CN105467640A - Manufacturing method for display panel substrate, display panel substrate, and touch panel display device - Google Patents

Manufacturing method for display panel substrate, display panel substrate, and touch panel display device Download PDF

Info

Publication number
CN105467640A
CN105467640A CN201510639546.6A CN201510639546A CN105467640A CN 105467640 A CN105467640 A CN 105467640A CN 201510639546 A CN201510639546 A CN 201510639546A CN 105467640 A CN105467640 A CN 105467640A
Authority
CN
China
Prior art keywords
composition
quality
photosensitive composite
substrate
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510639546.6A
Other languages
Chinese (zh)
Inventor
真崎庆央
安藤豪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN105467640A publication Critical patent/CN105467640A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/40—OLEDs integrated with touch screens

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Materials For Photolithography (AREA)
  • Position Input By Displaying (AREA)

Abstract

An objective of the invention is to provide a manufacturing method for a display panel substrate, a display panel substrate, and a touch panel display device, and the display panel substrate has micro concave-convex planarization of the surface of a display device, substrate tracking ability, and a protective film in excellent pencil hardness. The manufacturing method for a display panel substrate comprises: process 1, coating a photosensitive composition on the surface of a display panel, the surface being provided with a touch detection electrode; process 2, removing a solvent from the coated photosensitive composition; and process 3, through light and/or heat, hardening the photosensitive composition whose solvent is removed.

Description

The manufacture method of panel substrate, panel substrate and touch panel display device
Technical field
The present invention relates to a kind of manufacture method of panel substrate, panel substrate and touch panel display device.
Background technology
The flat-panel monitors (flatpaneldisplay) such as liquid crystal indicator, organic electroluminescent (Electroluminescence, EL) display device are widely used.
When manufacturing panel substrate, carrying out following operation: under the state being formed with electrode on the surface of the glass substrate had at display panel, be coated with curable adhensive compositions, forming diaphragm.
As the formation method of this diaphragm, the method recorded in known patent document 1 or patent documentation 2.
In addition, in recent years according to the lightweight of these displays and the requirement of slimming, carry out the operation that the glass substrate forming liquid crystal display is ground always.
[prior art document]
[patent documentation]
[patent documentation 1] Jap.P. No. 5201066 publication
[patent documentation 2] Jap.P. No. 5423004 publication
Summary of the invention
[invention institute for solution problem]
But the composition recorded in patent documentation 1 or patent documentation 2 is insufficient from the viewpoint of the smooth voltinism of the micro concavo-convex on surface, substrate tracing ability and pencil hardness.
The present invention be to provide a kind of manufacture method of panel substrate of diaphragm of the smooth voltinism of micro concavo-convex, substrate tracing ability and the pencil hardness excellence that possess surface for the problem solved, by the panel substrate manufactured by described manufacture method and the touch panel display device possessing described panel substrate.
[technological means of dealing with problems]
Described problem of the present invention is solved by the means described in following <1>, <5> or <6>.Be recorded in down together with <2> ~ <4> preferably.
The manufacture method of a <1> panel substrate, is characterized in that comprising successively: as the painting process possessed on the face touching detecting electrode photosensitive composite being coated on display panel of operation 1, as the solvent removal step removing desolventizing from be coated with photosensitive composite of operation 2, and as operation 3 by light and/or heat make through solvent removing photosensitive composite sclerosis hardening process, and described photosensitive composite contains as above (methyl) acrylate compounds of the face energy of composition A, as the Photoepolymerizationinitiater initiater of composition B, as organic filler or the inorganic particulate of composition C, and as the solvent of components D, relative to the total solid component amount beyond the composition C in photosensitive composite, the content of composition A is 50 quality % ~ 98 quality %, the viscosity of photosensitive composite is 3mPas ~ 30mPas, the surface tension of photosensitive composite is 20mN/m ~ 30mN/m, be 10 quality % ~ 50 quality % relative to the solid constituent amount of photosensitive composite total amount, and described display panel possesses touch detecting electrode at least one side, have touch detecting electrode face at least partially on possess the glass substrate of below thickness 0.3mm or the resin substrate of below thickness 1.0mm, the thickness of described touch detecting electrode is more than 30nm.
The manufacture method of the panel substrate of <2> described in <1>, wherein said photosensitive composite also contains surfactant as composition E.
The manufacture method of the panel substrate of <3> described in <1> or <2>, wherein fixes display panel by absorption in painting process.
The manufacture method of the panel substrate that <4> is described any one of <1> to <3>, be wherein glass substrate at the substrate possessed of going up at least partially in the face with described touch detecting electrode, and before described painting process, also comprise thinning (slimming) operation that glass substrate is ground.
<5> panel substrate, it is manufactured by the manufacture method of panel substrate described any one of <1> to <4>.
<6> touch panel display device, possesses the panel substrate described in <5>.
[effect of invention]
According to the present invention; a kind of manufacture method of panel substrate of diaphragm of the smooth voltinism of micro concavo-convex, substrate tracing ability and the pencil hardness excellence that possess display device surface can be provided, by the panel substrate manufactured by described manufacture method and the touch panel display device possessing described panel substrate.
Accompanying drawing explanation
Fig. 1 (a), Fig. 1 (b) represent the concept map of an example of panel substrate when being coated with photosensitive composite.
Fig. 2 represents the formation concept map of an example of liquid crystal indicator.And the schematic sectional view of active matrix (activematrix) substrate in expression liquid crystal indicator, there is the cured film 17 as interlayer dielectric.
Fig. 3 represents the formation concept map of an example of organic EL display.And represent the schematic sectional view of the substrate in the organic EL display of bottom-emission (bottomemission) type, there is planarization film 4.
Fig. 4 represents the formation concept map of an example of the liquid crystal indicator of the function with touch panel.
Fig. 5 represents the formation concept map of another example of the liquid crystal indicator of the function with touch panel.
Description of reference numerals
1,16,440:TFT (thin film transistor (TFT))
2: wiring
3,8,280: dielectric film
4: planarization film
5: the first electrodes
6,14,15: glass substrate
7,18,282: contact hole
10: liquid crystal indicator
12: back light unit
17: cured film
19:ITO transparency electrode
20: liquid crystal
22,122,330: colored filter
30: touch detecting electrode
32,126,420: protective seam
34: glass substrate
36: fine is concavo-convex
110: pixel substrate
111,128: Polarizer
112,123: transparency carrier
113,370: common electrode
114: insulation course
115: pixel electrode
116,121,350: alignment films
120: substrate in opposite directions
124: phase retardation film
125: sensing detecting electrode
127: following layer
130: detecting means
140,400: liquid crystal layer
200: bottom display board
210: the 1 insulated substrates
220: gate electrode
240: gate insulating film
250: semiconductor layer
260,262: ohmic contact layer
270: source electrode
272: drain electrode
290: pixel electrode
300: top display board
310: the 2 insulated substrates
320: light obstructing member
410: sensing electrode
430: drive electrode
Embodiment
Below, content of the present invention is described in detail.The explanation of the constitutive requirements below recorded is carry out according to representative embodiment of the present invention sometimes, but the present invention is not limited to this embodiment.In addition, in instructions of the present invention, so-called " ~ " comprises numerical value described before and after it to use as the connotation of lower limit and higher limit.In addition, in the present invention, so-called organic EL, refers to organic electroluminescent device.
In the statement of the group (atomic group) in this instructions, do not record the statement being substituted and being unsubstituted and comprise not there is substituent group, and comprise yet there is substituent group.Such as so-called " alkyl ", not only refers to do not have substituent alkyl (alkyl be unsubstituted), and comprises and have substituent alkyl (alkyl be substituted).
In addition; in this instructions; " (methyl) acrylate " represents acrylate and methacrylate, and " (methyl) acrylic acid " represents acrylic acid and methacrylic acid, and " (methyl) acryloyl group " represents acryloyl group and methacryl.
In addition, in the present invention, " quality % " and " % by weight " are synonymous, and " mass parts " and " weight portion " are synonymous.
In addition, in the present invention, the combination of preferred implementation more preferably.
In the present invention, about component of polymer, molecular weight is by with tetrahydrofuran (Tetrahydrofuran, the weight average molecular weight of the polystyrene conversion THF) measured as the gel permeation chromatography (GelPermeationChromatography, GPC) of the situation of solvent.
(manufacture method of panel substrate)
The manufacture method of panel substrate of the present invention comprises successively: as the painting process possessed in touch detecting electrode one side photosensitive composite being coated on display panel of operation 1, as the solvent removal step removing desolventizing from be coated with photosensitive composite of operation 2, and as operation 3 by light and/or heat make through solvent removing photosensitive composite sclerosis hardening process, and described photosensitive composite contains as above (methyl) acrylate compounds of the face energy of composition A, as the Photoepolymerizationinitiater initiater of composition B, as organic filler or the inorganic particulate of composition C, and as the solvent of components D, relative to the total solid component amount beyond the composition C in photosensitive composite, the content of composition A is 50 quality % ~ 98 quality %, the viscosity of photosensitive composite is 3mPas ~ 30mPas, the surface tension of photosensitive composite is 20mN/m ~ 30mN/m, be 10 quality % ~ 50 quality % relative to the solid constituent amount of photosensitive composite total amount, and described display panel possesses touch detecting electrode at least one side, have touch detecting electrode face at least partially on possess the glass substrate of below thickness 0.3mm or the resin substrate of below thickness 1.0mm, the thickness of described touch detecting electrode is more than 30nm.
In recent years, the slimming of display panel or light-weighted requirement strongly, use the glass substrate of slimming or the resin substrate of softness by grinding to manufacture display panel.In addition, when glass substrate, most thickness is below 0.3mm, and when resin substrate, most thickness is below 1.0mm.
But, have thickness be the glass substrate of below 0.3mm panel substrate due to the flexibility of glass substrate high, therefore be coated with photosensitive composite time substrate deformation, produce crooked.In addition, the panel substrate with the resin substrate of below thickness 1.0mm is also because the flexibility of resin substrate is high and produce same problem.
The discoveries such as the present inventor; the substrate of this distortion is coated with photosensitive composite; there is following problem: the composition be coated with does not follow the shape of substrate, the composition before drying is deposited in the crooked part of substrate, and the thickness of diaphragm becomes uneven.
In addition; according to the requirement of the low resistance of touch detecting electrode; the thickness most cases touching detecting electrode is issued to more than 30nm; when being formed with the touch detecting electrode of the thickness with more than 30nm; there is following problem: the concavo-convex surface also affecting protective seam formed by described touch detecting electrode, makes uneven surface.
And then, when using the glass substrate of below thickness 0.3mm, be mostly display panel make the operation of panel after.When being coated with photosensitive composite on a display panel and making it sclerosis after the operation making panel, in order to prevent the loss of the display panel becoming substrate, also require the hardening under low temperature (less than 200 DEG C, as far as possible 180 DEG C below).When using resin substrate, the thermotolerance of substrate self is low and have same problem.
Therefore; the discoveries such as the present inventor; by the content of (methyl) acrylate compounds above for the face energy in photosensitive composite, viscosity and surface tension are set as specific value; even if when using the glass substrate of below thickness 0.3mm or the resin substrate of below thickness 1.0mm and being coated with on the display panel that the thickness touching detecting electrode is such for more than 30nm, the diaphragm of the smooth voltinism of micro concavo-convex, substrate tracing ability and pencil hardness excellence also can be obtained.
With reference to Fig. 1 (a), Fig. 1 (b), content of the present invention is illustrated.
The panel substrate of Fig. 1 (a) manufactured by the manufacture method by panel substrate of the present invention, follows the distortion of glass substrate 34 and is formed with protective seam 32 with uniform thickness.In addition, the surface of glass substrate 34 is formed and touches detecting electrode 30, even if for being formed in the protective seam 32 touched on detecting electrode 30, the micro concavo-convex also planarization on surface.
The display panel of the situation that Fig. 1 (b) is the smooth voltinism of micro concavo-convex and substrate tracing ability difference, protective seam 32 is not followed the distortion of glass substrate 34 and occurs thin part and thick part.In addition, be formed in the surface not planarization of the protective seam 32 touched on detecting electrode 30, and occur fine concavo-convex 36.
< painting process >
The manufacture method of panel substrate of invention comprise photosensitive composite is coated on display panel possess painting process on the face touching detecting electrode as operation 1.
Hereinafter described to photosensitive composite used in the present invention.
[display panel]
Display panel used in the present invention possesses touch detecting electrode at least one side, at least one with the face touching detecting electrode possesses the glass substrate of below thickness 0.3mm or the resin substrate of below thickness 1.0mm, and the thickness of described touch detecting electrode is more than 30nm.
The thickness of described glass substrate is below 0.3mm, preferred below 0.2mm.The method of the thickness of adjustment glass substrate is not particularly limited, and adjusts thickness preferably by aftermentioned thinning operation.
The thickness touching detecting electrode is more than 30nm, preferred more than 40nm, more preferably more than 50nm.By thickness in described scope, the resistance touching detecting electrode can be reduced.
There is no particular restriction for the upper limit, from the viewpoint of the surface after operation later, and preferably 2, below 000nm, more preferably 1, below 000nm, and then more preferably below 300nm, most preferably below 200nm.
From the viewpoint of display characteristic, described touch detecting electrode preferably clear conductive layer.There is no particular restriction for transparency conducting layer, as long as well-known material is formed by the conductive metal as light transmission, such as can preferably enumerate tin indium oxide (IndiumTinOxide, or indium zinc oxide (IndiumZincOxide ITO), IZO), more preferably ITO.
In addition, touch detecting electrode except transparency conducting layer, also can use metal line.The metal that the preferred electric conductivity of metal is high.Such as can illustrate: aluminium, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, silver, tungsten, platinum, gold etc., in addition, also can be the alloy of these metals.Wherein, from the viewpoint of electric conductivity, pattern voltinism and Darkening process easiness, be preferably selected from the metal in the cohort be made up of the alloy of silver, copper, aluminium, titanium, chromium, molybdenum and these metals, more preferably the alloy of silver, copper or these metals, and then preferred silver-colored or copper, particularly preferably copper.By using this metal, the touch detecting electrode that electric conductivity is high can be formed.
In addition, display panel of the present invention preferably has two panels glass substrate or resin substrate, preferably possesses between two panels glass substrate or resin substrate and is used as display panel and the structure playing function.
As long as display panel of the present invention is the panel for showing, be then not particularly limited, preferred liquid crystal panel or organic EL panel.
When display panel of the present invention is liquid crystal panel, more preferably also there is colored filter, alignment films, liquid crystal layer, and then preferably there is glass substrate or resin substrate, colored filter, alignment films, liquid crystal layer, alignment films, glass substrate or resin substrate successively.
Display panel of the present invention preferably forms the such multilayer laminated boards structure of such as thin film transistor (TFT) (ThinFilmTransistor, TFT) element according to the form of final products.
In addition, when the touch panel etc. of outer (on-cell) structure is such, also liquid crystal display (the LiquidCrystalDisplay made for the time being can be used, LCD) unit or Organic Light Emitting Diode (OrganicLightEmittingDiode, OLED) unit is as display panel, and is coated with photosensitive composite used in the present invention on these unit.
In addition, display panel of the present invention also can at glass substrate or between resin substrate and touch detecting electrode or on glass substrate or resin substrate, containing other layers such as index matching (indexmatching) layers.
< glass substrate or resin substrate >
Substrate of the present invention can use glass substrate or resin substrate.
From the viewpoint of the lightweight of panel, slimming, substrate is preferably thin, is below 0.3mm when glass substrate, is below 1.0mm when resin substrate.
The thickness of substrate there is no special lower limit, from the viewpoint of the intensity of panel, and preferred more than 0.05mm, more preferably more than 0.1mm when glass substrate.
Preferred more than 0.1mm, more preferably more than 0.3mm when resin substrate.
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, polybenzoxazole, polyphenylene sulfide, polycyclic alkene, norbornene resin, the fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomeric resins, cyanate ester resin, crosslinked dimethyl ester resin, cyclic polyolefin, aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin etc.
From the viewpoint of dimensional accuracy and the transparency, substrate preferred glass substrate, in addition, to break and the viewpoint of bendability from light weight, not easily, preferred resin film substrate.Resin molding can adopt the manufacture method of so-called roll-to-roll (roll-to-roll) suitably.
Below, liquid crystal panel and organic EL panel are illustrated.
< liquid crystal panel >
There is no particular restriction for liquid crystal panel used in the present invention, can enumerate the well-known liquid crystal panel taking various structure.
In addition, the desirable liquid crystal drive mode of liquid crystal indicator of the present invention can be enumerated: twisted nematic (TwistedNematic, TN) mode, homeotropic alignment (VerticalAlignment, VA) (In-Plane-Switching is switched in mode, face, IPS) mode, fringing field switch (FringeFieldSwitching, FFS) mode, optical compensation curved (OpticallyCompensatedBend, OCB) mode etc.
In panel is formed, at colorful optical filter array (ColorFilteronArray, also cured film of the present invention be can use in the liquid crystal indicator of COA) mode, such as, the organic insulating film (115) of Japanese Patent Laid-Open 2005-284291 publication or the organic insulating film (212) of Japanese Patent Laid-Open 2005-346054 publication can be used as.In addition, the specifically aligned of the liquid crystal orientation film that liquid crystal indicator of the present invention is desirable enumerates friction orientation method, optical alignment method etc.In addition, also the polymkeric substance by recording in Japanese Patent Laid-Open 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication supports that orientation (PolymerSustainedAlignment, PSA) technology is to carry out polymer orientation support.
Fig. 2 is the conceptual sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.This color liquid crystal display arrangement 10 is the liquid crystal panel on the back side with back light unit 12, and in liquid crystal panel, configure with at the element that attached to the corresponding TFT16 of all pixels of configuring between the two panels glass substrate 14 of light polarizing film, glass substrate 15.For each element formed on the glass substrate, by the contact hole 18 formed in cured film 17, the ito transparent electrode 19 forming pixel electrode is connected up.On ito transparent electrode 19, the layer being provided with liquid crystal 20 and RGB (RedGreenBlue, the RGB) colored filter 22 being configured with black matrix".
In the present invention, display panel can be used as by there are article on the surface that touch detecting electrode at least one of the glass substrate 14 of described liquid crystal indicator and glass substrate 15.
The light source of backlight is not particularly limited, and can use well-known light source.Such as can enumerate: multi-colored led, fluorescent light (cold-cathode tube), organic EL etc. of white luminous diode (LightEmittingDiode, LED), blue red green etc.
In addition, liquid crystal indicator can be set as three-dimensional (threedimensional, 3D) (stereopsis) type, also can be set as touch panel type.And then also can be set as soft type, can be used as the interlayer dielectric (520) recorded in the 2nd interlayer dielectric (48) recorded in Japanese Patent Laid-Open 2011-145686 publication or Japanese Patent Laid-Open 2009-258758 publication.
< organic EL panel >
Organic EL panel used in the present invention uses except the planarization film that formed of described photosensitive composite of the present invention or interlayer dielectric except having, and there is no particular restriction, can enumerate the well-known various organic EL display taking various structure.
Such as, the concrete example of the TFT (Thin-FilmTransistor) that organic EL panel used in the present invention has can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to electrical characteristics excellence, therefore can be combined in these TFT and preferably uses.
Fig. 3 is the formation concept map of an example of organic EL panel.And represent the schematic sectional view of the substrate in the organic EL display of bottom emission type, there is planarization film 4.
Glass substrate 6 forms the TFT1 of bottom gate type, to cover the state of this TFT1 and to be formed and comprise Si 3n 4dielectric film 3.Formed after omitting illustrated contact hole in dielectric film 3 here, form the wiring 2 (height 1.0 μm) being connected to TFT1 via this contact hole on the insulating film 3.Wiring 2 is used to the wiring that will connect between TFT1 or be connected with TFT1 by the organic EL formed in subsequent handling.
And then, in order to make, because of the concavo-convex planarization formed caused by wiring 2, to form planarization film 4 on the insulating film 3 with the concavo-convex state be embedded into caused by wiring 2.
On planarization film 4, be formed with the organic EL of bottom emission type.That is, on planarization film 4, be connected with wiring 2 via contact hole 7 and form the first electrode 5 comprising ITO.In addition, the first electrode 5 is equivalent to the anode of organic EL.
Forming the dielectric film 8 of the shape at the edge 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 its subsequent handling can be prevented.
And then, in Fig. 1 (a), Fig. 1 (b) although not shown, but hole transmission layer, organic luminous layer, electron transfer layer can be set across required pattern mask successively evaporation, then on whole of surface, form the second electrode comprising Al, glass for sealing plate and ultraviolet ray hardening type epoxy resin is used to fit, seal thus, obtain and the active matrix organic EL display device being used for driving the TFT1 of this organic EL is connected to each organic EL.
In the present invention, at least one of the glass substrate 6 at described organic EL display can be had on the surface the article touching detecting electrode and be used as display panel.
[coating process]
There is no particular restriction for the method for coating photosensitive composite, can use well-known coating process, such as, can use the methods such as ink-jet method, slot coated method, spray-on process, rolling method, method of spin coating, cast coating method, slit and rotary process.And then, also can apply in Japanese Patent Laid-Open 2009-145395 publication and record such what is called and to prewet (pre-wet) method.
In addition, substrate is fixed preferably by absorption during coating.
The method of sorbing substrate is not particularly limited, and can use well-known method, from the cost of device or the viewpoint of yield, and preferred vacuum suction.
The wet coating thickness of photosensitive composite during coating is not particularly limited, and usually uses with the scope of 0.1 μm ~ 10 μm.
In addition, can photosensitive composite is applied to display panel possess touch detecting electrode face on before, carry out the cleaning of the substrates such as alkali cleaning or plasma clean.And then hexamethyldisilazane etc. can be utilized after base-plate cleaning to process possessing the face touching detecting electrode.By carrying out this process, there is the tendency that photosensitive composite improves the adhesion possessing the face touching detecting electrode.
< solvent removal step >
The manufacture method of panel substrate of the present invention comprises from be coated with photosensitive composite except the solvent removal step of desolventizing is as operation 2.
In described solvent removal step, from be coated with photosensitive composite, remove desolventizing preferably by decompression (vacuum) and/or heating etc., substrate forms dry coating.The heating condition preferably 70 DEG C ~ 130 DEG C of solvent removal step and 30 second ~ 300 seconds about.In addition, in described solvent removal step, without the need to the solvent in photosensitive composite is removed completely, as long as will remove at least partially.
< hardening process >
The manufacture method of panel substrate of the present invention comprises makes the hardening process of the photosensitive composite sclerosis removed through solvent as operation 3 by light and/or heat.
In hardening process, as long as hardened by light and/or heat, harden preferably by light and heat.
[by photogenic sclerosis]
In hardening process, when being hardened by light, preferably by more than wavelength 300nm and the actinic ray of below 450nm photosensitive composite is exposed.By described actinic ray, the polymerizable monomer in photosensitive composite is polymerized sclerosis by the effect of Photoepolymerizationinitiater initiater.
Exposure light source can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, LED light source, excimer laser generation device etc., can preferably use i ray (365nm), h ray (405nm), g ray (436nm) etc. to have more than 300nm and the actinic ray of the wavelength of below 450nm.In addition, optionally also irradiation light is adjusted by the such point optical filter of long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter (bandpassfilter).
Exposure device can use: the exposure machine of the various modes such as mirror surface projection aligner (mirrorprojectionaligner), stepper (stepper), scanner (scanner), close induction type (proximity), contact (contact), microlens array (microlensarray), lens scan instrument (lensscanner), laser explosure.
In addition, also there is no particular restriction for the exposure of described exposure, preferred 1mJ/cm 2~ 3,000mJ/cm 2, more preferably 1mJ/cm 2~ 500mJ/cm 2.
From the viewpoint promoting sclerosis, described exposure is preferably carried out under the state blocked through oxygen.The method blocking oxygen can illustrate carries out exposing or arrange oxygen barrier film in a nitrogen environment.
In addition, as long as exposure the carrying out at least partially the photosensitive composite removed through solvent in described hardening process, such as, can be blanket exposure, also can be pattern exposure.
[sclerosis caused by heat]
In hardening process, when being hardened by heat, there is no particular restriction for heat treated temperature, can carry out thermmohardening at the temperature of (methyl) acrylate compounds sclerosis.
From the viewpoint manufacturing adaptive, preferably less than 180 DEG C, more preferably less than 150 DEG C, and then preferably less than 130 DEG C.Lower limit preferably more than 80 DEG C, more preferably more than 90 DEG C.The method of heating is not particularly limited, and can use well-known method.Such as can enumerate heating plate, baking oven, infrared heater etc.
In addition, about the heat time, when heating plate preferably 1 minute ~ about 30 minutes, when in addition preferably 20 minutes ~ about 120 minutes.Can not harden with causing damage to substrate, device within the scope of this.
In addition, the sclerosis caused by light and/or heat in hardening process can be carried out continuously, also can carry out successively.
In addition, when heat-treating, by processing in a nitrogen environment, can further improve the transparency.
< thinning operation >
The manufacture method of panel substrate of the present invention, when using glass substrate as substrate, preferably also comprised the thinning operation of grinding glass substrate before painting process.
By thinning operation, the thickness of glass substrate can be adjusted to set scope.
Thinning operation was preferably carried out before forming touch detecting electrode on a display panel.After thinning operation, carry out the formation of images match layer (imagematchinglayer) etc. by well-known method or touch the formation of detecting electrode.
[Ginding process]
There is no particular restriction for Ginding process in thinning operation, can use well-known method, carries out preferably by chemical grinding.
The method of chemical grinding can be enumerated: the base material of glass substrate or laminating two panels glass substrate is immersed in the method in the chemical grinding liquid containing hydrofluorite.
Described chemical grinding liquid is preferably containing hydrofluorite and sulphur aqueous acid.The concentration preferably 10 quality % ~ 30 quality % of hydrofluorite, more preferably 15 quality % ~ 28 quality %, and then preferred 17 quality % ~ 25 quality %.In addition, the concentration preferably 20 quality % ~ 50 quality % of sulfuric acid, more preferably 30 quality % ~ 45 quality %, and then preferred 35 quality % ~ 42 quality %.
The method of chemical grinding is not particularly limited, and preferably can use the method recorded in Japanese Patent Laid-Open 2009-210719 publication or Japanese Patent Laid-Open 2001-100165 publication.
(photosensitive composite)
Photosensitive composite (hereinafter also referred to as " photosensitive composite " or " composition ") used in the present invention contains as above (methyl) acrylate compounds of the face energy of composition A, as the Photoepolymerizationinitiater initiater of composition B, as organic filler or the inorganic particulate of composition C, and as the solvent of components D, relative to the total solid component amount beyond the composition C in photosensitive composite, the content of composition A is 50 quality % ~ 98 quality %, the viscosity of photosensitive composite is 3mPas ~ 30mPas, the surface tension of photosensitive composite is 20mN/m ~ 30mN/m, be 10 quality % ~ 50 quality % relative to the solid constituent amount of photosensitive composite total amount.
The viscosity of photosensitive composite is 3mPas ~ 30mPas, preferred 5mPas ~ 25mPas, more preferably 7mPas ~ 22mPas.
The RE-80L type rotational viscosimeter that viscosity such as preferably uses eastern machine industry (stock) to manufacture measures at 25 DEG C ± 0.2 DEG C.About rotational speed when measuring, viscosity preferably measures with the rotational speed of 100rpm when being less than 5mPas, viscosity preferably measures with the rotational speed of 50rpm when being more than 5mPas and being less than 10mPas, viscosity preferably measures with the rotational speed of 20rpm when being more than 10mPas and being less than 30mPas, and the rotational speed preferably with 10rpm when viscosity is more than 30mPas measures.
The surface tension of photosensitive composite is 20mN/m ~ 30mN/m, preferred 22mN/m ~ 30mN/m, more preferably 24mN/m ~ 28mN/m.
The DM-701 that surface tension such as can use consonance interface science (stock) to manufacture is measured by hanging drop (pendantdrop) method.
From the viewpoint of micro concavo-convex flatness and substrate tracing ability, the thickness after the solvent removal step of photosensitive composite preferably 0.2 μm ~ 20 μm, more preferably 0.4 μm ~ 10 μm, and then preferably 0.8 μm ~ 5.0 μm, most preferably 1.2 μm ~ 4.0 μm.
Specifically, the composition of illustration containing following composition is as embodiment.
Composition A: (methyl) acrylate compounds that face can be above
Photosensitive composite used in the present invention contains above (methyl) acrylate compounds of face energy as composition A.
Composition A is the compound of (methyl) acryloyl group in molecule with more than five.
Composition A can be low molecular compound, also can be oligomer, but is not polymkeric substance.That is, from the viewpoint of the hardness of cured film, the molecular weight of composition A (being weight average molecular weight when having molecular weight distribution) is less than 10,000, preferably less than 5,000, and then preferably less than 3,000.
Composition A has (methyl) acryloyl group of more than five in molecule.The number preferably 5 ~ 15 of (methyl) acryloyl group that (in a part) has in molecule, more preferably 5 ~ 10, and then preferably 5 ~ 7.
If the number of (methyl) acryloyl group is in described scope, then hardness and reactive excellence.
As long as composition A adds up to acryloyl group (-C (=the O)-CH=CH with more than five in a part 2) and methacryl (-C (=O)-C (CH 3)=CH 2), preferably add up to acryloxy (-O-C (=the O)-CH=CH with more than five 2) and methacryloxy (-O-C (=O)-C (CH 3)=CH 2).In addition, preferably there is the acryloyl group of more than five, more preferably there is the acryloxy of more than five.
Compared with methacryl, acryloyl group is preferred in hardening (reactivity) excellence.In addition, if (methyl) acryloxy, be then easy to preferably from the viewpoint of reactive excellence, synthesis.
[composition A-1: the polymerizable monomer with carboxyl]
About composition A, as composition A-1 preferably in molecule (in a part) there is more than one carboxyl.The number of the carboxyl in a part preferably one ~ six, more preferably one ~ tri-, and then preferably one or two, particularly preferably one.
If the number of the carboxyl that composition A-1 has in a part is in described scope, then base material adhesion is excellent, therefore preferably.
In addition, the carboxyl that composition A-1 has also can form salt.Form the preferred organic cationic compound of kation of salt, transition metal coordination complexes kation or metal cation.Organic cation compound can be enumerated: level Four ammonium cation, level Four pyridylium, level Four quinoline kation, phosphorus kation, iodine kation, sulphur kation etc.Transition-metal cation can illustrate the compound recorded in Jap.P. No. 279143 publications.Metal cation can illustrate: Na +, K +, Li +, Ag +, Fe 2+, Fe 3+, Cu +, Cu 2+, Zn 2+, Al 3+, Ca 2+deng.
In addition, composition A-1 does not preferably have the acidic group beyond described carboxyl.Acidic group beyond carboxyl can illustrate sulfonic group, phosphate etc.If have the acidic group beyond carboxyl, then base material adhesion reduces sometimes.
Composition A-1 is the ester of polyol and unsaturated carboxylic acid, and preferably make the unreacted hydroxyl reaction of carboxylic acid anhydrides and polyol and there is the polymerizable monomer of acidic group (carboxyl), particularly preferably being polyol is pentaerythrite and/or dipentaerythritol.
Composition A-1 such as obtains by compound (hereinafter also referred to " hydroxyl multifunctional (methyl) acrylate ") the addition acid anhydrides to (methyl) acryloyl group and hydroxyl with more than five.
Hydroxyl multifunctional (methyl) acrylate can illustrate the polyol of the hydroxyl with more than five and (methyl) acrylic acid ester.
There is the polyol preferred aliphat polyol of the hydroxyl of more than five, specifically can illustrate dipentaerythritol, tripentaerythritol etc.In these compounds, preferred dipentaerythritol.
In addition, polyol also can use the alkylene oxide addition product of described illustrative polyol, and alkylene oxide can illustrate oxirane, epoxypropane etc.
As long as the manufacture method of hydroxyl polyfunctional acrylic ester suitably adopts well-known method, be not particularly limited.Specifically can illustrate: method polyol and (methyl) acrylic acid being added thermal agitation under acidic catalyst.Acidic catalyst can enumerate sulfuric acid, p-toluenesulfonic acid and methane-sulforic acid etc.In addition, as long as temperature of reaction suitably sets, preferably 70 DEG C ~ 140 DEG C according to used compound and object.If in described temperature range, then reaction is fast, and stably reacts, and the generation of inhibition of impurities or gelation.
During reaction, preferably use the organic solvent low with the solubleness of water that generates in esterification, one side promotes to dewater with water azeotropic one side.Preferred organic solvent such as can be enumerated: the aromatic hydrocarbons such as toluene, benzene and dimethylbenzene, the aliphatic hydrocarbon such as hexane and heptane, and the ketone such as methyl ethyl ketone and cyclohexanone etc.In addition, organic solvent can distill removal by reducing pressure after the reaction.
In addition, in order to prevent the polymerization of (methyl) acrylate of gained, polymerization inhibitor can be added in reactant liquor.This polymerization inhibitor such as can be enumerated: p-dihydroxy-benzene, hydroquinone monomethyl ether, BHT and phenothiazine etc.
Composition A-1 is reaction by multifunctional (methyl) acrylate of described hydroxyl and acid anhydrides and obtains.
Acid anhydrides can be enumerated: succinic anhydride, 1-dodecenylsuccinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, Nadic anhydride (endomethylene-tetra-hydrophthalicanhydride), methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabromophthalic anhydride and trimellitic anhydride etc. have the compound of an anhydride group in same a part, and pyromellitic dianhydride, phthalic anhydride dipolymer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic anhydride and trimellitic anhydride glycol ester (trade name that commercially available product such as has new Japan Chemical (stock) to manufacture keep house moral (Rikacid) TMEG-100) etc. have the compound of two anhydride group in same a part.
In these compounds, preferably there is in same a part the compound of an anhydride group.
As long as the manufacture method of composition A-1 is according to conventional method.
Such as can enumerate: make multifunctional (methyl) acrylate of hydroxyl and carboxylic acid anhydrides in the presence of a catalyst, at 60 DEG C ~ 110 DEG C, react the method etc. of 1 hour ~ 20 hours.The catalyzer of this situation can be enumerated: N, N-dimethyl benzylamine, triethylamine, tri-n-butylamine, triethylenediamine, zephiran chloride trimethyl ammonium, bromination benzyl triethyl ammonium, evolution tetramethyl-ammonium, evolution cetyltrimethylammonium ammonium and zinc paste etc.
Compound represented by composition A-1 preferred formula A-1.
[changing 1]
In formula A-1, X 2separately represent the alkyl of hydrogen atom, carbon number 1 ~ 6, acryloxy or methacryloxy, there is the X of five 2for acryloxy or methacryloxy, W 2represent the alkylidene of carbon number 1 ~ 6, the alkenylene of carbon number 2 ~ 6 or phenylene.
In formula A-1, there is the X of five 2represent acryloxy or methacryl, preferred acryloxy.
In addition, the X beyond acryloxy or methacryloxy 2represent the alkyl of hydrogen atom or carbon number 1 ~ 6.The alkyl of carbon number 1 ~ 6 can be arbitrary alkyl of straight-chain, branch-like, ring-type.In these groups, the X beyond (methyl) acryloxy 2the alkyl of preferred hydrogen atom or carbon number 1 ~ 4, more preferably hydrogen atom, methyl or ethyl, and then preferred hydrogen atom.
In formula A-1, W 2represent the alkylidene of carbon number 1 ~ 6, the alkenylene of carbon number 2 ~ 6 or phenylene, the alkylidene of carbon number 1 ~ 6 can be straight-chain, branch-like, ring-type any one.The preferred carbon number 2 ~ 6 of described alkylidene, can illustrate ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclohexylidene.
In formula A-1, W 2the alkylidene of preferred carbon number 1 ~ 6, the more preferably alkylidene of carbon number 2 ~ 6, and then the alkylidene of preferred carbon number 2 or 3, particularly preferably ethylidene.
Composition A-1 also can use the product of listing, such as, can enumerate M-510, M-520, TO-2349, TO-2359 etc. of sub-Luo Nisi (Aronix) (registered trademark) as modified by polyacid acrylic acid series oligomer series that East Asia synthesis (stock) manufactures.
Composition A-1 can be used alone one, also can and with two or more.
Relative to the total organic solid composition of photosensitive composite, the content preferably 3 quality % ~ 49.5 quality % of composition A-1, more preferably 3 quality % ~ 45 quality %, and then preferably 5 quality % ~ 40 quality %, most preferably 10 quality % ~ 35 quality %.
In addition, in the present invention, " solid constituent " in so-called photosensitive composite, refers to the composition except the volatile ingredients such as organic solvent.In addition, so-called " organic solid composition ", refers to the composition except the inorganic constituents such as volatile ingredient and inorganic particulate such as organic solvent from photosensitive composite.
[composition A-2: the polymerizable monomer without carboxyl]
Photosensitive composite used in the present invention contain (methyl) acryloyl group in molecule with more than five and the polymerizable monomer without carboxyl as composition A-2.Composition A-2 is that (in a part) has (methyl) acryloyl group of more than five and the polymerizable monomer different from composition A-1 in molecule.Composition A-2 does not have carboxyl in molecule, does not preferably also have other acidic groups, and other acidic groups can illustrate sulfonic group, phosphate etc.
Composition A-2 can be low molecular compound, also can be oligomer, but and non-polymer.That is, from the viewpoint of the hardness of cured film, the molecular weight of composition A-2 (being weight average molecular weight when having molecular weight distribution) is less than 10,000, preferably less than 5,000, and then preferably less than 3,000.
Composition A-2 has (methyl) acryloyl group of more than three in molecule.Preferably there are three ~ ten (methyl) acryloyl groups, more preferably there are three ~ six.By being set as described formation, and play effect of the present invention further.
The compound that composition A-2 can suitably apply in this composition of choice for use; such as can enumerate: in the paragraph 0011 of Japanese Patent Laid-Open 2006-23696 publication record composition or Japanese Patent Laid-Open 2006-64921 publication paragraph 0031 ~ paragraph 0047 in record composition in; there is in molecule the compound of (methyl) acryloyl group of more than three, these records are incorporated in instructions of the present invention.
Composition A-2 preferably can illustrate (methyl) acrylate of polyol, specifically can enumerate: dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol six (methyl) acrylated epoxy ethane (EthyleneOxide, EO) modifier etc.
Composition A-2 also can use the product of listing, such as, can enumerate: sub-Luo Nisi (Aronix) (registered trademark) M-309, sub-Luo Nisi (Aronix) M-400, sub-Luo Nisi (Aronix) M-405, sub-Luo Nisi (Aronix) M-450, sub-Luo Nisi (Aronix) M-7100, sub-Luo Nisi (Aronix) M-8030, sub-Luo Nisi (Aronix) M-8060, sub-Luo Nisi (Aronix) TO-1382, sub-Luo Nisi (Aronix) TO-1450 (East Asia synthesis (stock) manufactures), Ka Yala get (KAYARAD) TMPTA, Ka Yala get (KAYARAD) DPHA, Ka Yala get (KAYARAD) DPCA-20, Ka Yala get (KAYARAD) DPCA-30, Ka Yala get (KAYARAD) DPCA-60, Ka Yala get (KAYARAD) DPCA-120 (Japanese chemical drug (stock) manufacture), than this gram (Biscoat) 295, than this gram (Biscoat) 300, than this gram (Biscoat) 360, than this gram (Biscoat) GPT, than this gram (Biscoat) 3PA, than this gram (Biscoat) 400 (Osaka Organic Chemical Industry (stock) manufacture) etc.
In addition, even if the compound for being equivalent to composition A-2, the compound being equivalent to aftermentioned alkoxysilane compound containing trialkylsilyl group in molecular structure is also regarded as alkoxysilane compound containing trialkylsilyl group in molecular structure.
[(methyl) propenoic methyl carbamate]
In the present invention, (methyl) propenoic methyl carbamate also can be used as composition A-2.
Spendable in the present invention (methyl) propenoic methyl carbamate can illustrate and use the addition reaction of isocyanates and hydroxyl and the carbamate addition polymerization compound that manufactures, can illustrate in Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-fair 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication and record such propenoic methyl carbamate class, these records are incorporated in instructions of the present invention.
From the viewpoint of cured film hardness, the molecular weight of (methyl) propenoic methyl carbamate preferably 500 ~ 10,000, more preferably 650 ~ 6,000, and then preferably 800 ~ 3,000.
By being set as this formation, and more effectively play effect of the present invention.
(methyl) acryloxy in (methyl) propenoic methyl carbamate can be acryloxy, methacryloxy any one, also can be two kinds, preferred acryloxy.
The number of (methyl) acryloxy in (methyl) propenoic methyl carbamate preferably more than 5, more preferably more than 6, and then preferably more than 10.If described embodiment, then more effectively play effect of the present invention.
In addition, there is no particular restriction for the upper limit of the number of described (methyl) acryloxy, and preferably less than 50, more preferably less than 30, and then preferably less than 20.
Photosensitive composite of the present invention can, only containing a kind of (methyl) propenoic methyl carbamate, also can contain two or more.
(methyl) acryloxy in (methyl) propenoic methyl carbamate can be acryloxy, methacryloxy any one, also can be two kinds, preferred acryloxy.
There is no particular restriction for the number of the amino-formate bond in (methyl) propenoic methyl carbamate, and preferably 1 ~ 30, more preferably 1 ~ 20, and then preferably 2 ~ 10, particularly preferably 2 ~ 5, most preferably 2 or 3.
(methyl) propenoic methyl carbamate preferred aliphat (methyl) propenoic methyl carbamate.
In addition, (methyl) propenoic methyl carbamate preferably has isocyanuric acid ring (isocyanuricring) structure.
In addition, (methyl) propenoic methyl carbamate preferably comprise there is more than one amino-formate bond core part, with to be bonded in core part and there is the compound of the end section of more than one (methyl) acryloxy, in described core part, be more preferably bonded with the compound of plural described end section, and then in described core part, be preferably bonded with the compound of two ~ five described end sections, particularly preferably be the compound being bonded with end section described in two or three in described core part.
(methyl) propenoic methyl carbamate preferably at least has the compound of the group represented by following formula Ae-1 or formula Ae-2, more preferably at least has the compound of the group represented by following formula Ae-1.In addition, (methyl) propenoic methyl carbamate more preferably has the compound of the plural group be selected from the cohort that the group represented by following formula Ae-1 and the group represented by formula Ae-2 form.
In addition, the group represented by described end section preferred following formula Ae-1 or formula Ae-2 in (methyl) propenoic methyl carbamate.
[changing 2]
In formula Ae-1 and formula Ae-2, R separately represents acrylic or methacrylic acid group, and wave line part divides the bonding position represented with other structures.
In addition, (methyl) propenoic methyl carbamate preferably at least has the compound of the group represented by following formula Ac-1 or formula Ac-2, more preferably at least has the compound of the group represented by following formula Ac-1.
In addition, the group represented by described core part preferred following formula Ac-1 or formula Ac-2 in (methyl) propenoic methyl carbamate.
[changing 3]
In formula Ac-1 and formula Ac-2, L 1~ L 4separately represent the bivalent hydrocanbon radical of carbon number 2 ~ 20, wave line part divides the bonding position represented with other structures.
L 1~ L 4the separately alkylidene of preferred carbon number 2 ~ 20, the more preferably alkylidene of carbon number 2 ~ 10, and then the alkylidene of preferred carbon number 4 ~ 8.In addition, described alkylidene also can have branched structure or ring structure, preferred straight-chain alkyl-sub-.
In addition, (methyl) propenoic methyl carbamate particularly preferably is the group represented by formula Ac-1 or formula Ac-2, the compound with two or three group bondings in the cohort selecting the group represented by free style Ae-1 and formula Ae-2 to form.
Below, illustrate (methyl) propenoic methyl carbamate that can preferably use in the present invention, but the present invention is not limited to these examples certainly.
[changing 4]
[changing 5]
[changing 6]
In addition, spendable in the present invention (methyl) propenoic methyl carbamate can illustrate and use the addition reaction of isocyanates and hydroxyl and the carbamate addition polymerization compound that manufactures, can illustrate in Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-fair 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication and record such propenoic methyl carbamate class, these records are incorporated in instructions of the present invention.
The commercially available product of (methyl) propenoic methyl carbamate can illustrate: the U-6HA that can obtain from Xin Zhong village chemical industry (stock), UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, U-10PA, UA-53H, UA-33H (being registered trademark), or the UA-306H that can obtain from common prosperity society chemistry (stock), UA-306T, UA-306I, UA-510H, La Luomo (Laromer) UA-9048 that can obtain from BASF (BASF) company, La Luomo (Laromer) UA-9050, La Luomo (Laromer) PR9052, the Ai Bai gram force (EBECRYL) 220 that can obtain from Daicel-Ao fine jade Knicks (Daicel-Allnex) (stock), Ai Bai gram force (EBECRYL) 5129, Ai Bai gram force (EBECRYL) 8301, Ai Bai gram force (EBECRYL) KRM8200, Ai Bai gram force (EBECRYL) 8200AE, Ai Bai gram force (EBECRYL) 8452 etc.
Composition A-2 can be used alone one, also can and with two or more.
Relative to the total organic solid composition of photosensitive composite, the content preferably 20 quality % ~ 85 quality % of composition A-2, more preferably 30 quality % ~ 80 quality %, and then preferred 45 quality % ~ 75 quality %.
In the present invention, relative to the total content of composition A-1 and composition A-2, the content of composition A-1 is 10 quality % ~ 50 quality %.If relative to composition A-1 and the total content of composition A-2, the content of composition A-1 is less than 10 quality %, then the amount of the carboxyl in composition is few, and developability (pattern voltinism) is poor.In addition, if more than 50 quality %, then the poor reliability such as absorption of perspiration.
Relative to the total content of composition A-1 and composition A-2, the content preferably 12 quality % ~ 40 quality % of composition A-1, more preferably 15 quality % ~ 35 quality %, and then preferred 18 quality % ~ 30 quality %.
In addition, in the present invention, relative to the total organic solid composition of photosensitive composite, total content preferably more than the 40 quality % of composition A-1 and composition A-2.If the total content of composition A-1 and composition A-2 is in described scope, then developability and cured film is excellent in reliability.
Relative to the total solid component amount beyond the composition C in photosensitive composite, the content of composition A is 50 quality % ~ 98 quality %, more preferably 60 quality % ~ 95 quality %, and then preferred 70 quality % ~ 90 quality %.
Composition B: Photoepolymerizationinitiater initiater
Photosensitive composite used in the present invention contains Photoepolymerizationinitiater initiater as composition B.
Photoepolymerizationinitiater initiater is preferably containing radical polymerization initiator.
In the present invention, spendable Photoepolymerizationinitiater initiater is the compound causing, promote polymerization by light.Wherein, more preferably optical free radical polymerization initiator.
So-called " light ", as long as giving can produce by composition B the active energy ray causing the energy of planting by its irradiation, then there is no particular restriction, extensively comprises alpha ray, gamma-rays, X ray, ultraviolet (UltraViolet, UV), luminous ray, electron beam etc.In these, preferably at least bag light with violet rays.
Photoepolymerizationinitiater initiater such as can be enumerated: oxime ester compound, organic halogenation compound, oxygen base diazole compounds, carbonyls, ketal compound, styrax compound, acridine compounds, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, metallocene compound, six aryl united imidazoles, organic boric acid compounds, disulfonic acid compound, salt compound, acylphosphanes (oxide) compound.In these compounds, from the viewpoint of sensitivity, preferred oxime ester compound, six aryl united imidazole, more preferably oxime ester compounds.
Oxime ester compound can use: the compound recorded in Japanese Patent Laid-Open 2000-80068 publication, Japanese Patent Laid-Open 2001-233842 publication, Jap.P. spy table 2004-534797 publication, Japanese Patent Laid-Open 2007-231000 publication, Japanese Patent Laid-Open 2009-134289 publication.
The preferred following formula 1 of oxime ester compound or the compound represented by formula 2.
[changing 7]
In formula 1 or formula 2, Ar represents aromatic series base or heteroaromatic base, R 1represent alkyl, aromatic series base or alkyl oxy, R 2represent hydrogen atom or alkyl, and then R 2also can close with Ar base key and form ring.
Ar represents aromatic series base or heteroaromatic base, from benzene ring compound, naphthalene cycle compound or carbazole cyclic compound, preferably removes the group of a hydrogen atom gained on aromatic rings, more preferably with R 2form the naphthyl of ring, carbazyl together.Heteroatoms in heteroaromatic base can preferably enumerate nitrogen-atoms, oxygen atom and sulphur atom.
R 1represent alkyl, aromatic series base or alkyl oxy, preferable methyl, ethyl, benzyl, phenyl, naphthyl, methoxy or ethoxy, more preferably methyl, ethyl, phenyl or methoxyl.
R 2represent hydrogen atom or alkyl, preferred hydrogen atom or the alkyl be substituted, more preferably hydrogen atom, the alkyl be substituted forming ring together with Ar or toluene sulfanyl.
In addition, the group of the preferred carbon number 4 ~ 20 of Ar, R 1the group of preferred carbon number 1 ~ 30, and R 2the group of preferred carbon number 1 ~ 50.
Oxime ester compound and then preferably following formula 3, formula 4 or the compound represented by formula 5.
[changing 8]
In formula 3 ~ formula 5, R 1represent alkyl, aromatic series base or alkoxy, X represents-CH 2-,-C 2h 4-,-O-or-S-, R 3separately represent halogen atom, R 4the amino, arylthio, alkylthio group, alkoxy, aryloxy group or the halogen atom that separately represent alkyl, phenyl, replace through alkyl, R 5represent hydrogen atom, alkyl or aryl, R 6represent alkyl, n1 and n2 separately represents the integer of 0 ~ 6, and n3 represents the integer of 0 ~ 5.
R 1represent alkyl, aromatic series base or alkoxy, preferred R 11group (the R of-X '-alkylidene-represented 11represent alkyl or aryl, X ' expression sulphur atom or oxygen atom).R 11preferred aryl groups, more preferably phenyl.As R 11alkyl and aryl also can replace through halogen atom (preferred fluorine atom, chlorine atom or bromine atoms) or alkyl.
The preferred sulphur atom of X.
R 3and R 4can bonding on the optional position on aromatic rings.
R 4the amino, arylthio, alkylthio group, alkoxy, aryloxy group or the halogen atom that represent alkyl, phenyl, replace through alkyl, preferred alkyl, phenyl, arylthio or halogen atom, more preferably alkyl, arylthio or halogen atom, and then preferred alkyl or halogen atom.The alkyl of the preferred carbon number 1 ~ 5 of alkyl, more preferably methyl or ethyl.The preferred chlorine atom of halogen atom, bromine atoms or fluorine atom.
In addition, R 4carbon number preferably 0 ~ 50, more preferably 0 ~ 20.
R 5represent hydrogen atom, alkyl or aryl, preferred alkyl.The alkyl of the preferred carbon number 1 ~ 5 of alkyl, more preferably methyl or ethyl.The aryl of the preferred carbon number 6 ~ 10 of aryl.
R 6represent alkyl, the alkyl of preferred carbon number 1 ~ 5, more preferably methyl or ethyl.
N1 and n2 distinguishes the R on the aromatic rings in expression 3 or formula 4 3replacement number, the R on the aromatic rings in n3 expression 5 4replacement number.
N1 ~ n3 separately preferably 0 ~ 2 integer, more preferably 0 or 1.
Below, the example of the oxime ester compound that can preferably use in the present invention is shown.But oxime ester compound used in the present invention is not limited to these compounds certainly.In addition, Me represents methyl, and Ph represents phenyl.In addition, the Sys-trans isomerism of the double bond of the oxime in these compounds can be any one of EZ, also can be the potpourri of EZ.
[changing 9]
[changing 10]
The example of organic halogenation compound specifically can be enumerated: if " Japanization association publication (BullChem.Soc.Japan) " (42 of Lin Dengren, 2924 (1969)), United States Patent (USP) the 3rd, 905, No. 815 instructionss, Jap.P. examined patent publication 46-4605 publication, Japanese Patent Laid-Open No. Sho 48-36281 publication, Japanese Patent Laid-Open No. Sho 55-32070 publication, Japanese Patent Laid-Open No. Sho 60-239736 publication, Japanese Patent Laid-Open No. Sho 61-169835 publication, Japanese Patent Laid-Open No. Sho 61-169837 publication, Japanese Patent Laid-Open No. Sho 62-58241 publication, Japanese Patent Laid-Open No. Sho 62-212401 publication, Japanese Patent Laid-Open No. Sho 63-70243 publication, Japanese Patent Laid-Open No. Sho 63-298339 publication, M.P. " heterocyclic chemistry periodical (JournalofHeterocyclicChemistry) " (1 (No3) of Hunter (M.P.Hutt),) etc. (1970) compound recorded in, can enumerate especially and replace oxazole compounds through three halogenated methyl, s-triazine.
The example of six aryl united imidazoles such as can be enumerated: Japanese Patent Laid-fair 6-29285 publication, United States Patent (USP) the 3rd, 479, No. 185, United States Patent (USP) the 4th, 311, No. 783, the various compounds recorded in each instructions of United States Patent (USP) the 4th, 622, No. 286 grades.
Acylphosphanes (oxide) compound can illustrate monoacylphosphine oxides compound and two acylphosphine oxide compound; specifically, such as can enumerate: gorgeous good solid (Irgacure) 819 that BASF (BASF) company manufactures, reach Luo Gu (Darocure) 4265, reach Luo Gu (Darocure) TPO etc.
Photoepolymerizationinitiater initiater can use one or combinationally use two or more.
Relative to total solid composition 100 mass parts in composition, total amount preferably 0.5 mass parts ~ 30 mass parts of the Photoepolymerizationinitiater initiater in photosensitive composite used in the present invention, more preferably 1 mass parts ~ 20 mass parts, and then preferably 1 mass parts ~ 10 mass parts, particularly preferably 2 mass parts ~ 5 mass parts.
[sensitizer]
In photosensitive composite used in the present invention, except Photoepolymerizationinitiater initiater, also sensitizer can be added.
Sensitizer absorbs actinic ray or radioactive ray and becomes excited state.The sensitizer becoming excited state produces the effects such as electronics moves, energy moves, heating by the interaction with composition B, and cause, promote polymerization.
In the present invention, spendable typical sensitizer can be enumerated: " the advanced polymkeric substance science and technology (Adv.inPolymerSci.) " (62 of J.V. gram of Li Weiluo (J.V.Crivello), 1 (1984)) sensitizer disclosed in, specifically can enumerate: Bi, perylene, acridine orange, thioxanthones, CTX, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy anthracenes, anthraquinone, cumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine (phenothiazine) derivant etc.Relative to Photoepolymerizationinitiater initiater, sensitizer preferably adds with the ratio of 50 quality % ~ 200 quality %.
Composition C: organic filler or inorganic particulate
Photosensitive composite used in the present invention contains organic filler or inorganic particulate as composition C.By containing organic filler or inorganic particulate, the hardness of cured film becomes more excellent.
[organic filler]
Organic filler used in the present invention is not particularly limited, and can use well-known organic filler.From the viewpoint of the film hardness of cured film, preferred hollow-particle.So-called hollow-particle, as long as the particle for having space at inside particles.In addition, the profile of hollow-particle can be roughly spheroid, and also can be roughly ellipsoid, shape is not limit.
The organic filler of hollow can use: Japanese Patent Laid-Open 2004-292596 publication, Japanese Patent Laid-Open 2005-054084 publication, Japanese Patent Laid-Open 2005-215315 publication, Japanese Patent Laid-Open 2006-089648 publication, Japanese Patent Laid-Open 2006-096971 publication, Japanese Patent Laid-Open 2006-241226 publication, Japanese Patent Laid-Open 2006-291090 publication, Japanese Patent Laid-Open 2008-266504 publication, the organic polymer particulate of the hollow recorded in Jap.P. No. 4059912 publication etc.
About the macromolecule forming shell, following material can be used as the organic polymer particle of hollow: hydrophobic vinyl system monomer and the multipolymer of vinyl monomer with water wettability base, styrene-acryl copolymer, the combination of polyvinyl alcohol (PVA) and methyl acrylate/trimethylolpropane dimethylacrylate etc., comprise acrylic resin, epoxy resin, polyisocyanate lipophilicity reactive moieties with comprise the resin (carbamide resin, polyurethane resin) etc. that water, amine, polyvalent alcohol and/or polycarboxylic water wettability reactive moieties react.In this situation, react by polyisocyanate and water and/or amine and generate polyureas, generated polycarbamate by polyisocyanate and polyol reaction, react by polyisocyanate and polycarboxylic acid and generate polyamide.In addition, in the resin that the lipophilicity reactive moieties comprising polyisocyanate and the water wettability reactive moieties comprising water are reacted, not only containing urea key, and biuret structure can be contained.
Patience from the formation process of the dispersiveness of hollow-particle, sclerosis epithelium, preferably there is the hollow-particle of the shell containing at least one resin be selected from the cohort that is made up of styrene-acryl copolymer, acrylic resin, epoxy resin, carbamide resin and polyurethane resin, more preferably there is the hollow-particle of the shell of at least one resin in the cohort comprising and be selected from and be made up of styrene-acryl copolymer, acrylic resin, epoxy resin, carbamide resin and polyurethane resin.
Hollow-particle preferably mean grain size (external diameter) is 10nm ~ 1,000nm, more preferably 10nm ~ 200nm, and then preferred 20nm ~ 100nm, most preferably 20nm ~ 60nm.If described scope, then can play effect of the present invention further.In addition, the mean grain size of hollow-particle as long as no special instructions, is then mean outside diameter.
In hollow-particle, the ratio that space is shared in the volume of particle and voidage can design arbitrarily, and from the performance of insulation stability, voidage height is favourable.
The voidage of hollow-particle preferably 10% ~ 80%, more preferably 20% ~ 60%, most preferably 40% ~ 60%.
In addition, the preferred 0.1nm ~ 300nm of thickness of the shell of the shell of hollow-particle, the intensity owing to needing to be coated with, in development and the operation such as thermmohardening, therefore more preferably 1nm ~ 30nm.
In addition, about the assay method of the mean grain size (external diameter) of the hollow-particle in the present invention, be by approximate for the electron microscope image conversion balling-up (circle) of particle footpath, and by its 200 in addition arithmetic means.
[inorganic particulate]
Preferred 1nm ~ the 200nm of mean grain size of inorganic particulate used in the present invention, more preferably 5nm ~ 100nm, most preferably 5nm ~ 50nm.Mean grain size refers to the particle diameter that utilizes any 200 particles of determination of electron microscopy and the value of in addition arithmetic mean gained.In addition, particle shape and in aspheric situation, using longest edge as particle diameter.
In addition, from the viewpoint of the hardness of cured film, the voidage of inorganic particulate is preferably less than 10%, is more preferably less than 3%, most preferably tight.The voidage of particle is by the value of 200 of the gap of the cross-sectional image of electron microscope gained and the area ratio of overall particle arithmetic mean gained in addition.
Inorganic particulate is preferably containing beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), gadolinium (Gd), terbium (Tb), dysprosium (Dy), ytterbium (Yb), lutetium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), molybdenum (Mo), tungsten (W), zinc (Zn), boron (B), aluminium (Al), silicon (Si), germanium (Ge), tin (Sn), plumbous (Pb), antimony (Sb), bismuth (Bi), the metal oxide particle of the atom of tellurium (Te) etc., more preferably monox, titanium dioxide, titanium composite oxide, zinc paste, zirconia, indium/tin-oxide, antimony/tin-oxide, and then preferential oxidation silicon, titanium dioxide, titanium composite oxide, zirconia, from the stability of particle, obtain easiness, the hardness of cured film, the transparency, the viewpoints such as refractive index adjustment, particularly preferably monox or titanium dioxide.
Monox preferably can enumerate silicon dioxide, more preferably can enumerate silicon dioxide granule.
As long as silicon oxide particle is the particle of inorganic oxide containing silicon dioxide, then there is no special problem, preferably containing silicon dioxide or its hydrate particle as major component (preferably more than 80 quality %).Described particle also can containing aluminate as a small amount of composition (being such as less than 5 quality %).Sometimes the aluminate contained as a small amount of composition can enumerate sodium aluminate, potassium aluminate etc.In addition, silicon dioxide granule also can contain the organic salts such as inorganic salts or tetramethyl ammonium hydroxide such as NaOH, potassium hydroxide, lithium hydroxide, ammonium hydroxide.The example of this compound can illustrate cataloid.
There is no particular restriction for the dispersion medium of cataloid, can be the potpourri of water, organic solvent and these materials any one.These dispersion medium can be used alone one, also can and with two or more.
In the present invention, particle can be also prepare by using the mixing arrangement such as bowl mill, rod mill to carry out mixing dispersion in suitable spreading agent and solvent for, described dispersion liquid with the form of dispersion liquid.In addition, in photosensitive composite used in the present invention, cataloid is without the need to existing with colloidal state.
When allocating inorganic particulate, from the viewpoint of hardness, relative to the total solid composition of photosensitive composite, content preferably more than the 1 quality % of inorganic particulate, more preferably more than 5 quality %, and then preferred more than 10 quality %.In addition, preferably below 80 quality %, more preferably below 50 quality %, and then preferably below 40 quality %, particularly preferably below 30 quality %.
Inorganic particulate can, only containing a kind of, also can contain two or more.When containing two or more, preferably its total amount becomes described scope.
Components D: solvent
Photosensitive composite used in the present invention contains solvent as components D.Photosensitive composite used in the present invention is preferably prepared into as composition A, the composition B of required composition, composition C and aftermentioned any component dissolves solution in a solvent.
The preferred organic solvent of components D, the organic solvent used in photosensitive composite used in the present invention can use well-known solvent, 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, butylene glycol diacetate esters class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, alcohols, ester class, ketone, amide-type, lactone etc.The concrete example of these organic solvents can with reference to the paragraph 0062 of Japanese Patent Laid-Open 2009-098616 publication.
Specifically, preferred propylene glycol methyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-BDO diacetate esters, adnoral acetate, propylene-glycol diacetate, tetrahydrofurfuryl alcohol.
From the viewpoint of coating, the boiling point of organic solvent preferably 100 DEG C ~ 300 DEG C, more preferably 120 DEG C ~ 250 DEG C.
In the present invention, spendable solvent can be used alone one or and with two or more.Also preferably solvents different for boiling point is used.
About the content of the solvent in photosensitive composite used in the present invention, from being adjusted to the viewpoint being suitable for the viscosity be coated with, relative to total solid composition 100 mass parts of composition, preferably 100 mass parts ~ 3,000 mass parts, more preferably 200 mass parts ~ 2,000 mass parts, and then preferred 250 mass parts ~ 1,000 mass parts.
The solid component concentration preferably 3 quality % ~ 50 quality % of photosensitive composite, more preferably 20 quality % ~ 40 quality %.
Composition E: surfactant
Photosensitive composite used in the present invention also can containing surfactant as composition E.By containing composition E, the viscosity of adjustable photosensitive composite and surface tension.
Surfactant can use negative ion system, kation system, nonionic system or both sexes any one, preferred surfactant is nonionic system surfactant.Surfactant preferred nonionic system surfactant, more preferably fluorine system surfactant.
In the present invention, spendable surfactant such as can be enumerated: as Mei Jiafa (Megafac) F142D of commercially available product, Mei Jiafa (Megafac) F172, Mei Jiafa (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F177, Mei Jiafa (Megafac) F183, Mei Jiafa (Megafac) F479, Mei Jiafa (Megafac) F482, Mei Jiafa (Megafac) F554, Mei Jiafa (Megafac) F780, Mei Jiafa (Megafac) F781, Mei Jiafa (Megafac) F781-F, Mei Jiafa (Megafac) R30, Mei Jiafa (Megafac) R08, Mei Jiafa (Megafac) F-472SF, Mei Jiafa (Megafac) BL20, Mei Jiafa (Megafac) R-61, Mei Jiafa (Megafac) R-90 (Di Aisheng (DIC) (stock) manufactures), Fu Lade (Fluorad) FC-135, not rad (Fluorad) FC-170C, not rad (Fluorad) FC-430, not rad (Fluorad) FC-431, promise Bake (Novec) FC-4430 (Sumitomo 3M (stock) manufacture), rising sun Jiade (AsahiGuard) AG7105, rising sun Jiade (AsahiGuard) 7000, rising sun Jiade (AsahiGuard) 950, rising sun Jiade (AsahiGuard) 7600, Sha Fulong (Surflon) S-112, Sha Fulong (Surflon) S-113, Sha Fulong (Surflon) S-131, Sha Fulong (Surflon) S-141, Sha Fulong (Surflon) S-145, Sha Fulong (Surflon) S-382, Sha Fulong (Surflon) SC-101, Sha Fulong (Surflon) SC-102, Sha Fulong (Surflon) SC-103, Sha Fulong (Surflon) SC-104, Sha Fulong (Surflon) SC-105, Sha Fulong (Surflon) SC-106 (Asahi Glass (stock) manufacture), Ai Futuo (Eftop) EF351, Ai Futuo (Eftop) EF352, Ai Futuo (Eftop) EF801, Ai Futuo (Eftop) EF802 (Mitsubishi Materials electronics changes into (stock) and manufactures), Fu Jite (Ftergent) 250 (Ni Aosi (Neos) (stock) manufactures).In addition, except described, also can enumerate: KP (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Bao Lifuluo (Polyflow) (common prosperity society chemistry (stock) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials electronics changes into (stock) and manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (stock) manufactures), not rad (Fluorad) (Sumitomo 3M (stock) manufacture), rising sun Jiade (AsahiGuard), Sha Fulong (Surflon) (Asahi Glass (stock) manufacture), each series of precious reason Floex (PolyFox) (manufacture of Europe Nova (OMNOVA) company) etc.
In addition, surfactant can enumerate following multipolymer as preference, described multipolymer contains structural unit A represented by following formula W and structural unit B, and be 1 by the weight average molecular weight (Mw) of the polystyrene conversion measured using tetrahydrofuran as the gel permeation chromatography of solvent, more than 000 and 10, less than 000.
[changing 11]
In formula W, R w1and R w3separately represent hydrogen atom or methyl, R w2represent carbon number more than 1 and the straight-chain alkyl-sub-of less than 4, R w4represent hydrogen atom or carbon number more than 1 and the alkyl of less than 4, L wrepresent carbon number more than 3 and the alkylidene of less than 6, p and q is the quality percentage representing polymerization ratio, p represents more than 10 quality % and the numerical value of below 80 quality %, q represents more than 20 quality % and the numerical value of below 90 quality %, r represents more than 1 and the integer of less than 18, and s represents more than 1 and the integer of less than 10.
Described L wbranched alkylene groups represented by preferred following formula W-2.R in formula W-2 w5represent carbon number more than 1 and the alkyl of less than 4, from the viewpoint of compatibility and to the wetting quality of applied, preferred carbon number more than 1 and the alkyl of less than 3, the more preferably alkyl of carbon number 2 or 3.
P and q sum (p+q) in formula W is p+q=100 i.e. 100 quality % preferably.
The weight average molecular weight (Mw) of described multipolymer more preferably 1, more than 500 and 5, less than 000.
[changing 12]
About the content of the surfactant in photosensitive composite used in the present invention, when setup sheet surface-active agent, relative to the total solid composition of composition, preferably 0.001 quality % ~ 5.0 quality %, more preferably 0.01 quality % ~ 2.0 quality %.
Surfactant can, only containing a kind of, also can contain two or more.When containing two or more, preferably its total amount becomes described scope.
Composition N: blocked isocyanate (blockedisocyanate) compound
Photosensitive composite used in the present invention preferably contains blocked isocyanate compound as composition N.By containing composition N, the cured film that reliability is high can be obtained.Though its mechanism of action is indefinite, can think, by the heating after photo-hardening, the blocked isocyanate base of composition N is through deprotection.Can think in cured film, owing to deriving from the effect of the isocyanate group of composition N, improve with the adhesion of substrate, or isocyanate group and moisture, salt interact, and can obtain the high cured film of reliability thus.
As long as blocked isocyanate compound is for having the compound of blocked isocyanate base, then there is no particular restriction, from indurative viewpoint, in a part, preferably has the compound of plural blocked isocyanate base.The upper limit of the number of blocked isocyanate base is not particularly limited, and preferably less than 6.
In addition, about blocked isocyanate compound, its skeleton is not particularly limited, as long as have two isocyanate group in a part, then can be arbitrary compound, can be aliphatics, alicyclic or aromatic polyisocyanate, such as, can use suitably: 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 '-Anaesthetie 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, tetrachlorobenzene diisocyanate, norbornene alkyl diisocyanate, hydrogenation-1,3-Xylene Diisocyanate, the isocyanate compounds such as hydrogenation-Isosorbide-5-Nitrae-Xylene Diisocyanate, and the polymer of these compounds and by these compounds the compound of prepolymer type skeleton that derives.In these compounds; preferably by the blocked isocyanate compound that the compound be selected from the cohort that is made up of the polymer of toluene diisocyanate (TDI) or methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and these compounds is protected, the blocked isocyanate compound of compound protection more preferably will be selected from the cohort that is made up of the polymer of hexamethylene diisocyanate, isophorone diisocyanate and these compounds.
As long as the polymer of isocyanate compound is the polymer of more than dipolymer, then there is no particular restriction, can illustrate biuret body, isocyanuric acid ester body, adduction object etc., preferred biuret body.
The parent structure of the blocked isocyanate compound in photosensitive composite used in the present invention can be enumerated: biuret form, isocyanuric acid ester type, adduct type, two functional prepolymer types etc.
The sealer forming the enclosed construction of described blocked isocyanate compound can be enumerated: oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazole compound, imide series compound etc.In these compounds, preferred oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound or pyrazole compound, more preferably oxime compound and lactam compound, and then preferred oxime compound, particularly preferably methyl ethyl ketone oxime.
Described oxime compound can enumerate oxime and ketoxime, specifically can illustrate: acetoxime (acetoxime), formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone-oxime, diphenyl-ketoxime etc.
Described lactam compound can illustrate epsilon-caprolactams, butyrolactam etc.
Described phenolic compounds can illustrate: phenol, naphthols, cresols, xylenols, phenol etc. through halogen substiuted.
Described alcoholic compound can illustrate: methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, lactic acid alkyl ester etc.
Described amines can enumerate primary amine and secondary amine, can be aromatic amine, fatty amine, cycloaliphatic amines any one, aniline, diphenylamine, ethylenimine, polyethylene imine based etc. can be illustrated.
Described activity methene compound can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, methyl acetoacetate etc.
Described pyrazole compound can illustrate pyrazoles, methylpyrazole, dimethyl pyrazole etc.
Described mercaptan compound can Exemplary alkyl radicals mercaptan, aryl mercaptan etc.
In photosensitive composite used in the present invention, spendable blocked isocyanate compound can be used as commercially available product and obtains, such as, can preferably use: sieve Nat (Coronate) AP is (Stable) M firmly, Crow Nat (Coronate) 2503, Crow Nat (Coronate) 2515, Crow Nat (Coronate) 2507, Crow Nat (Coronate) 2513, Crow Nat (Coronate) 2555, rice Leo Nat (Millionate) MS-50 (being that Japanese polycarbamate industry (stock) manufactures above), Plutarch Nat (Takenate) B-830, Plutarch Nat (Takenate) B-815N, Plutarch Nat (Takenate) B-820NSU, Plutarch Nat (Takenate) B-842N, Plutarch Nat (Takenate) B-846N, Plutarch Nat (Takenate) B-870N, Plutarch Nat (Takenate) B-874N, Plutarch Nat (Takenate) B-882N (being Mitsui Chemicals (stock) manufacture above), Du draws Nat (Duranate) 17B-60P, Du draws Nat (Duranate) 17B-60PX, Du draws Nat (Duranate) 17B-60P, Du draws Nat (Duranate) TPA-B80X, Du draws Nat (Duranate) TPA-B80E, Du draws Nat (Duranate) MF-B60X, Du draws Nat (Duranate) MF-B60B, Du draws Nat (Duranate) MF-K60X, Du draws Nat (Duranate) MF-K60B, Du draws Nat (Duranate) E402-B80B, Du draws Nat (Duranate) SBN-70D, Du draws Nat (Duranate) SBB-70P, Du draws Nat (Duranate) K6000 (above is Asahi Chemical Industry's chemistry (stock) manufacture), desmodur (Desmodule) BL1100, desmodur (Desmodule) BL1265MPA/X, desmodur (Desmodule) BL3575/1, desmodur (Desmodule) BL3272MPA, desmodur (Desmodule) BL3370MPA, desmodur (Desmodule) BL3475BA/SN, desmodur (Desmodule) BL5375MPA, desmodur (Desmodule) VPLS2078/2, desmodur (Desmodule) BL4265SN, desmodur (Desmodule) PL340, desmodur (Desmodule) PL350, Soviet Union meter Du Er (Sumidule) BL3175 (above for living to change Bayer polycarbamate (Sumika-BayerUrethane) (stock) manufacture) etc.
About the content of the blocked isocyanate compound in photosensitive composite used in the present invention, relative to the total solid composition of photosensitive composite, preferably 0.1 quality % ~ 20 quality %, more preferably 0.5 quality % ~ 10 quality %, and then preferred 1 quality % ~ 5 quality %.
In addition, about the content of the blocked isocyanate compound in photosensitive composite used in the present invention, relative to the total organic solid composition of photosensitive composite, preferably 0.1 quality % ~ 20 quality %, more preferably 0.5 quality % ~ 10 quality %, and then preferred 1 quality % ~ 5 quality %.
If the content of composition N is in described scope, then can obtain cured film excellent in reliability, therefore preferably.
Composition K: polymerization inhibitor
Photosensitive composite used in the present invention preferably contains polymerization inhibitor as composition K.By containing composition K, and suppress by the photogenic polyreaction of leakage, developability is excellent.So-called polymerization inhibitor, refer to and play the following material acted on: hydrogen supply (or awarding hydrogen), energy supply (or awarding energy), supplied for electronic (or awarding electronics) etc. are implemented to the polymerization initiation radical composition produced by polymerization initiator by exposure or heat, make polymerization initiation radical inactivation, suppress polymerization to cause.Such as can use the compound etc. recorded in the paragraph 0154 ~ paragraph 0173 of Japanese Patent Laid-Open 2007-334322 publication.
About the kind of polymerization inhibitor, preferably can adopt hard and not reduce the compound of sensitivity.This polymerization inhibitor can be enumerated: phenothiazine, chlorpromazine (chlorpromazine), levomepromazine (levomepromazine), fluphenazine (fluphenazine), the phenothiazine derivative ， phenoxazines such as thioridazine (thioridazine), 3,7-two (diethylamino) phenoxazine-5-perchlorate, 5-amino-9-(dimethylamino)-10-methyl benzo [a] phenoxazine-7-chlorate, 7-(amoxy)-3H-phenoxazine-3-ketone, 5,9-diamido benzo [a] phenoxazine-7-acetate, the phenoxazine derivants such as 7-ethoxy-3H-phenoxazine-3-ketone, three-p-nitrophenyl ylmethyl, diphenyl bitter taste diazanyl (diphenylpicrylhydrazyl), the stabilized radicals such as jar (unit of capacitance) ten thousand oxygen base (galvinoxyl), quinone, benzoquinones, chloranil, 2,5-, bis--chloranil, 2,6-, bis--chloranil, 2,3-, bis--methylbenzoquinone, 2,5-, bis--methylbenzoquinone, methoxyl benzoquinones, methylbenzoquinone, tetrabromo-quinone, tetrachloroquinone, tetramethyl-benzoquinone, trichlorine benzoquinones, trimethylbenzoquinone, amyl group quinone, amoxy p-dihydroxy-benzene, 2,5-, bis--TBHQ, the quinones such as 2,5-diphenyl 1,4-benzoquinone, alpha-Naphthol, 2-nitro-1-naphthols, betanaphthol, the aphthols such as 1-nitro-beta naphthal, 4-metoxyphenol, 4-thanatol, p-dihydroxy-benzene, phenol, tert-butyl catechol, methyl hydroquinone, normal-butyl phenol, p-dihydroxy-benzene list propyl ether, tert-butyl group cresols, paracresol, 2,6-, bis--Butylated Hydroxytoluene, catechol resorcinol, o-tert-butylphenol, 2,6-, bis--p methoxy phenol, 2,6-, bis--tert-butyl phenol, 2,4-, bis--tert-butyl phenol, 3,5-, bis--tert-butyl phenol, 3,5-, bis--tertiary butyl-4-hydroxy benzoic acid, N, N '-bis--3-(3 ', 5 '-two-tert-butyl-hydroxy phenyl) propiono hexamethylene diamine, 2,2 '-di-2-ethylhexylphosphine oxide (6-Butylated Hydroxytoluene), 3-(4-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl) propionic acid n-octadecane base ester, (the 4-hydroxy-3-methyl-5-tert-butyl group) benzyl malonic acid distearyl ester, 2,4,6-, tri--tert-butyl phenol, 1,6-hexanediol-bis-[3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 2,2-sulfo--diethylene-bis-[3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], two [1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxyethyl-2,4,8,10-tetra-oxaspiro [5, the 5] undecane of 3,9-, 2,2 '-ethylidene-bis--(2,4-, bis--tert-butyl phenol), 1,1,3-tri--(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-tri-(3,5-, bis--tertiary butyl-4-hydroxy benzyl) benzene, three (3,5-, bis--tertiary butyl-4-hydroxy benzyl) isocyanates, three [2-(3 ', 5 '-two-tert-butyl group-4 '-hydroxy benzenes propionyloxy) ethyl] isocyanates, three (the 4-tert-butyl group-2,6-bis--methyl-3-hydroxybenzyl) isocyanates, the phenols such as four [methylene-3-(3 ', 5 '-two-tert-butyl group-4 '-hydroxy phenyl) propionic ester] methane, 2,4-DNP, o-nitrophenol, metanitrophenol, the nitrophenyl phenolics such as p-nitrophenol, gallic acid, gallicin, n-propyl gallate, the nutgall acids such as isoamyl gallate, methylene blue, the pigments such as peacock green, betanaphthyl amine, N-nitroso-cyclohexyl amine salt, two-to amines such as fluorophenyl amine, pyrogallol, single benzyl oxide, benzoquinones, triphenylphosphine, stannous chloride, phenothiazine, chloranil (chloranil), pyridine, nitrobenzene, dinitro benzene, para-totuidine, picric acid, gaultherolin etc.
Polymerization inhibitor particularly preferably is at least one illustrating and be selected from the derivant of phenothiazine, phenoxazine, hindered amine and these compounds.
Phenothiazine and derivant thereof can illustrate: phenothiazine, two-(α-methylbenzyl) phenothiazine, 3,7-dioctyl phenothiazine, two-(α-dimethylbenzyl) phenothiazine, preferred phenothiazine.
Phenoxazine and derivant thereof can illustrate: phenoxazine, 3,7-two (diethylamino) phenoxazine-5-perchlorate, 5-amino-9-(dimethylamino)-10-methyl benzo [a] phenoxazine-7-chlorate, 7-(amoxy)-3H-phenoxazine-3-ketone, 5,9-diamido benzo [a] phenoxazine-7-acetate, 7-ethoxy-3H-phenoxazine-3-ketone, preferred phenoxazine.
Hindered amine and derivant thereof can illustrate: intelligence Ma Suobu (CHIMASSORB) 2020FDL, refined (TINUVIN) 144 of slave, refined (TINUVIN) 765 of slave, slave refined (TINUVIN) 770 (above for BASF (BASF) company manufactures), preferably refined (TINUVIN) 144 of slave.
About the content of the composition K in photosensitive composite used in the present invention, relative to the total solid composition of photosensitive composite, the preferably scope of 0.01 quality % ~ 0.5 quality %, the more preferably scope of 0.1 quality % ~ 0.5 quality %.By adjusting the allotment amount of polymerization inhibitor, can distinguishing be improved and not undermine sensitivity.
Composition S: alkoxysilane compound containing trialkylsilyl group in molecular structure
Photosensitive composite used in the present invention preferably contains alkoxysilane compound containing trialkylsilyl group in molecular structure as composition S.If use alkoxysilane compound containing trialkylsilyl group in molecular structure, then can improve the adhesion of film and the substrate formed by photosensitive composite used in the present invention.
As long as alkoxysilane compound containing trialkylsilyl group in molecular structure is for having the compound of at least one alkoxy Direct Bonding group on the silicon atoms, then there is no particular restriction, preferably there is the compound of dialkoxy silicane base and/or trialkoxy silane base, more preferably there is the compound of trialkoxy silane base.
In the present invention, spendable alkoxysilane compound containing trialkylsilyl group in molecular structure preferably makes the compound that the adhesion of the metals such as the silicon compound such as base material, such as silicon, monox, silicon nitride, gold, copper, molybdenum, titanium, aluminium and cured film improves.Specifically, well-known silane coupling agent etc. are also effective.Preferably there is the silane coupling agent of ethene unsaturated link.
Silane coupling agent such as can be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl dialkoxy silicane, γ-(methyl) acryloxy propyl trialkoxy silane, γ-(methyl) acryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane.In these compounds, more preferably γ-methacryloxypropyl trialkoxy silane, γ-acryloxy propyl trialkoxy silane, vinyl trialkyl oxysilane, γ-glycidyloxypropyl silane.These compounds can be used alone one or combinationally use two or more.
Commercially available product can illustrate KBM-403 or KBM-5103 that SHIN-ETSU HANTOTAI's chemical industry (stock) manufactures.
About the content of the alkoxysilane compound containing trialkylsilyl group in molecular structure in photosensitive composite used in the present invention, relative to the total solid composition of photosensitive composite, preferably 0.1 quality % ~ 30 quality %, more preferably 2 quality % ~ 27 quality %, and then preferred 3 quality % ~ 24 quality %.Alkoxysilane compound containing trialkylsilyl group in molecular structure only can use one, also can containing two or more.When containing two or more, preferably total amount becomes described scope.
(other compositions)
Photosensitive composite used in the present invention, except described composition, also can contain other compositions.Other compositions can illustrate the compound with epoxy radicals, the compound with oxetanylmethoxy.
< has the compound of epoxy radicals and has the compound > of oxetanylmethoxy
Photosensitive composite used in the present invention also can containing at least one be selected from the cohort that is made up of the compound with epoxy radicals and the compound with oxetanylmethoxy.If described embodiment, then the hardness of gained hardening thing is more excellent.
[there is the compound of epoxy radicals]
Photosensitive composite used in the present invention also can containing the compound with epoxy radicals.The compound with epoxy radicals can only have an epoxy radicals in the molecule, preferably has two or more.
The concrete example in molecule with the compound of plural epoxy radicals can be enumerated: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc.
These compounds can be used as commercially available product and obtain.Such as bisphenol A type epoxy resin is JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above for japan epoxy resin (JapanEpoxyResin) (stock) manufactures), and Chinese mugwort is than cloning (EPICLON) 860, Chinese mugwort than clone (EPICLON) 1050, Chinese mugwort ratio clone (EPICLON) 1051, Chinese mugwort than clone (EPICLON) 1055 (being Di Aisheng (DIC) (stock) manufacture above) etc., bisphenol f type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above for japan epoxy resin (JapanEpoxyResin) (stock) manufactures), Chinese mugwort is than cloning (EPICLON) 830, Chinese mugwort than clone (EPICLON) 835 (being that Di Aisheng (DIC) (stock) manufactures above), LCE-21, RE-602S (above is Japanese chemical drug (stock) manufacture) etc., phenol novolak type epoxy resin is JER152, JER154, JER157S70, JER157S65 (above for japan epoxy resin (JapanEpoxyResin) (stock) manufactures), and Chinese mugwort is than cloning (EPICLON) N-740, Chinese mugwort than clone (EPICLON) N-770, Chinese mugwort ratio clone (EPICLON) N-775 (being that Di Aisheng (DIC) (stock) manufactures above) etc., cresol novolak type epoxy resin being Chinese mugwort ratio clone (EPICLON) N-660, ending than clone (EPICLON) N-665, ending than cloning (EPICLON) N-670, Chinese mugwort than cloning (EPICLON) N-673, Chinese mugwort ratio clone (EPICLON) N-680, Chinese mugwort ratio clone (EPICLON) N-690, ending than clone (EPICLON) N-695 (being Di Aisheng (DIC) (stock) manufacture above), EOCN-1020 (being Japanese chemical drug (stock) manufacture above) etc., aliphatic epoxy resin is Ai Dike resin (ADEKARESIN) EP-4080S, Ai Dike resin (ADEKARESIN) EP-4085S, Ai Dike resin (ADEKARESIN) EP-4088S (being that Ai Dike (ADEKA) (stock) manufactures above), Sai Luo West Germany (Celloxide) 2021P, Sai Luo West Germany (Celloxide) 2081, Sai Luo West Germany (Celloxide) 2083, Sai Luo West Germany (Celloxide) 2085, EHPE3150, Ai Boli obtains (EPOLEAD) PB3600, Ai Boli obtains (EPOLEAD) PB4700 (above for Daicel (Daicel) chemical industry (stock) manufactures) etc.In addition, also can enumerate: Ai Dike resin (ADEKARESIN) EP-4000S, Ai Dike resin (ADEKARESIN) EP-4003S, Ai Dike resin (ADEKARESIN) EP-4010S, Ai Dike resin (ADEKARESIN) EP-4011S (above for Ai Dike (ADEKA) (stock) manufactures), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (being that Ai Dike (ADEKA) (stock) manufactures above) etc.
In addition, also can use the carbamate compounds class with skeletal oxirane recorded in Jap.P. examined patent publication 58-49860 publication, Jap.P. examined patent publication 56-17654 publication, Jap.P. examined patent publication 62-39417 publication, Jap.P. examined patent publication 62-39418 publication suitably, these contents are incorporated in instructions of the present invention.
When photosensitive composite used in the present invention contains the compound with epoxy radicals, preferably contain with the scope of 0.1 quality % ~ 20 quality % of the total solid composition of composition, more preferably contain with the scope of 0.5 quality % ~ 10 quality %, and then preferably contain with the scope of 1 quality % ~ 5 quality %.
Photosensitive composite used in the present invention only can contain a kind of compound with epoxy radicals, also can containing two or more.When containing two or more, preferably total amount becomes described scope.
[there is the compound of oxetanylmethoxy]
Photosensitive composite used in the present invention also can containing the compound with oxetanylmethoxy.The compound with oxetanylmethoxy can only have an oxetanylmethoxy in the molecule, preferably has two or more.
The concrete example with the compound of oxetanylmethoxy can use sub-imperial oxetanes (AronOxetane) OXT-121, sub-imperial oxetanes (AronOxetane) OXT-221, sub-imperial oxetanes (AronOxetane) OX-SQ, sub-imperial oxetanes (AronOxetane) PNOX (above for East Asia synthesis (stock) manufactures).
In addition, the compound containing oxetanylmethoxy is preferably used alone or used in combination with the compound containing epoxy radicals.
When photosensitive composite used in the present invention contains the compound with oxetanylmethoxy, preferably contain with the scope of 0.1 quality % ~ 20 quality % of the total solid composition of composition, more preferably contain with the scope of 0.5 quality % ~ 10 quality %, and then preferably contain with the scope of 1 quality % ~ 5 quality %.
Photosensitive composite used in the present invention only can contain a kind of compound with oxetanylmethoxy, also can containing two or more.When containing two or more, preferably total amount becomes described scope.
In photosensitive composite used in the present invention, other compounds (such as containing the compound etc. of alkoxy methyl) beyond described in also can including in the scope not departing from purport of the present invention.Compound containing alkoxy methyl can enumerate the compound recorded in the paragraph 0192 ~ paragraph 0194 of Japanese Patent Laid-Open 2011-221494 publication.
< antioxidant >
In photosensitive composite used in the present invention, except described composition, also antioxidant can be contained.In addition, antioxidant is the compound beyond composition K mentioned above.About antioxidant, well-known antioxidant can be contained.By adding antioxidant, have can prevent cured film painted, maybe can reduce the thinning and advantage of heat resistant transparent excellence of thickness caused by decomposing.
This antioxidant such as can be enumerated: phosphorous antioxidant, amide-type, hydrazides class, hindered phenol system antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc.In these compounds, from painted, the viewpoint that thickness is thinning of cured film, particularly preferably hindered phenol system antioxidant, phosphorous antioxidant, most preferably hindered phenol system antioxidant.These antioxidants can be used alone one, also can mix two or more.
Preferred commercially available product can be enumerated: Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-80 (above for Ai Dike (ADEKA) (stock) manufactures), gorgeous good promise (Irganox) 1098 (being that BASF (BASF) company manufactures above).
There is no particular restriction for the content of antioxidant, relative to the total solid composition of photosensitive composite, and preferably 0.1 quality % ~ 10 quality %, more preferably 0.2 quality % ~ 5 quality %, and then preferred 0.5 quality % ~ 4 quality %.
< binder polymer >
From viewpoint such as raising distinguishing and epithelium characteristic etc., photosensitive composite used in the present invention also can contain binder polymer.
There is no particular restriction for binder polymer, can use well-known binder polymer, preferably use threadlike organic polymers.This threadlike organic polymers can use arbitrarily well-known polymkeric substance.Preferably select in water or alkalescent water as solubility or bloating tendency threadlike organic polymers in order to water development or alkalescent water development can be carried out.Threadlike organic polymers is according to not only as peel-forming agent, and as the purposes of water, alkalescent water or organic solvent developer choice for use.If such as use water dissolvable organic polymer, water development can be carried out.This threadlike organic polymers can be enumerated: the polymkeric substance on side chain with carboxylic acid group, such as Japanese Patent Laid-Open No. Sho 59-44615 publication, Jap.P. examined patent publication 54-34327 publication, Jap.P. examined patent publication 58-12577 publication, Jap.P. examined patent publication 54-25957 publication, Japanese Patent Laid-Open No. Sho 54-92723 publication, Japanese Patent Laid-Open No. Sho 59-53836 publication, the compound recorded in Japanese Patent Laid-Open No. Sho 59-71048 publication, namely, the monomer making to have carboxyl separately or the resin of copolymerization, be hydrolyzed making the monomer anhydride unit that is independent or copolymerization with acid anhydrides or resin that is half-esterification or half amide, with unsaturated monocarboxylic and acid anhydrides by the epoxy acrylate etc. of epoxy resin modification.The monomer with carboxyl can be enumerated: acrylic acid, methacrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, 4-carboxyl styrene etc., the monomer with acid anhydrides can enumerate maleic anhydride etc.
Wherein, preferably there is the acrylic resin of acidic group on side chain.In addition, so-called acrylic resin, refers to the polymkeric substance by (methyl) acrylate monomer or vinyl monomer copolymerization, also can contain the structural unit beyond the methacrylic acid acid esters such as the styrene of less than 20 % by mole.Acidic group optimization acid base or phenylol.Be used for importing preferred (methyl) acrylic acid of monomer of acidic group.
In addition, the acid cellulose derivant similarly on side chain with carboxylic acid group is had.In addition, on the polymkeric substance with hydroxyl, the compound etc. of addition cyclic acid anhydride is useful.
There is no particular restriction for the content of the binder polymer in photosensitive composite used in the present invention, relative to the total solid composition of photosensitive composite, preferably 0 quality % ~ 40 quality %, more preferably 0 quality % ~ 30 quality %, and then preferred 0 quality % ~ 20 quality %, particularly preferably 0 quality % ~ 10 quality %, most preferably 0 quality % ~ 5 quality %.
In photosensitive composite used in the present invention, relative to the total solid composition of photosensitive composite, weight average molecular weight is more than 10, the content preferably 0 quality % ~ 40 quality % of the component of polymer of 000, more preferably 0 quality % ~ 30 quality %, and then preferably 0 quality % ~ 20 quality %, particularly preferably 0 quality % ~ 10 quality %, most preferably 0 quality % ~ 5 quality %.
If the content of component of polymer is in described scope, then developability and hardening excellence.
[other compositions]
In photosensitive composite used in the present invention, optionally except described composition, also can add other compositions such as plasticiser, thermal acid generator, acid proliferation generator.About these compositions, such as, can use compound, other well-known compounds of recording in Japanese Patent Laid-Open 2009-98616 publication, Japanese Patent Laid-Open 2009-244801 publication.In addition, also the various ultraviolet light absorber recorded in " the new expansion (daily magazine industry newspaper office (stock)) of polymeric additive " or metal passivator etc. can be added in photosensitive composite used in the present invention.
(panel substrate)
The feature of panel substrate of the present invention is: it is manufactured by the manufacture method of panel substrate of the present invention.
Liquid crystal indicator and organic EL display is comprised in panel substrate of the present invention.
(touch panel display device)
The feature of touch panel display device of the present invention is to possess panel substrate of the present invention.Touch panel of the present invention can be any one of the well-known modes such as resistive film mode, electrostatic capacitance mode, ultrasound wave mode, way of electromagnetic induction.Wherein, preferred electrostatic capacitance mode.
The touch panel of electrostatic capacitance mode can enumerate touch panel disclosed in touch panel disclosed in Japanese Patent Laid-Open 2010-28115 publication or No. 2012/057165th, International Publication.Other touch panels can be enumerated: so-called embedded (in-cell) type (such as Fig. 5, Fig. 6, Fig. 7, Fig. 8 of Jap.P. spy table 2012-517051 publication), so-called outer insert-type (Figure 19 of such as Japanese Patent Laid-Open 2013-168125), one chip glass touch panel (OneGlassSolution, OGS) type, overlayer touches (TouchonLens, TOL) type, other form (such as Fig. 6 of Japanese Patent Laid-Open 2013-164871 publication).
In addition, Fig. 4 represents the formation concept map of an example of the liquid crystal indicator of the function with touch panel.
In addition, the alloy of the preferred silver of the detecting electrode of touch panel, copper, aluminium, titanium, molybdenum, these metals.
In Fig. 4,110 represent pixel substrate, and 140 represent liquid crystal layer, and 120 represent substrate in opposite directions, and 130 represent detecting means.Pixel substrate 110 has Polarizer 111, transparency carrier 112, common electrode 113, insulation course 114, pixel electrode 115, alignment films 116 successively from the downside of Fig. 4.Substrate 120 has alignment films 121, colored filter 122, transparency carrier 123 successively from the downside of Fig. 4 in opposite directions.Detecting means 130 has phase retardation film 124, protective seam 126, following layer 127, Polarizer 128 respectively.In addition, in Fig. 4,125 is sensing detecting electrode.
In the manufacture method of base plate of liquid crystal panel of the present invention, the photosensitive composite through sclerosis is used as protective seam 126.
And then, even if in the liquid crystal indicator of static drive mode, the pattern that also Display designing is high by application the present invention.About its example, the present invention can be applied as the dielectric film recording such polymer network type liquid crystal in Japanese Patent Laid-Open 2001-125086 publication.
In addition, Fig. 5 is the formation concept map of another example of the liquid crystal indicator of the function with touch panel.
Touch panel display device comprises: bottom display board 200, possesses thin film transistor (TFT) (TFT) 440, is equivalent to thin film transistor display panel; Top display board 300, with bottom display board 200 in opposite directions, with bottom display board 200 face in opposite directions on possess multiple colored filter 330, be equivalent to colored filter display board; And liquid crystal layer 400, be formed between bottom display board 200 and top display board 300.Liquid crystal layer 400 is containing liquid crystal molecule (not shown).
Bottom display board 200 comprises the 1st insulated substrate 210, the thin film transistor (TFT) (TFT) be configured on the 1st insulated substrate 210, the pixel electrode 290 that is formed in the dielectric film 280 on the upper surface of thin film transistor (TFT) (TFT) and is configured on dielectric film 280.Thin film transistor (TFT) (TFT) can contain the gate insulating film 240 of gate electrode 220, covering grid electrode 220, semiconductor layer 250, ohmic contact layer 260, ohmic contact layer 262, source electrode 270 and drain electrode 272.
In dielectric film 280, be formed with contact hole 282 in the mode that the drain electrode 272 of thin film transistor (TFT) (TFT) exposes.
Top display board 300 comprises: on the face being configured in the 2nd insulated substrate 310 and with the light obstructing member 320 of rectangular arrangement, the alignment films 350 be configured on the 2nd insulated substrate 310, be configured in the colored filter 330 in alignment films 350 and be configured on colored filter 330 and corresponding with the pixel electrode 290 of bottom display board 200 and execute alive common electrode 370 to liquid crystal layer 400.
In the liquid crystal indicator shown in Fig. 5, the another side of the 2nd insulated substrate 310 configures sensing electrode 410, protective seam 420, drive electrode 430 and dielectric film 280.Like this, in the manufacture of the liquid crystal indicator shown in Fig. 5, when forming top display board 300, the sensing electrode 410 of the inscape as touch-screen (touchscreen), protective seam 420 and drive electrode 430 etc. can be formed together.
In the manufacture method of base plate of liquid crystal panel of the present invention, the photosensitive composite through sclerosis is used as protective seam 420.
In addition, touch panel display device of the present invention can preferably be enumerated: in the what is called recorded in Japanese Patent Laid-Open 2012-230657 publication the touch panel of insert-type manufacture method in, use panel substrate of the present invention as herein with the embodiment of display element touching measuring ability; Or in the manufacture method of the touch panel of the outer insert-type of the what is called recorded in Japanese Patent Laid-Open 2013-168125 publication, use panel substrate of the present invention as the embodiment of liquid crystal indicator herein.
[embodiment]
Below enumerate embodiment more specifically to be illustrated the present invention.Material shown in following embodiment, use amount, ratio, contents processing, processing sequence etc. only otherwise depart from purport of the present invention, then can suitably change.Therefore, scope of the present invention is not limited to concrete example shown below.In addition, as long as no special instructions, then " part ", " % " are quality criteria.
The each composition used in embodiment and comparative example as described below.
(composition A)
A-1: the propenoic methyl carbamate (U-15HA, Xin Zhong village chemical industry (stock) manufacture) that face can be above
A-2: dipentaerythritol acrylate (DPHA, Japanese chemical drug (stock) manufactures)
A-3: tetramethylol methane tetraacrylate (A-TMMT, Xin Zhong village chemical industry (stock) manufacture)
(composition B)
B-1: compound 1 (composite, with reference to following), oxime ester compound
B-2: gorgeous good solid (IRGACURE) OXE02 (manufacture of BASF (BASF) company), oxime ester compound, following structure
[changing 13]
(composition C)
C-1:PMA-ST (Nissan Chemical Industries (stock) manufacture), silicon dioxide granule, mean grain size 10nm ~ 15nm
C-2:MIBK-ST-L (Nissan Chemical Industries (stock) manufacture), silicon dioxide granule, mean grain size 40nm ~ 50nm
C-3:SX866 (JSR (stock) manufacture), Styrene And Chloroalkyl Acrylates system hollow-particle (powder)
(components D)
D-1: Hai Suobu (Hisolve) EDM (eastern nation chemical industry (stock) manufacture), diethylene glycol ethyl methyl ether
D-2:PGMEA (Daicel (Daicel) chemical industry (stock) manufacture), propylene glycol methyl ether acetate
(composition E)
E-1: Mei Jiafa (Megafac) F554 (Di Aisheng (DIC) (stock) manufactures), fluorine system surfactant
(binder polymer)
F-1: propylene glycol methyl ether acetate 45% solution (BzMA: MAA (mass ratio)=70: 30 of benzyl methacrylate (BzMA)/methacrylic acid (MAA) multipolymer, weight average molecular weight=30,000) (Teng Cang changes into (stock) manufactures)
The synthesis > of < compound 1 (B-1)
[synthesis of compd A]
Ethyl carbazole (100.0g, 0.512mol) is dissolved in 260ml chlorobenzene, after being cooled to 0 DEG C, adds aluminum chloride (70.3g, 0.527mol).Then dripped toluoyl chlorine (81.5g, 0.527mol) with 40 minutes, be warmed up to room temperature (25 DEG C, identical below) and stir 3 hours.Then, after being cooled to 0 DEG C, aluminum chloride (75.1g, 0.563mol) is added.Dripped 4-chlorobutanoylchloride (79.4g, 0.563mol) with 40 minutes, be warmed up to room temperature and stir 3 hours.The 35 quality % aqueous hydrochloric acid solutions of 156ml and the mixed solution of 392ml distilled water are cooled to 0 DEG C, dropwise reaction solution.After the solid suction filtration of precipitation, clean with distilled water and methyl alcohol, after carrying out recrystallization with acetonitrile, obtain the compd A (output 164.4g, productive rate 77%) of following structure.
[changing 14]
[synthesis of compd B]
The compd A (20.0g, 47.9mmol) of described acquisition is dissolved in the tetrahydrofuran (THF) of 64ml, adds 4-chlorobenzenethiol (7.27g, 50.2mmol) and sodium iodide (0.7g, 4.79mmol).Then in reactant liquor, add NaOH (2.0g, 50.2mmol), reflux 2 hours.Then, after being cooled to 0 DEG C, dripping SM-28 (11.1g, 57.4mmol, first sodium oxide molybdena 28% methanol solution, and pure pharmaceutical worker's industry (stock) manufacture of light) with 20 minutes, be warmed up to room temperature and stir 2 hours.Then, after being cooled to 0 DEG C, dripping isoamyl nitrite (6.73g, 57.4mmol) with 20 minutes, be warmed up to room temperature and stir 3 hours.Reactant liquor being diluted in 120ml acetone, being added drop-wise in the 0.1N aqueous hydrochloric acid solution through being cooled to 0 DEG C.After the solid suction filtration of precipitation, clean with distilled water.Then carry out recrystallization with acetonitrile, obtain the compd B (output 17.0g, productive rate 64%) of following structure.
[changing 15]
[synthesis of compound 1]
Compd B (18.0g, 32.4mmol) is dissolved in the 1-METHYLPYRROLIDONE (NMP) of 90ml, adds triethylamine (Et 3n, 3.94g, 38.9mmol).Then, after being cooled to 0 DEG C, after dripping acetyl chloride (AcCl, 3.05g, 38.9mmol) with 20 minutes, being warmed up to room temperature and stirring 2 hours.Reactant liquor is added drop-wise to 150ml through being cooled in the distilled water of 0 DEG C, by separate out solid suction filtration after, clean with the isopropyl alcohol through being cooled to 0 DEG C of 200ml, after drying, obtain compound 1 (output 19.5g, productive rate 99%).
[changing 16]
In addition, the structure of the compound 1 of gained is identified by nuclear magnetic resonance (NuclearMagneticResonance, NMR).
1H-NMR(400MHz，CDCl 3)：δ＝8.86(s，1H)，8.60(s，1H)，8.31(d，1H，J＝8.0Hz)，8.81(d，1H，J＝8.0Hz)，7.51-7.24(m，10H)，7.36(q，2H，7.4Hz)，3.24-3.13(m，4H)，2.36(s，3H)，2.21(s，3H)，1.50(t，3H，7.4Hz)。
(embodiment 1 ~ embodiment 11 and comparative example 1 ~ comparative example 7)
The preparation > of < photosensitive composite
As recording in following table 1, each composition allotment stirred and make solution and/or the dispersion liquid of organic solvent, filtering with the teflon filtrator in 0.3 μm, aperture, obtain photosensitive composite of the present invention.Except solid component concentration, the unit of each composition of following table is mass parts.In addition, "-" in table represents not containing this composition.
The evaluation > of < coating film thickness homogeneity
(embodiment 1 ~ embodiment 11 and comparative example 1 ~ comparative example 7)
Prepare liquid crystal cells mother substrate (substrate size G5), this liquid crystal cells mother substrate is after the ITO sputter carrying out liquid crystal inclosure, laminating, thinning process, effects on surface, completes the patterning touching detecting electrode and forms.Slit coater (slit coater that Tokyo answers chemical industry (stock) to manufacture) is used to be coated with this photosensitive composite on liquid crystal cells mother substrate, utilize heating plate prebake conditions 120 second and solvent is volatilized at 90 DEG C, obtain the film after the solvent removing of the photosensitive composite of thickness 2.2 μm.Then high-pressure mercury-vapor lamp is utilized to carry out 500mJ/cm 2the illumination of (conversion of i ray) is penetrated, and then utilizes baking oven at 120 DEG C, carry out baking in 60 minutes, is produced on the panel substrate possessing diaphragm on the surface thus.After making display panel, panel is cut out, carry out each mensuration.
In addition, the thickness touching detecting electrode measures as following.Completing on the described liquid crystal cells mother substrate touching detecting electrode patterning, using ET200 (jump/film thickness gauge that little Ban research institute (stock) manufactures), being measured the height of described touch detecting electrode wiring by contact pin type.Using the glass surface of gained with touch detecting electrode surface height difference as touching detecting electrode thickness.
(embodiment 12 ~ embodiment 14)
Except the starting material of substrate and thickness being set as the content of record in table, all carry out the process identical with embodiment 2.About the substrate raw materials in table, PC refers to polycarbonate, and PI refers to polyimide, and PET refers to polyethylene terephthalate.
(embodiment 15)
Except being set as except 51nm by the thickness touching detecting electrode, carry out the process identical with embodiment 2.
(embodiment 16)
Except being set as except 153nm by the thickness touching detecting electrode, carry out the process identical with embodiment 2.
(embodiment 17)
The material touching detecting electrode is set as copper, and thickness is set as 153nm, in addition, carry out the process identical with embodiment 2.
(embodiment 18)
Except the thickness after being removed by the solvent of photosensitive composite is set as, except 3.0 μm, carrying out the process identical with embodiment 2.
(embodiment 19)
Except the thickness after being removed by the solvent of photosensitive composite is set as, except 1.8 μm, carrying out the process identical with embodiment 2.
[the smooth voltinism evaluation of micro concavo-convex]
For the diaphragm in the panel substrate of gained, ET200 (jump/film thickness gauge that little Ban research institute (stock) manufactures) is used to measure ITO wiring and the difference of height that there is no the part that ITO connects up.1,2 is usage range.
On 1 film, jump is less than 10nm
On 2 films, jump is more than 10nm and is less than 20nm
On 3 films, jump is more than 20nm and is less than 30nm
On 4 films, jump is more than 30nm and is less than 40nm
On 5 films, jump is more than 40nm
[evaluation of substrate tracing ability]
ET200 (jump/film thickness gauge that little Ban research institute (stock) manufactures) is used to measure the film thickness distribution (without wiring portion) of the diaphragm in the panel substrate of gained; calculate (maximal value-minimum value)/mean value, measure the film thickness uniformity of film on substrate thus.1,2 is usage range.
1 film thickness distribution is less than 2%
2 film thickness distribution are less than 3%
3 film thickness distribution are less than 4%
4 film thickness distribution are less than 5%
5 film thickness distribution are more than 5%
[evaluation of pencil hardness (skin hardness)]
Each photosensitive composite of described preparation is spin-coated on glass substrate (100mm × 100mm), at 90 DEG C, carries out the prebake conditions in 120 seconds, obtain the coated film of thickness 2.0 μm.Then, high-pressure mercury-vapor lamp is utilized to carry out 500mJ/cm 2the illumination of (conversion of i ray) is penetrated, and then utilizes baking oven at 120 DEG C, carry out baking in 60 minutes, makes cured film thus.
The method (heavy burden 750g) according to JISK5600 is utilized to carry out pencil hardness test, evaluated for film intensity to the cured film of gained.More than 2H is usage range.
[table 2]
Picture, indicated by described table 2, according to the manufacture method of panel substrate of the present invention, can manufacture the panel substrate of the smooth voltinism of micro concavo-convex of diaphragm, substrate tracing ability and pencil hardness excellence.
(making of touch panel display device)
The panel substrate of gained in various embodiments of the present invention is used to make touch panel display device.Other parts of display device make according to the manufacture method recorded as Fig. 6 in Japanese Patent Laid-Open 2013-164871 publication.Display performance, the touch detection perform of made display device are all excellent.

Claims (6)

1. a manufacture method for panel substrate, is characterized in that comprising successively:
As the painting process possessed on the face touching detecting electrode photosensitive composite being coated on display panel of operation 1;
As the solvent removal step removing desolventizing from be coated with described photosensitive composite of operation 2; And
As the hardening process being made the described photosensitive composite sclerosis through solvent removing by light and/or heat of operation 3,
Described photosensitive composite contains as above (methyl) acrylate compounds of the face energy of composition A, as the Photoepolymerizationinitiater initiater of composition B, as organic filler or the inorganic particulate of composition C, and as the solvent of components D, relative to the total solid component amount beyond the described composition C in described photosensitive composite, the content of described composition A is 50 quality % ~ 98 quality %, the viscosity of described photosensitive composite is 3mPas ~ 30mPas, the surface tension of described photosensitive composite is 20mN/m ~ 30mN/m, be 10 quality % ~ 50 quality % relative to the solid constituent amount of described photosensitive composite total amount, and
Described display panel possesses touch detecting electrode at least one side, have described touch detecting electrode face at least partially on possess the glass substrate of below thickness 0.3mm or the resin substrate of below thickness 1.0mm, the thickness of described touch detecting electrode is more than 30nm.
2. the manufacture method of panel substrate according to claim 1, wherein said photosensitive composite also contains surfactant as composition E.
3. the manufacture method of panel substrate according to claim 1 and 2, wherein fixes display panel by absorption in described painting process.
4. the manufacture method of panel substrate according to claim 1 and 2, the substrate wherein possessed at least one of face with described touch detecting electrode is glass substrate, and before described painting process, also comprise the thinning operation that glass substrate is ground.
5. a panel substrate, it is manufactured by the manufacture method of panel substrate described any one of Claims 1-4.
6. a touch panel display device, it possesses panel substrate according to claim 5.
CN201510639546.6A 2014-09-30 2015-09-30 Manufacturing method for display panel substrate, display panel substrate, and touch panel display device Pending CN105467640A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-202215 2014-09-30
JP2014202215A JP2016071246A (en) 2014-09-30 2014-09-30 Manufacturing method of display panel substrate, display panel substrate, and touch panel display device

Publications (1)

Publication Number Publication Date
CN105467640A true CN105467640A (en) 2016-04-06

Family

ID=55605505

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510639546.6A Pending CN105467640A (en) 2014-09-30 2015-09-30 Manufacturing method for display panel substrate, display panel substrate, and touch panel display device

Country Status (2)

Country Link
JP (1) JP2016071246A (en)
CN (1) CN105467640A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107087883A (en) * 2017-04-27 2017-08-25 涿州皓原箔业有限公司 A kind of manicure aluminium foil and its manufacture method
CN109643062A (en) * 2016-08-30 2019-04-16 富士胶片株式会社 Photosensitive polymer combination, transfer film, touch panel protective film, touch panel and its manufacturing method and image display device
CN110023084A (en) * 2016-12-05 2019-07-16 富士胶片株式会社 The front panel of optical film and the image display device with the optical film, image display device, the reflecting mirror with image display function, resistive touch panel and capacitive touch panel

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108899330A (en) * 2018-07-06 2018-11-27 京东方科技集团股份有限公司 Display panel and preparation method thereof, display device

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155440A (en) * 2007-12-26 2009-07-16 Nippon Shokubai Co Ltd Antistatic hardcoat composition, and optical article
JP5197089B2 (en) * 2008-03-27 2013-05-15 株式会社ジャパンディスプレイセントラル Method and apparatus for manufacturing flat display device
JP2010254795A (en) * 2009-04-24 2010-11-11 Fujifilm Corp Compound, photosensitive composition, and method for producing processed substrate
JP5520187B2 (en) * 2010-10-14 2014-06-11 日東電工株式会社 Adhesive layer for transparent conductive film, transparent conductive film with adhesive layer, transparent conductive laminate, and touch panel
JP5914978B2 (en) * 2011-03-31 2016-05-11 大日本印刷株式会社 Photocurable resin composition
JP6277617B2 (en) * 2012-07-23 2018-02-14 セントラル硝子株式会社 Adhesive composition, adhesion method thereof, and peeling method after adhesion

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109643062A (en) * 2016-08-30 2019-04-16 富士胶片株式会社 Photosensitive polymer combination, transfer film, touch panel protective film, touch panel and its manufacturing method and image display device
CN109643062B (en) * 2016-08-30 2023-03-03 富士胶片株式会社 Photosensitive resin composition, transfer film, protective film for touch panel, method for producing touch panel, and image display device
CN110023084A (en) * 2016-12-05 2019-07-16 富士胶片株式会社 The front panel of optical film and the image display device with the optical film, image display device, the reflecting mirror with image display function, resistive touch panel and capacitive touch panel
CN110023084B (en) * 2016-12-05 2021-03-09 富士胶片株式会社 Optical film, front panel of image display device having the same, image display device, mirror with image display function, resistive touch panel, and capacitive touch panel
CN107087883A (en) * 2017-04-27 2017-08-25 涿州皓原箔业有限公司 A kind of manicure aluminium foil and its manufacture method

Also Published As

Publication number Publication date
JP2016071246A (en) 2016-05-09

Similar Documents

Publication Publication Date Title
TWI693260B (en) Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device
CN103019032B (en) Photosensitive resin composition, the forming method of cured film, cured film, organic EL display and liquid crystal display device
CN105683838B (en) Photosensitive polymer combination, the manufacturing method of cured film, cured film, liquid crystal display device and organic EL display device
CN106575078A (en) Photosensitive composition, method for producing curable film, curable film, touch panel, touch panel display device, liquid crystal display device, and organic el display device
TWI690559B (en) Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device
JP6215346B2 (en) Curable composition, method for producing cured film, cured film, and display device
CN105911818A (en) Photoresist composition, hardening film making method, hardening film and application thereof
CN104412161A (en) Photosensitive resin composition, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device
CN107015434A (en) Photosensitive composite, solidfied material preparation method, cured film, display device and Trackpad
CN105467640A (en) Manufacturing method for display panel substrate, display panel substrate, and touch panel display device
TW201714966A (en) Photosensitive compositions and use thereof for producing a hardened film having excellent heat resistance, flatness, transparency, and resolvability
CN106933031A (en) Photosensitive composite, cured film preparation method, cured film, Trackpad and display device
CN105467765A (en) Photosensitive composition, manufacturing method for hard coating film, hard coating film, and applications thereof
CN105911819A (en) Photoresist composition, hardening film making method, hardening film and application thereof
TWI676080B (en) Curable composition, cured film, organic electroluminescence display device, liquid crystal display device, and touch panel display device
CN104272188A (en) Photosensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid-crystal display device
KR101791452B1 (en) Curable composition, method for producing cured film, cured film, and display device
JP6309624B2 (en) Photosensitive composition, method for producing cured film, cured film, liquid crystal display device, organic EL display device, touch panel and touch panel display device
CN105911817A (en) Photo-electric sensitivity composition, hardening film making method, hardening film, touch screen and display screen
JP2019172864A (en) Thermosetting composition
JP2015196739A (en) Curable composition, production method of cured film, cured film, and display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160406

WD01 Invention patent application deemed withdrawn after publication