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, uses high-pressure mercury-vapor lamp to irradiate 45mJ/cm on mask
2(energy intensity is 20mW/cm
2) i ray (365nm), then utilize alkaline aqueous solution to carry out developing and forming pattern, and carry out the heating of 30 minutes at 230 DEG C.
Coating during photosensitive resin coating composition is good, in the cured film obtained, does not see the generation of gauffer or slight crack after exposure, development, calcining.And then the average jump of distribution 2 is 500nm, the thickness of made planarization film 4 is 2,000nm.
Then, obtained planarization film 4 is formed the organic EL of bottom emission type.First, the first electrode 5 comprising ITO is made to be connected to distribution 2 via contact hole 7 and to be formed on planarization film 4.Thereafter, painting erosion resistant agent, and carry out prebake conditions, the mask across desired pattern exposes, and then develops.Using this Resist patterns as mask, carry out pattern processing by using the Wet-type etching of ITO etchant.Thereafter, at 50 DEG C, use anticorrosive additive stripping liquid controlling (remover (Remover) 100, peace intelligence electronic material (AZ Electronic Materials) company manufactures) to be peeled off by above-mentioned Resist patterns.The first electrode 5 obtained in the above described manner is equivalent to the anode of organic EL.
Then, the dielectric film 8 of the shape of the periphery of covering first electrode 5 is formed.The photosensitive polymer combination of embodiment 1 is used for dielectric film 8, forms dielectric film 8 in the same way as described above.By arranging this dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and step thereafter can be prevented.
And then, in vacuum deposition apparatus, carry out evaporation successively to arrange hole transmission layer, organic luminous layer, electron transfer layer across desired pattern mask.Then, whole of surface forms the second electrode comprising Al.In evaporator, taking out obtained aforesaid substrate, being undertaken fitting sealing by using ultraviolet ray hardening type epoxy resin and glass for sealing plate.
As described above, the organic EL display connecting the active array type in order to the TFT1 driven it on each organic EL is obtained.Execute alive result via driving circuit, known its is manifest good display characteristic and the high organic EL display of reliability.
(embodiment 15)
Utilize the method for the following stated, and use the hardening resin material of high index of refraction of the present invention to make touch panel display device.
The formation > of < first transparent electrode pattern
[formation of transparent electrode layer]
The front panel of the intensive treatment glass (300mm × 400mm × 0.7mm) being formed with mask layer is in advance directed in vacuum chamber, uses SnO
2containing ratio is the ITO target (indium: tin=95: 5 (mol ratios)) of 10 quality %, by direct current (DirectCurrent, DC) magnetic control sputtering plating (condition: the temperature of base material is 250 DEG C, argon pressure is 0.13Pa, oxygen pressure is 0.01Pa) form the ito thin film that thickness is 40nm, and obtain the front panel being formed with transparent electrode layer.The surface resistance of ito thin film is 80 Ω/.
Then, commercially available etching resist to be coated on ITO and to carry out drying, and forming etching resist layer.Exposed mask (having the quartzy exposed mask of the transparent electrode pattern) distance between face and above-mentioned etching resist layer is set as 100 μm, with 50mJ/cm
2after the exposure of (i ray) carries out pattern exposure, utilize special developer solution to develop, and then at 130 DEG C, carry out the rear baking process of 30 minutes, and obtain the front panel being formed with transparent electrode layer and etching ray hardening resin layer pattern.
The front panel being formed with transparent electrode layer and etching ray hardening resin layer pattern is made to impregnated in add and have ITO etchant (hydrochloric acid, potassium chloride solution; Liquid temperature is 30 DEG C) etching bath in, carry out process in 100 seconds, the transparent electrode layer in region exposed not covered by etching resist layer dissolves to be removed, and obtains the front panel with the transparency electrode layer pattern with etching resist layer pattern.
Then, make the front panel with the transparency electrode layer pattern with etching resist layer pattern impregnated in special anticorrosive additive stripping liquid controlling, etching ray hardening resin layer is removed, and obtains the front panel being formed with mask layer and the first transparent electrode pattern.
[formation of insulation course]
The photosensitive polymer combination of embodiment 1 to be coated on the front panel being formed with mask layer and the first transparent electrode pattern and to carry out drying (thickness is 1 μm, 90 DEG C, 120 seconds), and obtaining photosensitive polymer combination layer.Exposed mask (having the quartzy exposed mask curtain of the transparent electrode pattern) distance between face and above-mentioned photosensitive polymer combination layer is set as 30 μm, with 50mJ/cm
2the exposure of (i ray) carries out pattern exposure.
Then, at 23 DEG C, by 2.38 quality % tetramethyl ammonium hydroxide aqueous solution and utilize leaching to cover liquid method to carry out development in 15 seconds, and then utilize ultrapure water to carry out drip washing in 10 seconds.Then, at 220 DEG C, carry out the rear baking process of 45 minutes, and obtain the front panel being formed with mask layer, the first transparent electrode pattern, insulating layer pattern.
The formation > of < second transparent electrode pattern
[formation of transparent electrode layer]
DC magnetic control sputtering plating process (condition: the temperature of base material is 50 DEG C is carried out to the front panel till being formed to insulating layer pattern in the mode identical with the formation of above-mentioned first transparent electrode pattern, argon pressure is 0.13Pa, oxygen pressure is 0.01Pa), forming thickness is the ito thin film of 80nm, and obtains the front panel being formed with transparent electrode layer.The surface resistance of ito thin film is 110 Ω/.
In the mode that the formation of the formation with the first transparent electrode pattern is identical, the front panel of the insulating layer pattern using commercially available etching resist acquisition to be formed with the first transparent electrode pattern, to utilize the photosensitive polymer combination of embodiment 1 to be formed, transparent electrode layer, etching Resist patterns (toasts process afterwards; 130 DEG C, 30 minutes).
And then, etch in the mode that the formation of the formation with the first transparent electrode pattern is identical, and remove etching resist layer, obtain the front panel being formed with mask layer, the first transparent electrode pattern, the insulating layer pattern utilizing the photosensitive polymer combination of embodiment 1 to be formed, the second transparent electrode pattern thus.
The formation > of the electric conductivity key element that < is different from the first transparent electrode pattern and the second transparent electrode pattern
In the mode identical with the formation of above-mentioned first transparent electrode pattern and the second transparent electrode pattern, the process of DC magnetic control sputtering plating is carried out to the front panel of the insulating layer pattern being formed with the first transparent electrode pattern, utilize the photosensitive polymer combination of embodiment 1 to be formed, the second transparent electrode pattern, and obtains the front panel being formed with aluminium (Al) film that thickness is 200nm.
In the mode identical with the formation of above-mentioned first transparent electrode pattern and the second transparent electrode pattern, the front panel of the insulating layer pattern using commercially available etching resist acquisition to be formed with the first transparent electrode pattern, to utilize the photosensitive polymer combination of embodiment 1 to be formed, the second transparent electrode pattern, etching Resist patterns.(toast process afterwards; 130 DEG C, 30 minutes).
And then, carry out etching (30 DEG C, 50 seconds) in the mode that the formation of the formation with the first transparent electrode pattern is identical, and resist layer removal (45 DEG C, 200 seconds) will be etched, obtain the front panel being formed with mask layer, the first transparent electrode pattern, the insulating layer pattern utilizing the photosensitive polymer combination of embodiment 1 to be formed, the second transparent electrode pattern, the electric conductivity key element different from the first transparent electrode pattern and the second transparent electrode pattern thus.
The formation > of < protective clear layer
Be formed in the mode identical from the formation of insulation course with above-mentioned first transparent electrode pattern and the different electric conductivity key element of the second transparent electrode pattern till front panel on, the photosensitive polymer combination of coating Examples 1 also carries out drying (thickness is 1 μm, 90 DEG C, 120 seconds), and obtain photosensitive polymer combination film.And then, not across exposed mask with 50mJ/cm
2the exposure of (i ray) carries out preceding exposure, then carries out developing, post-exposure (1,000mJ/cm
2), rear baking process; and obtaining the front panel of the stacked insulation course (protective clear layer) utilizing the photosensitive polymer combination of embodiment 1 to be formed as follows, which is mode mask layer, the first transparent electrode pattern, the insulating layer pattern utilizing the photosensitive polymer combination of embodiment 1 to be formed, the second transparent electrode pattern, the electric conductivity key element different from the first transparent electrode pattern and the second transparent electrode pattern all covered.
The making > of < image display device (touch-screen)
Utilizing the front panel that the liquid crystal display cells manufactured by the method recorded in Japanese Patent Laid-Open 2009-47936 publication manufactures before laminating, utilizing known method to make and possess the image display device of capacitive input device as inscape.
The evaluation > of < front panel and image display device
First transparent electrode pattern, the second transparent electrode pattern and the electric conductivity key element electric conductivity separately different from two do not have problems, on the other hand, between first transparent electrode pattern and the second transparent electrode pattern, there is insulativity, as touch-screen, obtain good display characteristic.And then, the first transparent electrode pattern and the second transparent electrode pattern not easily in sight, obtain the image display device of display characteristic excellence.
The explanation of symbol
1:TFT (thin film transistor (TFT))
2: distribution
3: dielectric film
4: planarization film
5: the first electrodes
6: glass substrate
7: contact hole
8: dielectric film
10: liquid crystal indicator
12: back light unit
14,15: glass substrate
16：TFT
17: cured film
18: contact hole
19:ITO transparency electrode
20: liquid crystal
22: colored filter
30: capacitive input device
31: front panel
32: mask layer
33: the first transparent electrode patterns
33a: pad part
33b: coupling part
34: the second transparent electrode patterns
35: insulation course
36: electric conductivity key element
37: protective clear layer
38: peristome
X: first direction
Y: second direction
Claims (15)
1. a photosensitive polymer combination, is characterized in that comprising:
(composition A) containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base,
(composition B) does not have aromatic series ehter bond and phenolic group and has the compound of epoxy radicals and/or oxetanylmethoxy,
(composition C) metal oxide particle,
(components D) light acid producing agent, and
(composition E) solvent.
2. photosensitive polymer combination according to claim 1, wherein composition C is Titanium particles or Zirconia particles.
3. photosensitive polymer combination according to claim 1 and 2, it also comprises (composition F) spreading agent.
4. photosensitive polymer combination according to claim 3, wherein composition F contains the spreading agent with at least one acidic group.
5. photosensitive polymer combination according to claim 4, wherein composition F contains by following formula (S) expression and has the spreading agent of at least one acidic group,
(in formula (S), R
3represent the concatenating group of (m+n) valency, R
4and R
5separately represent the concatenating group of singly-bound or divalence, A
2represent the organic group of the monovalence containing the following part-structure of at least one, the group that alkyl, alkoxysilane group, epoxy radicals, isocyanate group and hydroxyl that it is more than 4 that described part-structure is 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 form, n A
2, R
4can be identical, also can be different, m represents that 0 ~ 8, n represents that 2 ~ 9, m+n is 3 ~ 10, P
2represent macromolecular scaffold, m P
2, R
5can be identical, also can be different).
6. photosensitive polymer combination according to any one of claim 1 to 5, wherein said have the Component units of the base that acidic group is protected by sour decomposability base for the Component units represented by following formula,
(in formula, R
121represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, L
1represent carbonyl or phenylene, R
122~ R
128separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4).
7. photosensitive polymer combination according to any one of claim 1 to 6, wherein components D is oxime sulfonate compounds.
8. a manufacture method for hardening thing, is characterized in that: comprise step (a) ~ step (c) at least successively:
A () application step, coats on substrate by photosensitive polymer combination according to any one of claim 1 to 7;
B () solvent removal step, removes solvent in the resin combination be coated with; And
C () heat treatment step, heat-treats the resin combination eliminating solvent.
9. a resin pattern manufacture method, is characterized in that: comprise step (1) ~ step (5) at least successively:
(1) application step, coats on substrate by photosensitive polymer combination according to any one of claim 1 to 7;
(2) solvent removal step, removes solvent in the resin combination be coated with;
(3) step of exposure, utilizes actinic ray that the resin combination eliminating solvent is exposed into pattern-like;
(4) development step, utilizes aqueous developer solution to develop to the resin combination through exposure; And
(5) heat treatment step, heat-treats the resin combination through development.
10. a hardening thing, it utilizes the manufacture method of hardening thing according to claim 8 or resin pattern manufacture method according to claim 9 and obtains.
11. 1 kinds of cured films, it makes photosensitive polymer combination according to any one of claim 1 to 7 harden and be formed.
12. cured films according to claim 11, it is interlayer dielectric.
13. 1 kinds of liquid crystal indicators, it comprises the cured film according to claim 11 or 12.
14. 1 kinds of organic electroluminescence display device and method of manufacturing same, it comprises the cured film according to claim 11 or 12.
15. 1 kinds of touch panel display devices, it comprises the cured film according to claim 11 or 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-236402 | 2012-10-26 | ||
| JP2012236402 | 2012-10-26 | ||
| PCT/JP2013/078767 WO2014065352A1 (en) | 2012-10-26 | 2013-10-24 | Photosensitive resin composition, cured product and manufacturing method thereof, resin pattern production method, cured film, organic el display device, liquid crystal display device, and touch panel display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104756010A true CN104756010A (en) | 2015-07-01 |
| CN104756010B CN104756010B (en) | 2019-07-30 |
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|---|---|---|---|
| CN201380055865.1A Expired - Fee Related CN104756010B (en) | 2012-10-26 | 2013-10-24 | Photosensitive polymer combination, hardening thing and its manufacturing method, resin pattern manufacturing method, cured film and its application |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6012750B2 (en) |
| CN (1) | CN104756010B (en) |
| TW (1) | TWI637236B (en) |
| WO (1) | WO2014065352A1 (en) |
Cited By (2)
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| CN107728428A (en) * | 2016-08-11 | 2018-02-23 | 东友精细化工有限公司 | Chemical amplification type photosensitive polymer combination and the dielectric film being produced from it |
| CN113574684A (en) * | 2019-03-19 | 2021-10-29 | 柯尼卡美能达株式会社 | LED light-emitting device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102408329B1 (en) * | 2016-01-08 | 2022-06-10 | 동우 화인켐 주식회사 | Film Touch Sensor and Method for Fabricating the Same |
| TW201908362A (en) * | 2017-06-15 | 2019-03-01 | 學校法人東京理科大學 | Curable resin composition, cured product, concave-convex structure and manufacturing method thereof |
| KR102300781B1 (en) * | 2017-08-31 | 2021-09-10 | 후지필름 가부시키가이샤 | Curable composition, hardened|cured material, color filter, manufacturing method of a color filter, solid-state image sensor, and image display apparatus |
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Also Published As
| Publication number | Publication date |
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| TW201423266A (en) | 2014-06-16 |
| WO2014065352A1 (en) | 2014-05-01 |
| JPWO2014065352A1 (en) | 2016-09-08 |
| JP6012750B2 (en) | 2016-10-25 |
| CN104756010B (en) | 2019-07-30 |
| TWI637236B (en) | 2018-10-01 |
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