CN101450837A - Composition for forming flat panel display component, transfer printing film and application thereof - Google Patents

Composition for forming flat panel display component, transfer printing film and application thereof Download PDF

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CN101450837A
CN101450837A CNA2008101765132A CN200810176513A CN101450837A CN 101450837 A CN101450837 A CN 101450837A CN A2008101765132 A CNA2008101765132 A CN A2008101765132A CN 200810176513 A CN200810176513 A CN 200810176513A CN 101450837 A CN101450837 A CN 101450837A
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methyl
acrylate
flat panel
panel display
display component
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菅原哲德
井上靖健
间嶋宽
三田伦广
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JSR Corp
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/22—Electrodes, e.g. special shape, material or configuration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/38—Dielectric or insulating layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/44—Optical arrangements or shielding arrangements, e.g. filters, black matrices, light reflecting means or electromagnetic shielding means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems

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  • Compositions Of Macromolecular Compounds (AREA)
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  • Gas-Filled Discharge Tubes (AREA)
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Abstract

The present invention provides a composition for forming a FPD component capable of forming a FPD panel component with high luminous transmittance, reflectance ratio, surface smoothness and film thickness uniformity. Further the invention provides a composition layer transfer film for forming the FPD component formed with above composition with excellent flexibility, transfer performance and maneuverability. Further the invention provides a method for manufacturing the FPD panel component for forming the FPD panel component with high luminous transmittance, reflectance ratio, surface smoothness and film thickness uniformity, and excellent flexibility, transfer performance and maneuverability. The composition for forming the FPD component contains: (A) inorganic powder, (B) agglutinate resin, (C) compound containing silicon alkyl and (D) metal alkoxide, wherein the agglutinate resin (B) contains (B-1) (methyl) acrylic polymers, which has polyoxyalkylenes section, and weight average molecular weight is from 10,000 to 50,000.

Description

Flat panel display component forms with composition, transfer film and application thereof
Technical field
The present invention relates to be suitable for form the resin combination that contains inorganic powder of the panel component of flat-panel monitor, the flat panel display component manufacture method that has the transfer film of the resin layer that contains inorganic powder that forms by said composition and use this transfer film.
Background technology
In recent years, as flat fluorescence display body, plasma display panel (PDP) (below be also referred to as " PDP " } and flat-panel monitor such as electroluminescent display (below be also referred to as " FED ") (below be also referred to as " FPD ") noticeable.PDP is by forming transparency electrode, enclose rare gas elementes such as argon or neon between two sheet glass that are close, and causes plasma discharge and makes gas luminescence, thereby make light-emitting phosphor, demonstrates the indicating meter of information.On the other hand, FED discharges electronics by applying electric field from negative electrode to vacuum, on the fluor of this electron irradiation to the anode, thereby makes light-emitting phosphor, demonstrates the indicating meter of information.Fig. 1 is the synoptic diagram that the cross-sectional shape of AC type PDP is shown.
As the manufacture method of dielectric medium, next door, electrode, fluor, colour filter and the blackstreak (matrix) of this FPD, the known resin layer that contains inorganic powder that for example on substrate, forms, and with the method (with reference to patent documentation 1) of its roasting.
According to this method, on substrate, form in the operation of the resin layer that contains inorganic powder, use is transferred to method on the substrate with this resin layer that contains inorganic powder having on the flexible supporting film transfer film that forms the resin layer that contains inorganic powder that contains inorganic powder and binding resin, can form film uniformity and the good panel component of surface uniformity well by operating efficiency, therefore preferably be adopted.
Patent documentation 1: the spy opens flat 9-102273 communique
Summary of the invention
But in traditional transfer film, the resin layer that contains inorganic powder does not have flexible fully and transfer printing (with respect to the heating adaptation of substrate, below identical).If flexible deficiency cracks in the time of then can occurring the film coiling or produces problems such as slight crack at the resin layer surface that contains inorganic powder that is transferred on the substrate.If the transfer printing deficiency then when the above-mentioned resin layer that contains inorganic powder is carried out roasting, can occur problem such as peeling off from substrate.
In order to address these problems, can consider to adopt formation is contained the method that the second-order transition temperature of the binding resin in the resin layer of inorganic powder reduces, or improve flexible and method transfer printing by the heavy addition softening agent, but exist the operability of the transfer film that obtains to reduce, the problem of the very difficult resin layer that contains inorganic powder with higher position precision transfer printing efficiently formation etc.
In addition, according to traditional material design as described above, when preparation contains the resin paste of inorganic powder, cause that easily dispersion is bad.If it is bad that dispersion takes place, will in paste, there be the inorganic powder of cohesion, therefore can be created in and form pin hole in the transfer film, or the problem of surface smoothing and film uniformity reduction.
And then, in traditional transfer film, will contain the resin layer roasting of inorganic powder and residual in the inorganic layer that forms numerous air-bubble arranged, therefore produce the transparency of inorganic layer and the problem of undercapacity.
Therefore, the objective of the invention is to, the FPD parts that provide a kind of residual gas that can suppress after the roasting to embrace and can form the good FPD panel component (inorganic layer) of surface smoothing and film uniformity form uses composition.
In addition, the present invention also aims to, provide a kind of flexible, transfer printing and operability good, and have the transfer film of the inorganic powder resin layer that forms by above-mentioned composition.
Flat panel display component of the present invention forms and uses composition, it is characterized in that, contains:
(A) inorganic powder,
(B) binding resin,
(C) contain silylation compound and
(D) metal alkoxide,
And contain (B-1) (methyl) acrylic polymers in this binding resin (B), should have polyoxyalkylene portion by (B-1) (methyl) acrylic polymers, and weight-average molecular weight is 10,000～50,000.
Above-mentioned polymkeric substance (B-1) preferably contains:
From structural unit 5～30 weight % of (methyl) acrylic compound with polyoxyalkylene portion,
From structural unit 30～50 weight % of (methyl) acrylic compound that does not have polyoxyalkylene portion and
Structural unit 30～50 weight % from aromatic ethenyl compound.
Above-mentioned (methyl) acrylic compound with polyoxyalkylene portion is preferably from polyethyleneglycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, at least a kind of (methyl) acrylic compound selecting in oxyethyl group polypropylene glycol (methyl) acrylate and Nonylphenoxy polypropylene glycol (methyl) acrylate.
The above-mentioned compound (C) that contains silylation is preferably the compound of following formula (1) expression:
Figure A200810176513D00061
In the formula (1), p represents 3～20 integer, and m represents 1～3 integer, and n represents 1～3 integer, and a represents 1～3 integer.
Above-mentioned metal alkoxide (D) is preferably at least a kind that selects from titanium alkoxide, aluminium alkoxide and alkanol magnesium.
FPD parts formation of the present invention preferably also contains plasticity with composition gives material (E).
FPD parts of the present invention form and use transfer film, it is characterized in that, on supporting film, have the resin combination layer that contains inorganic powder (below be also referred to as " FPD parts formation composition layer ").
FPD member manufacturing method of the present invention (below be also referred to as " manufacture method of FPD (I) ") is characterized in that, comprise with form on the supporting film, the FPD parts form with composition layer and are transferred to operation on the substrate; And the operation of this FPD parts formation being carried out calcination process with composition layer.
Above-mentioned flat panel display component is preferably dielectric medium or next door.
Use FPD parts of the present invention to form the transfer film of the present invention that has formed the resin layer that contains inorganic powder with composition, have flexible and excellent transferability, the also good effect of while operability.In addition, can also reduce residual bubble in the resin layer that contains inorganic powder that after roasting, forms.Therefore, the transfer film of the application of the invention can form surface smoothing after the roasting and film uniformity is good, panel component (dielectric layer, next door etc.) with high-transmission rate and high-intensity FPD expeditiously with the higher position precision.
Description of drawings
Fig. 1 is the synoptic diagram that the cross-sectional shape of AC type PDP is shown.
Fig. 2 is the sketch chart of the configuration example of transfer film of the present invention.
Nomenclature
1 glass substrate
2 glass substrates
3 next doors
4 transparency electrodes
5 bus electrodes
6 addressing-electrodes
7 fluorescent substances
8 dielectric layers
9 dielectric layers
10 protective layers
11 next doors
The F1 supporting film
The F2 parts form material layer
The F3 protective membrane
Embodiment
Below explain the manufacture method that FPD parts of the present invention form the panel component of using composition, transfer film and FPD.
(the FPD parts form and use composition)
[inorganic powder (A)]
FPD parts of the present invention form with the inorganic powder that uses in the composition (A), according to the kind of formed panel component and difference.Below describe by the kind of panel component.
Form material and the next door forms the inorganic powder that uses in the material as dielectric medium, can enumerate for example glass powder, preferably can enumerate softening temperature and be 400～600 ℃ glass powder.
When the softening temperature of glass powder is lower than 400 ℃, in the calcining process of the resin layer that contains inorganic powder, because glass powder decomposes the stage remove fully at organic substances such as binding resins will fusion, therefore, residual sometimes a part of organic substance in formed parts, the gaseous diffusion of emitting in the FPD that obtains, the result might make the lost of life of fluor.On the other hand, when the softening temperature of glass powder surpasses 600 ℃,, therefore, on glass substrate, produce sometimes and be out of shape etc. as the transfer printing body of this resin layer because the resin layer that must will contain inorganic powder carries out roasting being higher than under 600 ℃ the high temperature.
As the preferred concrete example of above-mentioned glass powder, can enumerate plumbous oxide, boron oxide, silicon oxide and calcium oxide (PbO-B 2O 3-SiO 2-CaO) class;
Zinc oxide, boron oxide and silicon oxide (ZnO-B 2O 2-SiO 2) class;
Plumbous oxide, boron oxide, silicon oxide and aluminum oxide (PbO-B 2O 3-SiO 2-Al 2O 3) class;
Plumbous oxide, zinc oxide, boron oxide and silicon oxide (PbO-ZnO-B 2O 3-SiO 2) class;
Plumbous oxide, zinc oxide, boron oxide, silicon oxide and titanium oxide (PbO-ZnO-B 2O 3-SiO 2-TiO 2) class;
Bismuth oxide, boron oxide and silicon oxide (Bi 2O 3-B 2O 3-SiO 2) class etc.
The median size of above-mentioned glass powder is preferably 0.5～2.5 μ m.In addition, also can for example mixing in above-mentioned glass powder, inorganic oxides such as aluminum oxide, chromic oxide, manganese oxide, titanium oxide, zirconium white, silicon oxide, cerium oxide and cobalt oxide use.The content of blended inorganic oxide is preferably below the 40 weight % of inorganic powder total amount (glass powder+inorganic oxide).
Form the inorganic powder that uses in the material as electrode, can enumerate for example Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr and Co etc.
Form the inorganic powder that uses in the material as resistance element, can enumerate for example RuO 2Deng.
Form the inorganic powder that uses in the material as fluor, can enumerate for example Y 2O 3: Eu 3+, Y 2SiO 5: Eu 3+, Y 3Al 5O 12: Eu 3+, YVO 4: Eu 3+, (Y, Gd) BO 3: Eu 3+, Zn 3(PO 4) 2: the red fluor of using such as Mn;
Zn 2SiO 4: Mn, BaAl 12O 19: Mn, BaMgAl 14O 23: Mn, LaPO 4: (Ce, Tb), Y 3(Al, Ga) 5O 12: the green fluor of using such as Tb:
Y 2SiO 5: Ce, BaMgAl 10O 17: Eu 2+, BaMgAl 14O 23: Eu 2+, (Ca, Sr, Ba) 10(PO 4) 6C 12: Eu 2+, (Zn, Cd) S:Ag etc. is blue with fluor etc.
Form the inorganic powder that uses in the material as colour filter, can enumerate for example Fe 2O 3, Pb 3O 4, CdS, CdSe, PbCrO 4, PbSO 4, Fe (NO 3) 3Deng the red pigment of using;
Cr 2O 3, TiO 2-CoO-NiO-ZnO, CoO-CrO-TiO 2-Al 2O 3, Co 3(PO 4) 2, the green pigment of using such as CoO-ZnO;
2 (Al 2Na 2Si 3O 10) Na 2S 4), CoO-Al 2O 3Use pigment Deng blue, in addition, the mineral dye that revisal is used as look can be enumerated PbCrO 4-PbSO 4, PbCrO 4, PbCrO 4-PbO, CdS, TiO 2-NiO-Sb 2O 3Deng yellow ultramarine;
Pb (Cr-Mo-S) O 4Deng orange pigments;
Co 3(PO 4) 2Deng violet pigment.
[binding resin (B)]
Constitute FPD parts of the present invention and form the binding resin (B) of using composition, contain (methyl) acrylic polymers (B-1) with polyoxyalkylene portion.
＜polymkeric substance (B-1) 〉
The polymkeric substance that uses among the present invention (B-1) is (methyl) acrylic polymers of 10,000～50,000 for having polyoxyalkylene portion and weight-average molecular weight (Mw).If contain polymkeric substance (B-1), then can be so that transfer film of the present invention have good flexible and transfer printing, wherein, described transfer film of the present invention has by FPD parts of the present invention and forms the resin layer that contains inorganic powder that obtains with composition.That is, because polymkeric substance (B-1) is as softening agent performance function, therefore, even will contain the resin molding bending of inorganic powder, small be full of cracks (crackle) can not take place in the surface of resin layer yet, in addition, preserve even be wound into web-like, its storage stability also is good.
In addition, contain polymkeric substance (B-1) by the FPD parts are formed with composition, can improve the pyrolytic of the resin paste that contains inorganic powder, after the resin layer that contains inorganic powder was carried out roasting, number of bubbles residual in the inorganic layer was reduced.And polymkeric substance (B-1) is decomposed easily when being heated and removes, and therefore, the function of the above-mentioned inorganic layer that contains the resin layer roasting of inorganic powder and obtain can not reduced.
And then if contain polymkeric substance (B-1), the dispersiveness of resin paste and the storage stability that then contain inorganic powder improve, and contain the resin layer of inorganic powder and with the surface smoothing raising of the above-mentioned inorganic layer that contains the resin layer roasting of inorganic powder and obtain.
The polymkeric substance (B-1) that constitutes binding resin of the present invention preferably contains: from the structural unit of (methyl) acrylic compound with polyoxyalkylene portion, from the structural unit of (methyl) acrylic compound that does not have polyoxyalkylene portion and from the structural unit of aromatic ethenyl compound.In addition, in the polymkeric substance (B-1), except the said structure unit, can also contain following structural unit from other co-polymerized monomers.
As above-mentioned polymkeric substance (B-1), can enumerate the homopolymer of (methyl) acrylic compound with polyoxyalkylene portion (below be also referred to as " specific (methyl) acrylic compound "); And by at least a kind of multipolymer that forms in above-mentioned specific (methyl) acrylic compound and (methyl) acrylic compound that does not have polyoxyalkylene portion that is selected from following general formula (2) expression (below be also referred to as " (methyl) acrylic compound (1) "), aromatic ethenyl compound and other the polymer monomers.
Figure A200810176513D00101
In the formula (2), R 1Expression hydrogen atom or methyl, R 2Expression univalent organic group.
Below explanation forms the unitary compound that constitutes polymkeric substance (B-1) respectively.
Form with in the composition at FPD parts of the present invention, the preferred molecular weight of polymkeric substance (B-1), the weight-average molecular weight by polystyrene conversion (following also abbreviate as " weight-average molecular weight " or " the Mw ") expression of adopting gel permeation chromatography (GPC) to measure, be 10,000～50,000, more preferably 20,000～40,000.
Specific (methyl) acrylic compound
As specific (methyl) acrylic compound of the constituent that belongs to polymkeric substance (B-1), can enumerate polyethyleneglycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, oxyethyl group polypropylene glycol (methyl) acrylate and Nonylphenoxy polypropylene glycol (methyl) acrylate etc.
(methyl) acrylic compound (1)
As (methyl) acrylic compound (1) of the constituent that belongs to polymkeric substance (B-1), can enumerate (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, (methyl) vinylformic acid phenoxyalkyl ester, (methyl) alkoxyalkyl acrylate, (methyl) vinylformic acid cycloalkyl ester, (methyl) glycidyl acrylate, (methyl) benzyl acrylate and (methyl) tetrahydrofurfuryl acrylate etc.
As the example of above-mentioned (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid Lauryl Ester, (methyl) stearyl acrylate base ester and (methyl) vinylformic acid iso stearyl ester etc.
As the example of above-mentioned (methyl) acrylic acid hydroxy alkyl ester, can enumerate (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxy butyl ester and (methyl) vinylformic acid 4-hydroxy butyl ester etc.
As the example of above-mentioned (methyl) vinylformic acid phenoxyalkyl ester, can enumerate (methyl) vinylformic acid phenoxy ethyl and (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester etc.
As the example of above-mentioned (methyl) alkoxyalkyl acrylate, can enumerate (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy-ethyl ester, (methyl) vinylformic acid 2-butoxy ethyl ester and (methyl) vinylformic acid 2-methoxyl group butyl ester etc.
As the example of above-mentioned (methyl) vinylformic acid cycloalkyl ester, can enumerate (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 4-butyl cyclohexyl, (methyl) vinylformic acid two (tetrahydro-dicyclopentadiene base) ester, (methyl) vinylformic acid two (dihydro bicyclic pentadiene) ester, (methyl) vinylformic acid dicyclopentadienyl ester, (methyl) vinylformic acid norbornene ester, (methyl) isobornyl acrylate and (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems etc.
As the preferred example of (methyl) acrylic compound (1), can enumerate (methyl) butyl acrylate, (methyl) EHA, (methyl) lauryl acrylate, (methyl) isodecyl acrylate and (methyl) vinylformic acid 2-ethoxy ethyl ester etc.
Aromatic ethenyl compound
Aromatic ethenyl compound as the constituent that belongs to polymkeric substance (B-1), so long as can with the compound of above-mentioned specific (methyl) acrylic compound or (methyl) acrylic compound (1) copolymerization, just there is not particular restriction, for example can enumerate aromatic ethenyl compound classes such as vinylbenzene, alpha-methyl styrene, vinyl benzoic acid, vinyl phthalic acid, vinyl benzyl methyl ether and Vinyl toluene; End has the polystyrene of (methyl) acryl etc.They can use a kind separately, also can will be used in combination more than 2 kinds.
As the preferred example of above-mentioned aromatic ethenyl compound, can enumerate vinyl benzoic acid, vinyl benzyl methyl ether, vinylbenzene and alpha-methyl styrene.
Other co-polymerized monomer
Above-mentioned polymkeric substance (B-1) also can with co-polymerized monomer (below be also referred to as " other the co-polymerized monomer ") reaction beyond above-mentioned specific (methyl) acrylic compound, (methyl) acrylic compound (1) and the aromatic ethenyl compound.As other co-polymerized monomer, can enumerate unsaturated carboxylic acid aminoalkyl ester classes such as acrylic-amino ethyl ester; Vinyl esters of carboxylic acids classes such as vinyl-acetic ester and vinyl propionate base ester; Acrylonitrile compound classes such as (methyl) vinyl cyanide and α-Lv Daibingxijing; Aliphatics such as 1,3-butadiene and isoprene conjugated diene; Unsaturated monocarboxylic acids such as (methyl) vinylformic acid and Ba Dousuan; Unsaturated dicarboxylic acids such as methylene-succinic acid, toxilic acid and fumaric acid; Other unsaturated carboxylic acid; Vinyl ethers such as vinyl benzyl methyl ether and vinyl glycidyl ether; Macromonomer classes such as poly-(methyl) methyl acrylate, poly-(methyl) butyl acrylate and silicone etc.
As other the preferred example of co-polymerized monomer, can enumerate (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid and vinyl phthalic acid; Vinyl glycidyl ether, vinylbenzene, divinyl and isoprene.
Polymkeric substance (B-1)
As mentioned above, as polymkeric substance (B-1), can enumerate the homopolymer of above-mentioned specific (methyl) acrylate; And this specific (methyl) acrylate and the multipolymer that is selected from least a kind of formation in (methyl) acrylic compound (1), aromatic ethenyl compound and other the co-polymerized monomer.As the preferred concrete example of above-mentioned multipolymer, can enumerate the multipolymer that above-mentioned specific (methyl) acrylate and above-mentioned (methyl) acrylic compound (1) and aromatic ethenyl compound class form.
Ratio of components as above-mentioned multipolymer, with respect to polymkeric substance (B-1) 100 weight %, generally, specific (methyl) acrylate is 5～30 weight %, (methyl) acrylic compound (1) is 30～50 weight %, and the aromatic ethenyl compound class is 30～50 weight %; More preferably specific (methyl) acrylate is 10～25 weight %, and (methyl) acrylic compound (1) is 35～45 weight %, and the aromatic ethenyl compound class is 35～45 weight %.In addition, when containing other polymer monomers, with respect to polymkeric substance (B-1) 100 weight %, according to 1～20 weight %, more preferably the ratio of components of 5～15 weight % contains other polymer monomers, can further improve the flexible and transfer printing of the resin transfer film that contains inorganic powder, be preferred therefore.
As the polymkeric substance that uses among the present invention (B-1), can enumerate polymethylene glycol (methyl) acrylate-poly-n-butyl methacrylate multipolymer, polyoxyethylene glycol (methyl) acrylate-poly-n-butyl methacrylate multipolymer, polypropylene glycol (methyl) acrylate-poly-n-butyl methacrylate multipolymer, polyoxyethylene glycol gathers (methyl) acrylate-methyl methacrylate-butyl methacrylate multipolymer, polyoxyethylene glycol gathers (methyl) acrylate-methyl methacrylate-(methyl) n butyl acrylate styrene, polyoxyethylene glycol gathers (methyl) acrylate-(methyl) vinylformic acid-styrol copolymer, polypropylene glycol gathers (methyl) acrylate-(methyl) vinylformic acid 2-ethoxy ethyl ester-styrol copolymer, polymethylene glycol (methyl) acrylate-2-EHA-styrol copolymer, polyoxyethylene glycol (methyl) acrylate-2-EHA-styrol copolymer and polypropylene glycol (methyl) acrylate-2-EHA-styrol copolymer etc.
Polymkeric substance (B-1) is by adopting known method, makes above-mentioned specific (methyl) acrylic compound and above-mentioned (methyl) acrylic compound (1) as required, other co-polymerized monomer carry out polymerization and obtains.Should illustrate that the molecular weight of polymkeric substance (B-1) can be regulated by consumption, polymerization temperature and the polymerization time of suitable adjusting polymerization starter.
＜polymkeric substance (B-2) 〉
The polymkeric substance that uses among the present invention (B-2) so long as not above-mentioned polymkeric substance (B-1), just can use above-mentioned resin in addition with being not particularly limited.Wherein, (methyl) acrylic ester polymer (following also abbreviate as " acrylic resin ") that does not preferably have polyoxyalkylene portion.FPD parts of the present invention form and use composition, by containing acrylic resin as polymkeric substance (B-2), form the resin layer that contains inorganic powder that forms with composition by these FPD parts and can bring into play good (heating) adaptation to substrate.Therefore, FPD parts of the present invention are formed with composition and be applied on the supporting film and the transfer film of making can make the resin layer that contains inorganic powder show good transfer printing (to the heating adaptation of substrate).
As the aforesaid propylene acid resin, be preferably cementability, can make inorganic powder (A) bonding with appropriateness, and can be by the resin layer that contains inorganic powder being carried out calcination process (400～600 ℃) oxidized (being total to) polymkeric substance of removing fully.
As this class acrylic resin, comprise the multipolymer that the homopolymer of above-mentioned (methyl) acrylic compound (1), the multipolymer that contains above-mentioned (methyl) acrylic compound (1) more than 2 kinds and above-mentioned (methyl) acrylic compound (1) and other co-polymerized monomer form.
As (methyl) acrylic compound (1) that uses in the above-mentioned polymkeric substance (B-2), can use with structural unit and use the same compound of (methyl) acrylic compound (1) as above-mentioned polymkeric substance (B-1).For example can enumerate (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, (methyl) vinylformic acid phenoxyalkyl ester, (methyl) alkoxyalkyl acrylate, (methyl) vinylformic acid cycloalkyl ester, (methyl) benzyl acrylate and (methyl) tetrahydrofurfuryl acrylate etc.Concrete example below is shown.
As the example of above-mentioned (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid Lauryl Ester, (methyl) stearyl acrylate base ester and (methyl) vinylformic acid iso stearyl ester etc.
As the example of above-mentioned (methyl) acrylic acid hydroxy alkyl ester, can enumerate (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxy butyl ester and (methyl) vinylformic acid 4-hydroxy butyl ester etc.
As the example of above-mentioned (methyl) vinylformic acid phenoxyalkyl ester, can enumerate (methyl) vinylformic acid phenoxy ethyl and (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester etc.
As the example of above-mentioned (methyl) alkoxyalkyl acrylate, can enumerate (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy-ethyl ester, (methyl) vinylformic acid 2-butoxy ethyl ester and (methyl) vinylformic acid 2-methoxyl group butyl ester etc.
As the example of above-mentioned (methyl) vinylformic acid cycloalkyl ester, can enumerate (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 4-butyl cyclohexyl, (methyl) vinylformic acid two (tetrahydro-dicyclopentadiene base) ester, (methyl) vinylformic acid two (dihydro bicyclic pentadiene) ester, (methyl) vinylformic acid dicyclopentadienyl ester, (methyl) vinylformic acid bornyl ester, (methyl) isobornyl acrylate and (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems etc.
Wherein, in the above-mentioned general formula (2) with R 2The group of expression, be preferably alkyl or contain the group of oxyalkylene group, as (methyl) acrylic compound, can especially preferably enumerate (methyl) butyl acrylate, (methyl) EHA, (methyl) vinylformic acid Lauryl Ester, (methyl) isodecyl acrylate and (methyl) vinylformic acid 2-ethoxy ethyl ester.
In addition, as above-mentioned other the example of co-polymerized monomer, so long as can just not have particular restriction, can enumerate unsaturated carboxylic acid classes such as (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid and vinyl phthalic acid with the compound of above-mentioned (methyl) acrylic compound (1) copolymerization; Vinyl benzyl methyl ether, vinyl glycidyl ether, vinylbenzene, alpha-methyl styrene, divinyl and isoprene etc. contain the free-radical polymerised compound of vinyl.
Form with in the polymkeric substance (B-2) of composition constituting FPD parts of the present invention, the copolymer composition from (methyl) acrylic compound of above-mentioned general formula (2) expression is generally more than the 70 weight %, is preferably more than the 90 weight %.
As the concrete example of preferred acrylic resin, can enumerate polymethylmethacrylate, poly-n-butyl methacrylate and methyl methacrylate-butyl methacrylate multipolymer, butyl methacrylate-methacrylic acid 2-ethylhexyl-methacrylic acid 2-hydroxypropyl acrylate multipolymer etc.
Constituting the molecular weight that FPD parts of the present invention form the polymkeric substance (B-2) of using composition, with weight-average molecular weight (Mw) expression by polystyrene conversion, is 4,000～300,000, is preferably 10,000～200,000.
The use level of＜binding resin (B) 〉
Above-mentioned binding resin (B-2) with respect to inorganic powder (A) 100 weight parts, uses 5～80 weight parts, preferably uses 10～50 weight parts.When the amount of binding resin (B-2) is too small, can not keep the inorganic powder bonding sometimes reliably.On the other hand, when the amount of binding resin (B-2) was excessive, calcining process needed the long time sometimes, or formed sintered compact (for example dielectric layer) does not have enough intensity, thickness sometimes.
The consumption of polymkeric substance (B-1) with respect to inorganic powder (A) 100 weight parts, is generally 0.01～50 weight part, is preferably 0.05～30 weight part, more preferably 0.1～10 weight part.If the amount of polymkeric substance (B-1), then contains the resin layer operability at room temperature and the transfer printing of this resin layer that contains inorganic powder (to the heating adaptation of the substrate) variation of inorganic powder sometimes less than above-mentioned scope.In addition, if the amount of polymkeric substance (B-1) is higher than above-mentioned scope, then formed sometimes adaptation and the transfer printing of resin layer when transfer printing that contains inorganic powder became strong, supporting film become be difficult to peel off, and make the operability variation of the transfer film with this resin layer that contains inorganic powder.
[compound (C) that contains silylation]
The compound that contains silylation (C) that uses among the present invention is the compound of following formula (1) expression.
Figure A200810176513D00171
In the formula (1), p represents 3～20 integer, and m represents 1～3 integer, and n represents 1～3 integer, and a represents 1～3 integer.
Even contain (alkyl) organoalkoxysilane that the p value is lower than 3 saturated alkyl, contain in the resin layer of inorganic powder at this that obtains, can not embody flexible fully sometimes.On the other hand, contain (alkyl) organoalkoxysilane that the p value surpasses 20 saturated alkyl, because decomposition temperature height, therefore contain in the calcining process of resin layer of inorganic powder at this, containing the stage that the compound of silylation (C) is not decomposed fully and removes, frit generation fusion, residual a part of organic substance in formed dielectric layer, thus the optical transmittance of dielectric layer is reduced.
The concrete example that contains the compound (C) of silylation and use as above-mentioned below is shown.
As saturated alkyl dimethyl methyl TMOS class (a=1, m=1, n=1), for example can enumerate n-propyl dimethyl methyl TMOS, normal-butyl dimethyl methyl TMOS, positive decyl dimethyl methyl TMOS, n-hexadecyl dimethyl methyl TMOS and NSC 62789 base dimethyl methyl TMOS etc.
As saturated alkyl diethyl methoxy silane class (a=1, m=1, n=2), for example can enumerate n-propyl diethyl methoxy silane, normal-butyl diethyl methoxy silane, positive decyl diethyl methoxy silane, n-hexadecyl diethyl methoxy silane, NSC 62789 base diethyl methoxy silane etc.
As saturated alkyl dipropyl methoxy silane class (a=1, m=1, n=3), for example can enumerate normal-butyl dipropyl methoxy silane, positive decyl dipropyl methoxy silane, n-hexadecyl dipropyl methoxy silane, NSC 62789 base dipropyl methoxy silane etc.
As saturated alkyl dimethylethoxysilane class (a=1, m=2, n=1), for example can enumerate n-propyl dimethylethoxysilane, normal-butyl dimethylethoxysilane, positive decyl dimethylethoxysilane, n-hexadecyl dimethylethoxysilane, NSC 62789 base dimethylethoxysilane etc.
As saturated alkyl diethyl Ethoxysilane class (a=1, m=2, n=2), for example can enumerate n-propyl diethyl Ethoxysilane, normal-butyl diethyl Ethoxysilane, positive decyl diethyl Ethoxysilane, n-hexadecyl diethyl Ethoxysilane, NSC 62789 base diethyl Ethoxysilane etc.
As saturated alkyl dipropyl Ethoxysilane class (a=1, m=2, n=3), for example can enumerate normal-butyl dipropyl Ethoxysilane, positive decyl dipropyl Ethoxysilane, n-hexadecyl dipropyl Ethoxysilane, NSC 62789 base dipropyl Ethoxysilane etc.
As saturated alkyl dimethyl propylene TMOS class (a=1, m=3, n=1), for example can enumerate n-propyl dimethyl propylene TMOS, normal-butyl dimethyl propylene TMOS, positive decyl dimethyl propylene TMOS, n-hexadecyl dimethyl propylene TMOS, NSC 62789 base dimethyl propylene TMOS etc.
As saturated alkyl diethyl propoxy-silicane (a=1, m=3, n=2), for example can enumerate n-propyl diethyl propoxy-silane, normal-butyl diethyl propoxy-silane, positive decyl diethyl propoxy-silane, n-hexadecyl diethyl propoxy-silane, NSC 62789 base diethyl propoxy-silane etc.
As saturated alkyl dipropyl propoxy-silicane (a=1, m=3, n=3), for example can enumerate normal-butyl dipropyl propoxy-silane, positive decyl dipropyl propoxy-silane, n-hexadecyl dipropyl propoxy-silane, NSC 62789 base dipropyl propoxy-silane etc.
As saturated alkyl methyl dimethoxysilane class (a=2, m=1, n=1), for example can enumerate n-propyl methyl dimethoxysilane, n-butylmethyldimethoxyforane, positive decyl methyl dimethoxysilane, n-hexadecyl methyl dimethoxysilane, NSC 62789 ylmethyl dimethoxy silane etc.
As saturated alkyl ethyl dimethoxy silicane (a=2, m=1, n=2), for example can enumerate n-propyl ethyl dimethoxy silane, normal-butyl ethyl dimethoxy silane, positive decyl ethyl dimethoxy silane, n-hexadecyl ethyl dimethoxy silane, NSC 62789 base ethyl dimethoxy silane etc.
As saturated alkyl propyl group dimethoxy silicane (a=2, m=1, n=3), for example can enumerate normal-butyl propyl group dimethoxy silane, positive decyl propyl group dimethoxy silane, n-hexadecyl propyl group dimethoxy silane, NSC 62789 base propyl group dimethoxy silane etc.
As saturated alkyl methyldiethoxysilane class (a=2, m=2, n=1), for example can enumerate n-propyl methyldiethoxysilane, normal-butyl methyldiethoxysilane, positive decyl methyldiethoxysilane, n-hexadecyl methyldiethoxysilane, NSC 62789 ylmethyl diethoxy silane etc.
As saturated alkyl ethyl diethoxy silane class (a=2, m=2, n=2), for example can enumerate n-propyl ethyl diethoxy silane, normal-butyl ethyl diethoxy silane, positive decyl ethyl diethoxy silane, n-hexadecyl ethyl diethoxy silane, NSC 62789 base ethyl diethoxy silane etc.
As saturated alkyl propyl group diethoxy silane class (a=2, m=2, n=3), for example can enumerate normal-butyl propyl group diethoxy silane, positive decyl propyl group diethoxy silane, n-hexadecyl propyl group diethoxy silane, NSC 62789 base propyl group diethoxy silane etc.
As saturated alkyl methyl dipropoxy silicane (a=2, m=3, n=1), for example can enumerate n-propyl methyl dipropoxy silane, normal-butyl methyl dipropoxy silane, positive decyl methyl dipropoxy silane, n-hexadecane ylmethyl dipropoxy silane, NSC 62789 ylmethyl dipropoxy silane etc.
As saturated alkyl ethyl dipropoxy silicane (a=2, m=3, n=2), for example can enumerate n-propyl ethyl dipropoxy silane, normal-butyl ethyl dipropoxy silane, positive decyl ethyl dipropoxy silane, n-hexadecyl ethyl dipropoxy silane, NSC 62789 base ethyl dipropoxy silane etc.
As saturated alkyl propyl group dipropoxy silicane (a=2, m=3, n=3), for example can enumerate normal-butyl propyl group dipropoxy silane, positive decyl propyl group dipropoxy silane, n-hexadecyl propyl group dipropoxy silane, NSC 62789 base propyl group dipropoxy silane etc.
As saturated alkyl Trimethoxy silane class (a=3, m=1), for example can enumerate n-propyl Trimethoxy silane, normal-butyl Trimethoxy silane, positive decyl Trimethoxy silane, n-hexadecyl Trimethoxy silane, NSC 62789 base Trimethoxy silane etc.
As saturated alkyl triethoxysilicane alkanes ((a=3, m=2), for example can enumerate n-propyl triethoxyl silane, ne-butyltriethoxysilaneand, positive decyl triethoxyl silane, n-hexadecyl triethoxyl silane, NSC 62789 ethyl triethoxy silicane alkane etc.
As saturated alkyl tripropoxy silicane (a=3, m=3), for example can enumerate n-propyl tripropoxy silane, normal-butyl tripropoxy silane, positive decyl tripropoxy silane, n-hexadecyl tripropoxy silane, NSC 62789 base tripropoxy silane etc.
Proportional as containing of the compound (C) that contains silylation of the present invention, with respect to inorganic powder (A) 100 weight parts, be preferably 0.01～10 weight part, more preferably 0.1～5 weight part.When the ratio of the compound that contains silylation (C) is too small, contain the surface smoothing reduction of the resin layer of inorganic powder sometimes, maybe will contain the resin layer roasting of inorganic powder and the transparency of the sintered membrane that obtains reduces.On the other hand, when this ratio was excessive, the storage stability that contains the resin combination of inorganic powder sometimes reduced, and the operability of the transfer film that obtains reduces.
[metal alkoxide (D)]
In the resin layer that contains inorganic powder of the present invention, contain metal alkoxide (D).Metal alkoxide (D) can react rapidly with the hydroxyl that contained in the glass powder as inorganic powder (A), then carries out replacement(metathesis)reaction with the above-mentioned compound (C) that contains silylation expeditiously.Therefore, the effect that presents the dispersiveness of further raising glass powder and improve the surface smoothing of formed film formation material layer.Because it is insufficient to contain the reaction independent and glass powder of the compound of silylation, therefore can not expect that dispersiveness has significant improvement.
As the metal alkoxide that uses among the present invention (D), can enumerate titanium alkoxide, aluminium alkoxide, alkanol magnesium etc.Wherein, consider, especially preferably use titanium alkoxide from reactive aspect.
As the concrete example of the metal alkoxide that uses among the present invention, preferably can enumerate the compound of following formula (3) expression.
R SM(OR’) t-s
Figure A200810176513D0020132034QIETU
(3)
In the formula (3), M is atoms metals such as aluminium, titanium or magnesium, and R is any monovalent organic radical group of carbonatoms 1～8, and R ' is the alkyl of carbonatoms 1～6, and t is the valency of M, and s is the integer of 0～t-1.When having a plurality of R or R ' time, they can be identical or different separately.
In above-mentioned formula (3), any monovalent organic radical group as carbonatoms 1～8 for example can enumerate, alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl; Acyl groups such as ethanoyl, propionyl, butyryl radicals, pentanoyl, benzoyl, toluyl; Acyloxy such as acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, benzoyloxy, toluene acyloxy; The hydrogen atom of part or all that is contained in vinyl, allyl group, cyclohexyl, phenyl, glycidyl, (methyl) acryloxy, urea groups, amide group, fluoro acetamido, isocyanate group etc. and these groups is by halogen atom, replacement or unsubstituted amino, hydroxyl, sulfydryl, isocyanate group, glycidoxy, 3, the group that 4-epoxy group(ing) cyclohexyl, (methyl) acryloxy, urea groups, ammonium salt base etc. replace.
In addition, as the alkyl of the carbonatoms 1～6 of R ', for example can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-hexyl etc.
As this metalloid alkoxide, for example can enumerate titanium alkoxide classes such as tetramethyl alcohol titanium, titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums; Aluminium alkoxide classes such as three aluminum methylates, three aluminum ethylates, aluminum isopropylate, three aluminium butoxides; Alkanol magnesium classes such as diformazan magnesium alkoxide, diethyl magnesium alkoxide.These metal alkoxides can use a kind separately, perhaps will be used in combination more than 2 kinds.
Proportional as FPD parts formation of the present invention with containing of metal alkoxide in the composition (D), with respect to inorganic powder (A) 100 weight parts, be preferably 0.001～10 weight part, more preferably 0.01～1 weight part.If the ratio of metal alkoxide (D) is too small, then can not give full play to the effect that improves the glass powder dispersiveness, the effect that improves surface smoothing in the formed film formation material layer sometimes.On the other hand, if this ratio is excessive, then when composition was used in preservation FPD parts formation of the present invention, viscosity rose in time sometimes, or reacts between metal alkoxide (D), becomes the reason of the optical transmittance reduction of dielectric layer.
[plasticity is given material (E)]
FPD parts of the present invention form and use composition, for transfer film being given good flexibility, can also contain plasticity and give the auxiliary agent of material (E) as above-mentioned binding resin (B).Give the FPD parts of material (E) and form the resin layer that contains inorganic powder that forms with composition by containing plasticity, have sufficient flexibility.
Give material (E) as above-mentioned plasticity, can enumerate co-polymerized monomer such as the softening agent selected the compound of compound from following general formula (4) expression, following general formula (5) expression, polypropylene glycol, above-mentioned (methyl) acrylic compound and following solvent etc., wherein, preferred boiling point is the material more than 150 ℃.This quasi-plastic property is given material (E) can use a kind separately, also can will be used in combination more than 2 kinds.
Figure A200810176513D00221
(in the formula (4), R 3And R 6The monovalence chain type alkyl of representing carbonatoms 1～30 independently of one another, R 4And R 5The divalence chain type alkyl of representing methylene radical or carbonatoms 2～30 independently of one another.S is 0～5 integer, and t is 1～10 integer).
In above-mentioned general formula (4), R 3Perhaps R 6The monovalence chain type alkyl of expression can be straight chain shape or catenate alkyl (saturated group) or alkenyl (unsaturated group), and the carbonatoms of chain type alkyl is 1～30, is preferably 2～20, more preferably 4～10.When the carbonatoms of chain type alkyl exceeded above-mentioned scope, the solvability in following solvent reduced sometimes, is difficult to give good flexibility to the resin layer that contains inorganic powder.
R 4Perhaps R 5The divalence chain type alkyl of expression is straight chain shape or catenate alkylidene group (saturated group) or alkylene group (unsaturated group).
As the example of the compound of above-mentioned general formula (4) expression, can enumerate Polycizer W 260, diisobutyl adipate, di-2-ethylhexyl adipate, di(2-ethylhexyl)azelate, Uniflex DBS and hexanodioic acid dibutyl glycol ether ester etc.
Figure A200810176513D00222
In the formula (5), R 7The monovalence chain type alkyl of expression carbonatoms 1～30.
In above-mentioned general formula (5), R 7The monovalence chain type alkyl of expression is straight chain shape or catenate alkyl (saturated group) or alkenyl (unsaturated group), and the carbonatoms of chain type alkyl is 1～30, is preferably 2～20, more preferably 10～18.
As the example of the compound of above-mentioned general formula (5) expression, can enumerate mono laurate propylene glycol ester and single oleic acid propylene glycol ester etc.
When using polypropylene glycol to give material (E) as plasticity, this polypropylene glycol preferably is in 200～3,000 scope by the weight-average molecular weight (Mw) of polystyrene conversion, especially preferably is in 300～2,000 scope.If Mw is less than 200, then be difficult on supporting film, form the big resin layer that contains inorganic powder of film toughness sometimes, the resin layer that this is contained inorganic powder is transferred to operation on the glass substrate from supporting film, when supporting film is peeled off from being heated this resin layer that contains inorganic powder that is bonded on the glass substrate, cause that sometimes the cohesion of this resin layer destroys.On the other hand, if Mw surpasses 3,000, then can not get sometimes and the good resin layer that contains inorganic powder of heating adaptation as the glass substrate of transfer printing body.
Above-mentioned plasticity is given the consumption of material (E), for forming from FPD parts of the present invention with more than the 3 weight % that removed solvent total composition afterwards the composition, is preferably 4～15 weight %.Give the content of material (E) when too small when plasticity, be difficult to sometimes give good flexibility formed transfer film.
＜solvent 〉
FPD parts of the present invention form and contain solvent usually with composition.As this kind solvent, preferably with the affinity of inorganic powder (A) and to the favorable solubility of binding resin (B), and can form the viscosity of giving appropriateness with composition to the FPD parts, just can easily be evaporated the solvent of removing as long as carry out drying treatment simultaneously.
In addition, as particularly preferred solvent, can enumerate normal boiling point (boiling point under 1 normal atmosphere) and be 60～200 ℃ ketone, alcohols and ester class (following they are called " specific solvent ").
As the example of above-mentioned specific solvent, can enumerate ketones such as methyl ethyl ketone, metacetone, methyl butyl ketone, butyrone and pimelinketone;
Alcohols such as Pentyl alcohol, 4-methyl-2-amylalcohol, hexalin and diacetone alcohol;
Ethers such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol list ethyl ether are alcohols;
Representative examples of saturated aliphatic such as n-butyl acetate and pentyl acetate monocarboxylic acid alkyl esters;
Lactic acid ester such as ethyl lactate and n-butyl lactate:
Ethers such as methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether and ethyl 3-ethoxy-c acid esters are ester class etc.Wherein, preferable methyl butyl ketone, pimelinketone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxy-c acid esters etc.These specific solvents can use a kind separately, also can will be used in combination more than 2 kinds.
In addition, as the spendable solvent beyond the above-mentioned specific solvent, for example can enumerate turps, ethyl cellosolve, methylcyclohexane, Terpineol 350, acetate of butyl carbitol, diethylene glycol monobutyl ether, Virahol and benzylalcohol etc.
The consumption of above-mentioned solvent maintains viewpoint consideration in the suitable scope from the FPD parts being formed viscosity with composition, with respect to inorganic powder (A) 100 weight parts, is 5～50 weight parts, is preferably 10～40 weight parts.In addition, the ratio that specific solvent accounts for whole solvents is more than the 50 weight %, is preferably more than the 70 weight %.In addition, the formation of FPD parts is preferably 2,000～200, the scope of 000cps usually with the viscosity of composition.
[various additive]
FPD parts of the present invention form and use composition, also can contain the various additives such as dispersion agent, development accelerant, bonding auxiliary agent, anti-halation agent, flow agent, preserving stabilizer, defoamer, antioxidant and/or chain-transfer agent as any composition.
(transfer film)
FPD parts of the present invention form with transfer film (following also abbreviate as " transfer film "), it is characterized in that, on supporting film, have by containing inorganic powder (A), binding resin (B), containing the compound (C) of silylation and the FPD parts of metal alkoxide (D) form the resin layer that contains inorganic powder that forms with composition.In addition, above-mentioned FPD parts form and can also contain plasticity with composition and give material (E).
Transfer film of the present invention also can be the transfer film (laminate-type transfer film) that has the laminate film that is formed by resist film and the above-mentioned resin layer that contains inorganic powder on supporting film.
In addition, as required, on the surface of the resin layer that contains inorganic powder, also can have protective membrane.
Below, specifically describe each integrant of transfer film.
(1) supporting film
Transfer film of the present invention has the supporting film that support contains the resin layer of inorganic powder.This supporting film had preferably not only had thermotolerance and solvent resistance, but also had had the flexible resin molding.Flexible by supporting film is had, can adopt roller coating machine or scraper-type coating machine etc. that the FPD parts are formed and be applied on the surface of supporting film with composition, the transfer film that obtains can be preserved or supplied with the state that is wound into web-like.
As the example of the resin that forms supporting film, can enumerate fluorine resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, fluorinated ethylene propylene, nylon and Mierocrystalline cellulose etc.
The thickness of supporting film is 20～100 μ m.In addition, preferably the surface to supporting film imposes demoulding processing, can easily carry out the strip operation of supporting film in the transfer printing process of glass substrate thus.
(2) protective membrane
In transfer film of the present invention,, also can on this contains the surface of resin layer of inorganic powder, protective membrane be set in order to protect the surface of the resin layer that contains inorganic powder.This protective membrane is preferably has the flexible resin molding, thus, the transfer film that obtains can be preserved or is supplied with the state that is wound into web-like.
As the example that constitutes the protective membrane resin, can enumerate polyethylene terephthalate film, polyethylene film and polyvinyl alcohol film etc.
The thickness of protective membrane is 20～100 μ m.In addition, also can impose the demoulding to the surface of protective membrane and handle, preferably make this protective membrane little with the adaptation of supporting film with the adaptation ratio of the resin layer that contains inorganic powder.
(3) contain the resin layer of inorganic powder
The resin layer (FPD parts form use composition layer) that contains inorganic powder normally by the formation of FPD parts is applied on the supporting film with composition, makes the coated film drying that is obtained, and whole or a part of solvent removed form.
Be applied to method on the supporting film as above-mentioned FPD parts being formed with composition, preferably can form the method for filming of the good and thickness of film uniformity big (for example more than the 10 μ m) with high-level efficiency, can enumerate particularly, adopt the coating process of the coating process of roller coating machine, the coating process that adopts scraper-type coating machine, the coating process that adopts curtain formula curtain coater and the excellent coating machine of employing coiling etc.The thickness that contains the resin layer of inorganic powder depends on the height of the panel component that will form, and is generally 10～300 μ m.
As the drying conditions of filming, for example be 50～150 ℃ dry about 0.5～30 minute down, the residual ratio of dried solvent (containing the containing ratio in the resin layer of inorganic powder) is generally in the 2 weight %.
[manufacture method of FPD]
As the manufacture method of FPD of the present invention, can enumerate following proposal.
[1] by adopting following method, thereby form the method (manufacture method of FPD (I)) as the dielectric layer of panel component on substrate, this method comprises the operation that the resin layer that contains inorganic powder with transfer film of the present invention carries out the operation of transfer printing and the resin layer that contains inorganic powder that will be transferred carries out roasting.
[2] by adopting following method, thereby on substrate, form as panel component from dielectric layer, electrode, the next door, fluor, resistance element, at least a method of selecting in colour filter and the black matrix" (manufacture method of FPD (II)), this method comprises the operation of the resin layer that contains inorganic powder of transfer film of the present invention being carried out transfer printing, on the resin layer that contains inorganic powder that is transferred, form the operation of resist pattern, the resin layer that contains inorganic powder is carried out etch processes and form operation with the corresponding pattern of resist pattern, this pattern is carried out the operation of calcination process.
[3] by adopting following method, thereby on substrate, form as panel component from dielectric layer, electrode, the next door, fluor, resistance element, at least a method of selecting in colour filter and the black matrix" (manufacture method of FPD (III)), this method comprise so that contain the operation that the mode of the resin layer of inorganic powder and substrate butt is carried out the laminate film of laminate-type transfer film transfer printing, resist film in the laminate film that is transferred is carried out exposure-processed and form the operation of the latent image of resist pattern, resist film is carried out development treatment and manifest the operation of resist pattern, the resin layer that contains inorganic powder is carried out etch processes and form operation with the corresponding pattern of resist pattern, this pattern is carried out the operation of calcination process.
[4] by adopting following method, thereby on substrate, form as panel component from dielectric layer, electrode, the next door, fluor, resistance element, at least a method of selecting in colour filter and the black matrix" (manufacture method of FPD (IV)), this method comprises the operation of the resin layer that contains inorganic powder of photosensitive transfer printing film being carried out transfer printing, the resin layer that contains inorganic powder that is transferred is carried out exposure-processed and form the operation of the latent image of pattern, this resin layer that contains inorganic powder is carried out development treatment and form the operation of pattern, this pattern is carried out the operation of calcination process.
[5] by adopting following method, thereby on substrate, form at least a method of from dielectric layer, electrode, next door, fluor, resistance element, colour filter and black matrix", selecting (V) as panel component, this method comprise with the resin layer that contains inorganic powder of transfer film of the present invention carry out transfer printing operation, to the resin layer that contains inorganic powder that is transferred carry out roasting and form the operation of mineral membrane, on this mineral membrane, form the resist pattern operation, mineral membrane is carried out etch processes and forms operation with the corresponding pattern of resist pattern.
The manufacture method (I) of FPD of the present invention below is described.
＜FPD member manufacturing method (I) 〉
One example of the transfer printing process in the above-mentioned FPD member manufacturing method (I) below is shown.
(1) transfer film that will be wound into the state of web-like is cut into and the area of substrate size accordingly.
(2) as required protective membrane is peeled off from the resin layer surface that contains inorganic powder of the transfer film that is cut into after, with the mode that substrate surface connects transfer film is overlapped with the surface of the resin layer that contains inorganic powder with substrate surface.
(3) with transfer film that substrate overlaps on mobile warming mill, thereby make its hot pressing.
(4) peel off and remove supporting film from be fixed on the resin layer that contains inorganic powder on the substrate by hot pressing.
By aforesaid operation, the resin layer that contains inorganic powder on the supporting film is transferred on the substrate.As the transfer printing condition of this moment, for example, the surface temperature of warming mill is 60～120 ℃, and the roll-in that is applied by warming mill is 1～5kg/cm 2And the translational speed of warming mill is 0.2～10.0m/ minute.This operation (transfer printing process) can be undertaken by laminater.Should illustrate, also basal plate preheating as preheating temperature, for example can be 40～100 ℃.
Transfer printing and the resin layer that contains inorganic powder that is formed on the substrate surface become inorganic sintered body (dielectric layer) through roasting.As roasting method, can enumerate transfer printing and the substrate that formed the resin layer that contains inorganic powder are configured in method under the high-temperature atmosphere.By calcination process, contain the organic substance that is contained in the resin layer of inorganic powder and be decomposed and remove, and make the inorganic powder fusion and sintering.As maturing temperature, according to the melt temperature of substrate and contain constitute in the resin layer of inorganic powder etc. and different, for example be 300～800 ℃, be preferably 400～620 ℃.
(embodiment)
Below be described more specifically the present invention based on embodiment, but the present invention is not subjected to the qualification of these embodiment.Following " part " expression " weight part " should be described.
＜synthesis example 1 〉
With 20 parts of 40 parts of 40 parts of polymethyl acrylic acid glycol esters (below be also referred to as " PEGMA "), 2-EHA (below be also referred to as " EHA "), vinylbenzene (below be also referred to as " ST ") and N, N '-Diisopropyl azodicarboxylate joins in the autoclave that has stirrer for 0.75 part, is stirred under room temperature in nitrogen atmosphere evenly.After the stirring, under 80 ℃, make its polyase 13 hour, and then add N, 0.25 part of N '-Diisopropyl azodicarboxylate, polymerization 1 hour after proceeding 1 hour polyreaction under 100 ℃, is cooled to room temperature, obtains polymers soln.The percent polymerization of the polymers soln that obtains is 98%, and the Mw of the polymkeric substance of separating out from this polymers soln (B-1) (hereinafter referred to as " resin (1) ") is 30,000.The results are shown in table 1.
In addition, in synthesis example 1, except use monomer according to the amount shown in the table 1, all the other and synthesis example 1 be synthetic resins (2)～(5) similarly.
＜synthesis example 6 〉
With PEGMA20 part, EHA40 part, ST40 part and N, N '-Diisopropyl azodicarboxylate joins in the autoclave that has stirrer for 1.5 parts, is stirred under room temperature in nitrogen atmosphere evenly.After the stirring, under 90 ℃, make its polyase 13 hour, and then add N, 0.5 part of N '-Diisopropyl azodicarboxylate, polymerization 1 hour after proceeding 1 hour polyreaction under 100 ℃, is cooled to room temperature, obtains polymers soln.The percent polymerization of the polymers soln that obtains is 96%, and the Mw of the resin of separating out from this polymers soln (6) is 10,000.The results are shown in table 1.
＜synthesis example 7 〉
With PEGMA20 part, EHA40 part, ST40 part and N, N '-Diisopropyl azodicarboxylate joins in the autoclave that has stirrer for 0.5 part, is stirred under room temperature in nitrogen atmosphere evenly.After the stirring, under 75 ℃, make its polymerization 4 hours, and then add N, 0.25 part of N '-Diisopropyl azodicarboxylate, polymerization 2 hours after proceeding 1 hour polyreaction under 100 ℃, is cooled to room temperature, obtains polymers soln.The percent polymerization of the polymers soln that obtains is 98%, and the Mw of the resin of separating out from this polymers soln (7) is 50,000.The results are shown in table 1.
Table 1
Figure A200810176513D00291
[embodiment 1]
(1) preparation of glass paste composition (the FPD parts form and use composition)
Will be as the PbO-B of the composition with plumbous oxide 70 weight %, boron oxide 10 weight % and silicon oxide 20 weight % of glass powder (inorganic powder (A)) 2O 3-SiO 2100 parts in the mixture (500 ℃ of softening temperatures) of system, as 20 parts in 10 parts in the polymkeric substance (B-1) of binding resin (B) and polymkeric substance (B-2), as 5 parts of the positive decyl Trimethoxy silanes of the compound that contains silylation (C) (below be also referred to as " nDTMS "), as 1 part of the titanium tetraisopropylate of metal alkoxide (D) (below be also referred to as " TTiPO "), as plasticity give 3 parts of nonane diacid two (2-ethylhexyl) esters (below be also referred to as " EHAz ") of material (E) and carry out with dispersion machine as 35 parts of the propylene glycol monomethyl ether of solvent mixing, thereby preparation viscosity is the FPD parts of 3Pas to be formed and uses composition.
(2) manufacturing of transfer film and evaluation (flexible and operability)
Use scraper-type coating machine, the FPD parts of preparation in above-mentioned (1) are formed with composition be applied to supporting film (the wide 400mm that handles through the demoulding in advance, form by polyethylene terephthalate (PET); Length 30m; Thickness 38 μ m) on, filming of forming desolvated to remove down at 100 ℃ in dry 5 minutes, thereby on supporting film, form the resin layer that contains inorganic powder of thickness 50 μ m.Then, on the above-mentioned resin layer that contains inorganic powder, stick in advance protective membrane (the wide 400mm that forms by PET that handles through the demoulding; Length 30m; Thickness 25 μ m), make transfer film of the present invention thus with structure shown in Figure 2.
The transfer film that obtains has flexibility, can easily be wound into the operation of web-like.In addition, even with this transfer film bending, contain on the surface of resin layer of inorganic powder and also do not crack (crooked be full of cracks), this resin layer has good flexible.
In addition, protective membrane is peeled off from this transfer film,, this transfer film is overlapped with glass substrate with the resin layer surface that contains inorganic powder and the mode of glass baseplate surface butt, then, with the sur-face peeling of this transfer film from glass substrate.Its result, above-mentioned resin layer demonstrates the cementability to the glass substrate appropriateness, and, can transfer film be peeled off not causing under this resin layer cohesion destructive situation, good as the operability of transfer film.
(3) contain the transfer printing of the resin layer of inorganic powder
After the transfer film that protective membrane is obtained from above-mentioned (2) is peeled off; the mode of glass baseplate surface (fixed face of the bus electrode) butt of using with the resin layer surface that contains inorganic powder and 20 inches panels; this transfer film is overlapped, then with this transfer film warming mill hot pressing with the surface of glass substrate.As the pressing condition, the surface temperature that makes warming mill is 110 ℃, and roll-in is 3kg/cm 2, the translational speed of warming mill is 1m/ minute.
After the hot pressing processing finishes, supporting film peeled off at the resin layer that contains inorganic powder on the surface of glass substrate from fixing (adding heat bonding) remove, thereby finish the transfer printing of this resin layer.
In this transfer printing process, when supporting film is peeled off, do not cause that the cohesion of the resin layer that contains inorganic powder destroys, this resin layer has enough big film toughness.And the resin layer that contains inorganic powder that is transferred has good cementability to the surface of glass substrate.The results are shown in table 2.
(4) contain the calcining process of the resin layer of inorganic powder
To fix the calcination process that (adding heat bonding) carried out in stoving oven, under 590 ℃ temperature atmosphere at the resin that contains inorganic powder on the glass baseplate surface 20 minutes as mentioned above.Can obtain on the surface of glass substrate, to be formed with the panel component that the dielectric medium of thickness 40 μ m forms thus.The results are shown in table 2.
The evaluation method of＜transfer film 〉
The evaluation method of transfer film of the present invention below is shown.
(1) flexible
When with the transfer film bending, on the surface of the resin layer that contains inorganic powder, do not crack (crooked be full of cracks) person and be evaluated as zero, the person of cracking is evaluated as *.
(2) residual bubble
With the inorganic layer that obtains after the transmissive optical microscopic examination roasting, be determined at the mean diameter of bubble residual in the inorganic layer.Residual bubble is estimated according to following benchmark.
A: less than 5 μ m
More than the B:5 μ m, less than 10 μ m
More than the C:10 μ m
(3) surface smoothing
Use non-contact three-dimensional shape measuring apparatus (model: NH-3 three hawk light devices (strain)), at measurement range 500 μ m * 500 μ m, measure under the condition of spacing 10 μ m and measure, with 10 mean roughness (Rz) as surfaceness.Surfaceness is estimated according to following benchmark.
Zero: less than 0.01 μ m
*: more than the 0.01 μ m
[embodiment 2～9]
In embodiment 1, as FPD parts formation composition, use the composition of record in the table 2, in addition carry out similarly to Example 1, preparation FPD parts form uses composition and transfer film.The results are shown in table 2.
[comparative example 1]
In embodiment 3, except not using polymkeric substance (B-1), all the other carry out similarly to Example 3, and preparation FPD parts form with composition and transfer film.The results are shown in table 2.
[comparative example 2]
In embodiment 3, except not using positive decyl Trimethoxy silane (compound (C) that contains silylation), all the other carry out similarly to Example 3, and preparation FPD parts form with composition and transfer film.The results are shown in table 2.
[comparative example 3]
In embodiment 3, except not using titanium tetraisopropylate (metal alkoxide (D)), all the other carry out similarly to Example 3, and preparation FPD parts form with composition and transfer film.The results are shown in table 2.
[table 2]

Claims (9)

1. a flat panel display component forms and uses composition, it is characterized in that, contains:
(A) inorganic powder,
(B) binding resin,
(C) contain silylation compound and
(D) metal alkoxide,
And contain (B-1) (methyl) acrylic polymers in this binding resin (B), described (B-1) (methyl) acrylic polymers has polyoxyalkylene portion, and weight-average molecular weight is 10,000～50,000.
2. flat panel display component according to claim 1 forms and uses composition, it is characterized in that described polymkeric substance (B-1) contains:
From structural unit 5～30 weight % of (methyl) acrylic compound with polyoxyalkylene portion,
From structural unit 30～50 weight % of (methyl) acrylic compound that does not have polyoxyalkylene portion and
Structural unit 30～50 weight % from aromatic ethenyl compound.
3. flat panel display component according to claim 2 forms uses composition, it is characterized in that described (methyl) acrylic compound with polyoxyalkylene portion is from polyethyleneglycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, at least a kind of (methyl) acrylic compound selecting in oxyethyl group polypropylene glycol (methyl) acrylate and Nonylphenoxy polypropylene glycol (methyl) acrylate.
4. form according to each described flat panel display component in the claim 1～3 and use composition, it is characterized in that, the described compound that contains the compound (C) of silylation for following formula (1) expression:
Figure A200810176513C00021
In the formula (1), p represents 3～20 integer, and m represents 1～3 integer, and n represents 1～3 integer, and a represents 1～3 integer.
5. form according to each described flat panel display component in the claim 1～4 and use composition, it is characterized in that described metal alkoxide (D) is at least a kind that selects from titanium alkoxide, aluminium alkoxide and alkanol magnesium.
6. form according to each described flat panel display component in the claim 1～5 and use composition, it is characterized in that, also contain plasticity and give material (E).
7. a flat panel display component forms and uses transfer film, it is characterized in that, on supporting film, has and forms the flat panel display component that makes with composition by each described flat panel display component in the claim 1～6 and form and use composition layer.
8. the manufacture method of a flat panel display component is characterized in that, comprises following operation:
With form on the supporting film, form the flat panel display component that makes with composition by each described flat panel display component in the claim 1～6 and form with composition layer and be transferred to operation on the substrate; And
This flat panel display component is formed the operation of carrying out calcination process with composition layer.
9. the manufacture method of flat panel display component according to claim 8 is characterized in that, described flat panel display component is dielectric medium or next door.
CNA2008101765132A 2007-12-07 2008-11-07 Composition for forming flat panel display component, transfer printing film and application thereof Pending CN101450837A (en)

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JP2007317046A JP2009140805A (en) 2007-12-07 2007-12-07 Composition for forming flat panel display member, transfer film for forming flat panel display member, and method for manufacturing flat panel display member
JP2007317046 2007-12-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103038063A (en) * 2010-07-30 2013-04-10 佳能株式会社 Intermediate transfer member for transfer ink jet recording

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103038063A (en) * 2010-07-30 2013-04-10 佳能株式会社 Intermediate transfer member for transfer ink jet recording
US8802221B2 (en) 2010-07-30 2014-08-12 Canon Kabushiki Kaisha Intermediate transfer member for transfer ink jet recording
CN103038063B (en) * 2010-07-30 2015-03-04 佳能株式会社 Intermediate transfer member for transfer ink jet recording

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