JP5858517B2 - Manufacturing method of organic device - Google Patents

Description

The present invention relates to a manufacturing method of the organic device.

  In recent years, organic devices including organic layers made of organic materials have attracted attention as devices such as light-emitting elements and power generation elements. For example, organic electroluminescence devices are attracting attention as next-generation light sources that can be used as flat panel displays, backlights for liquid crystal display devices, light sources for illumination, etc., because they can emit light with high brightness and low voltage. Collecting. The organic electroluminescence device generally has a structure in which an anode, an organic light emitting layer, and a cathode are sequentially laminated on a support substrate, and an electron injection layer, an electron transport layer, a hole transport layer, a hole as necessary. An injection layer is also provided.

  The layer constituting such an organic device is generally formed by a vapor deposition method such as physical vapor deposition or sputtering. However, in recent years, in order to increase the area of organic devices such as organic electroluminescence elements, to reduce costs, and to simplify the manufacturing process, it is possible to form layers that constitute organic devices by a transfer method or a bonding method. It has been tried.

  For example, in Patent Document 1, when manufacturing an organic electroluminescence element, at least one organic layer A is formed on a substrate A by a wet process, and at least p-type hole transport is performed on a substrate B. It is disclosed that an organic layer B including a layer or an n-type electron transport layer is formed in advance, and the organic layer B is formed on the organic layer A by a transfer method or a bonding method.

JP 2009-76241 A

  However, when the organic layer is formed by a transfer method, it is necessary to form the organic material constituting the organic layer in advance, and the film-like organic material is transferred without any chipping or residue. There is a need. It is difficult to satisfy these simultaneously, and it is therefore difficult to produce an organic device with a high yield using a transfer method.

This invention is made | formed in view of the said reason, and it aims at providing the manufacturing method of the organic device which can manufacture an organic device with a sufficient yield using a transfer method.

The method for manufacturing an organic device according to the present invention includes the following steps;
Providing an intermediate member forming part of the organic device;
Providing a transfer member comprising a release layer;
Providing a coating solution containing an organic material and a solvent that dissolves the organic material and has an affinity for the release layer; and applying the coating solution on the release layer of the transfer member. Forming an organic layer on the release layer by coating, and then transferring the organic layer from the release layer onto the intermediate member;

  In the present invention, the release layer is preferably formed of a silicone material.

  In the present invention, the contact angle of water on the surface of the release layer is preferably 90 ° or more.

In the present invention, the solvent is a mixed solvent containing a first solvent in which the organic material is dissolved and a second solvent having affinity for the release layer,
Both the solubility parameter of the first solvent and the solubility parameter of the second solvent are 10 or less,
The difference in boiling point between the first solvent and the second solvent is preferably within 20 ° C.

An organic device manufacturing apparatus according to the present invention includes an organic material on a release layer of a transfer member including a release layer, and a solvent that dissolves the organic material and has an affinity for the release layer. An application part for applying an application liquid containing
A heating unit that forms an organic layer on the release layer by volatilizing the solvent by heating the coating solution on the release layer;
The intermediate member which comprises a part of organic device is provided with the transfer part which transcribe | transfers the said organic layer from the said mold release layer on the said intermediate member by pressing the said organic layer on the said mold release layer.

  According to the present invention, an organic device can be manufactured with high yield using a transfer method.

(A) thru | or (c) is a schematic sectional drawing which shows the one aspect | mode of embodiment of this invention. (A) thru | or (c) is a schematic sectional drawing which shows another aspect of embodiment of this invention. (A) thru | or (c) is a schematic sectional drawing which shows the example of a structure of the organic device obtained by this invention. It is the schematic which shows the manufacturing apparatus of the organic device which concerns on one Embodiment of this invention.

<Organic device configuration>
In this embodiment, an organic electroluminescence element is mentioned as an example of the organic device 1. The organic device 1 has a structure in which, for example, a first electrode 3, one or more organic layers 4, and a second electrode 5 are sequentially stacked. The organic device 1 includes at least a light emitting layer 43 as the organic layer 4. Furthermore, the organic device 1 includes appropriate layers such as a hole injection layer 41, a hole transport layer 42, an electron block layer, a hole block layer, an electron transport layer 44, and an electron injection layer as the organic layer 4 as necessary. For example, the organic device 1 has a laminated structure of the first electrode 3 (anode) / hole injection layer 41 / hole transport layer 42 / light emitting layer 43 / electron transport layer 44 / electron injection layer / second electrode 5 (cathode). . The base material 2 has a function of supporting a layer laminated on the base material 2. In some cases, the organic device 1 may have a structure in which the base material 2, the second electrode 5, one or more organic layers 4, and the first electrode 3 are sequentially laminated. Moreover, the organic device 1 does not include the base material 2 and may exhibit a function of supporting a layer in which the second electrode 5 is laminated on the second electrode 5, for example.

  In the present embodiment, the organic device 1 includes, for example, a first electrode 3, a hole transport layer 42, a light emitting layer 43, an electron transport layer 44, and a second electrode 5 on the substrate 2 as shown in FIG. It is obtained by laminating and forming these layers in this order. Further, the organic device 1 includes, for example, a second electrode 5, an electron transport layer 44, a light emitting layer 43, a hole transport layer 42, and the first electrode 3 on the substrate 2 as shown in FIG. These layers are obtained by stacking in this order. In addition, the organic device 1 includes an electron transport layer 44, a light emitting layer 43, a hole transport layer 42, and the first electrode 3 on the second electrode 5 as shown in FIG. 3C, for example. It is obtained by laminating in this order.

  The base material 2 is made of a flexible film-like or sheet-like member such as a plastic film or a plastic sheet produced by an arbitrary method from a resin such as polyester, polyolefin, polyamide, or epoxy, or a fluorine-based resin. It is formed. The substrate 2 may be formed from a material having rigidity such as glass.

In the present embodiment, the first electrode 3 functions as an anode. In the present embodiment, the anode is an electrode for injecting holes into the light emitting layer 43. As the anode material, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function. In particular, a material having a work function of 4 eV or more is preferably used. Specific examples of such anode materials include metals such as gold; CuI, ITO (indium-tin oxide), SnO ₂ , ZnO, IZO (indium-zinc oxide), GZO (gallium-zinc oxide). And the like; conductive polymers such as PEDOT and polyaniline; conductive polymers doped with any acceptor and the like; conductive light-transmitting materials such as carbon nanotubes and the like.

  The first electrode 3 is formed, for example, by forming the material as described above on the surface of the substrate 2 by an appropriate method such as a vacuum deposition method, a sputtering method, or a coating method.

  When the first electrode 3 is required to have light transmittance, the light transmittance of the first electrode 3 is preferably 70% or more. The sheet resistance of the first electrode 3 is preferably several hundred Ω / □ or less, and more preferably 100Ω / □ or less.

  The thickness of the first electrode 3 varies depending on the material in order to adjust the light transmittance, sheet resistance, and other characteristics of the first electrode 3 as described above, but is preferably 500 nm or less. The range of 10 to 200 nm is more preferable.

In the present embodiment, the second electrode 5 functions as a cathode. In the present embodiment, the cathode is an electrode for injecting electrons into the light emitting layer 43. The cathode material is preferably a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a low work function. It is particularly preferable if the work function of the cathode material is 5 eV or less. Specific examples of such cathode materials include alkali metals, alkali metal halides, alkali metal oxides, alkaline earth metals, and the like, and alloys of these with other metals. Examples include sodium, sodium-potassium alloy, lithium, magnesium, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / LiF mixture, and the like. As the cathode material, aluminum, Al / Al ₂ O ₃ mixture or the like can also be used. An electron injection layer formed of an alkali metal oxide, an alkali metal halide, a metal oxide or the like may be overlaid on the surface of the cathode on the light emitting layer 43 side, and the cathode is a conductive material such as a metal. It may be composed of one or more layers formed from Examples of the laminated structure of the electron injection layer and the cathode include an alkali metal / Al laminate, an alkali metal halide / alkaline earth metal / Al laminate, and an alkali metal oxide / Al laminate. . When the cathode is a light-reflective electrode, the light-reflective cathode may be configured by combining a transparent cathode and a light-reflective layer.

  When the cathode is formed as a light transmissive electrode, the cathode may be formed from a transparent electrode material typified by ITO, IZO or the like. In this case, the cathode may be formed on the substrate 2.

  The organic layer 4 directly overlapping the second electrode 5 may be doped with an alkali metal such as lithium, sodium, cesium, or calcium, or an alkaline earth metal.

  The second electrode 5 is formed, for example, by forming the above-described material into a film by an appropriate method such as a vacuum deposition method, a sputtering method, or a coating method.

  When the second electrode 5 is a light reflective electrode, the light transmittance of the second electrode 5 is preferably 10% or less. On the other hand, when the second electrode 5 is a light transmissive electrode, the light transmittance of the second electrode 5 is preferably 70% or more.

  The thickness of the second electrode 5 varies depending on the material in order to appropriately adjust characteristics such as light transmittance of the second electrode 5, but is preferably 500 nm or less, and may be in the range of 100 to 200 nm. More preferred.

  As described above, the second electrode 5 may be formed on the substrate 2. Further, when the second electrode 5 exhibits a function of supporting a layer laminated thereon, the second electrode 5 may be composed of a conductive metal plate, metal foil, metal film, or the like. Good.

  Examples of the organic layer 4 include a light emitting layer 43, a hole transport layer 42, a hole injection layer 41, and an electron transport layer 44 described below. The organic device 1 includes at least a light emitting layer 43 among these organic layers 4.

<Light emitting layer>
The light emitting layer 43 emits light by recombination of electrons injected from the cathode or electron transport layer 44 into the light emitting layer 43 and holes injected from the anode or hole transport layer 42 into the light emitting layer 43 in the light emitting layer 43. Is a layer. As a material of the light emitting layer 43, any material known as a material for an organic electroluminescence element can be used. The material of the light emitting layer 43 is not particularly limited, but preferably a carbazole derivative, a distyrylbenzene derivative, a distyrylarylene derivative, a distyrylamine derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic ring. Examples thereof include compounds, thiophene derivatives, furan derivatives, fluorene derivatives, polyfluorene derivatives, polyphenylene vinylene derivatives, and various fluorescent dyes. Examples of the material of the light emitting layer 43 include those described above and their derivatives. Two or more selected from these compounds may be used in combination.

  As a material of the light emitting layer 43, a host material serving as a matrix and a dopant material (guest material) responsible for light emission may be used in combination. The host material is not particularly limited in terms of structure, but typically, the carbazole derivative, triarylamine derivative, aromatic borane derivative, nitrogen-containing heterocyclic compound, thiophene derivative, furan derivative, oligoarylene compound, etc. And those having the basic skeleton. As the dopant material, not only a compound that emits fluorescence typified by the above compound, but also a material system that emits light from a spin multiplet, for example, a phosphorescent material that emits phosphorescence, such as an iridium complex compound, a platinum complex compound, An osmium complex compound, a rare earth complex compound, etc., and a compound having a site composed thereof in a part of the molecule can also be suitably used.

  An example of a particularly preferable material for the light-emitting layer 43 in the present embodiment is 2,7-bis (4′-hexyl- [1,1′biphenyl] -4-yl) -9,9′-spirobi, which is a fluorene derivative. [fluorene] (BHBPSF), 4,4 '-(9,9'-spirobi [fluorene] -2,7-diyl) bis (N, N-diphenylaniline) (SFBDPA), 2,7-bis (4- ( 9H-carbazol-9-yl) phenyl) -9,9'-spirobi [fluorene] (SFP-Cz); Poly [{9,9-dihexyl-2,7-bis (1-cyanovinylene)], a polyfluorene derivative fluorenylene} -alt-co- {2,5-bis (N, N′-di-phenylamino) -1,4-phenylene}]; Poly (9-vinylcarbazole) which is a carbazole derivative.

  When the host material and the guest material are combined, particularly preferred host materials in the present embodiment include 1,3-Bis (carbazol-9-yl) benzene (m-CP), 4,4′-, which is a carbazole derivative. Bis (carbazol-9-yl) biphenyl (CBP), 4,4'-Bis (carbazol-9-yl) -2,2'-dimethylbiphenyl (CDBP), 2,2'-bis (4- (carbazol-9 -yl) phenyl) -biphenyl (BCBP); and Dibenzo {[f, f ']-4,4', 7,7'-tetraphenyl} diindeno [1,2,3-cd: 1 ', 2', 3 '-lm] perylene (DBP). In addition, particularly preferred guest materials in the present embodiment include Tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3), Tris [2- (p-tolyl) pyridine] iridium (III) (Ir (mppy) 3).

<Hole transport layer>
The material of the hole transport layer 42 is selected from, for example, a group of compounds having hole transport properties. This type of compound is not particularly limited, and examples thereof include 4,4′-bis [N-naphthyl-N-phenylamino] -biphenyl (α-NPD), N, N′-bis (3-methylphenyl)-( 1,1′-biphenyl) -4,4′diamine (TPD), 2-TNATA, 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (MTDATA) , 4,4′-N, N′-dicarbazole biphenyl (CBP), spiro-NPD, spiro-TPD, spiro-TAD, TNB, and the like as triarylamine compounds; amine compounds containing a carbazole group; And amine compounds containing a fluorene derivative, etc., as well as polymer compounds into which these groups are introduced, etc. These materials can also be used as materials for the electron blocking layer. As the material of 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl (α-NPD), N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4 4,4′-diamine (TPD), 4,4′-N, N′-dicarbazolebiphenyl (CBP), 2,2′-bis (4- (carbazol-9-yl) phenyl) -biphenyl (BCBP) Can be mentioned.

<Hole injection layer>
The material of the hole injection layer 41 is not particularly limited, and any generally known hole injection material can be used. Preferable examples of the material of the hole injection layer 41 include low molecular weight organic compounds such as copper phthalocyanine (CuPc) and triarylamine derivatives, and polymer materials such as polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS). It is done. Any material can be used for the ho transport layer as long as it has good hole injectability. A particularly preferable example in this embodiment includes N4, N4 ′-(biphenyl-4,4′-diyl) bis (N4, N4 ′, N4′-triphenylbiphenyl-4,4′-diamine) (TPT1).

<Electron transport layer>
The material of the electron transport layer 44 is appropriately selected from, for example, a group of compounds having electron transport properties. This type of compound is not particularly limited, and any generally known electron transporting material can be used. As the material for the electron transport layer 44, a material having a particularly high charge transport property is preferably used. Examples of such materials for the electron transport layer 44 include compounds having a heterocycle such as phenanthroline derivatives, pyridine derivatives, imidazole derivatives, triazine derivatives, tetrazine derivatives, oxadiazole derivatives, phosphine oxide compounds, and the like. These materials can also be used as the material for the hole blocking layer.

<Material type>
The organic materials constituting these organic layers 4 are not limited to the above materials as long as they have characteristics suitable for each organic layer 4. Moreover, as this organic material, a low molecular material, an oligomer material, a dendrimer material, a high molecular material, etc. can be used, and these mixtures can also be used. In particular, the present embodiment has an advantage that the organic layer 4 can be formed efficiently and with a high yield by the transfer method even when a low molecular material that is difficult to apply to the transfer method is used. Here, the low molecular weight material means a material having a molecular weight of 1200 or less. The molecular weight distribution of the low molecular weight material is preferably monodispersed (monodispersed). Moreover, the organic material which comprises the organic layer 4 may contain the substance which improves film forming property in the range which does not inhibit the characteristic of this organic material.

<Production method>
In the present embodiment, at least one of the organic layers 4 of the organic device 1 is formed by a transfer method as shown in FIGS. When the organic device 1 includes a plurality of organic layers 4, all the organic layers 4 may be formed by a transfer method.

  When the organic layer 4 is formed by the transfer method, a transfer member 9 including a release layer 7 is used. The transfer member 9 includes, for example, a sheet-like base material (donor base material 6) and a release layer 7 formed on the donor base material 6.

  The donor substrate 6 is preferably a flexible sheet-like member. As the donor substrate 6, for example, a flexible film-like or sheet-like material such as a plastic film or a plastic sheet produced by an arbitrary method from a resin such as polyester, polyolefin, polyamide, epoxy, or a fluorine-based resin. It is formed from a member. Moreover, when the organic device 1 provided with the base material 2 is manufactured, when the base material 2 is formed from a film-like or sheet-like member having flexibility, the donor base material 6 has flexibility. It may be formed from a film-like or sheet-like member, or may be formed from a material having rigidity such as glass. That is, it is preferable that at least one of the base material 2 and the donor base material 6 is formed from a flexible film-like or sheet-like member. In particular, the substrate 2 is formed from a material having rigidity, or is formed from a flexible film or sheet member, and the donor substrate 6 is formed from a flexible film or sheet member. Preferably it is formed.

  The release layer 7 has a function of improving the peelability of the organic layer 4 from the transfer member 9 when the organic layer 4 is transferred.

  The release layer 7 can be formed of an appropriate material, but is preferably formed of a silicone-based material, and is particularly preferably formed of siloxane such as poly (monomethylsiloxane). In this case, the organic layer 4 formed from an organic material is easily peeled off from the release layer 7.

The release layer 7 is formed from, for example, a silicone composition containing the following components (A), (B), and (C).
(A) Conditions under which 0.001 to 0.5 mol of water is used per 1 mol equivalent of X in colloidal silica in which a hydrolyzable organosilane represented by the following general formula (I) is dispersed in an organic solvent or water Solution prepared by partial hydrolysis underneath.
R ³ _k SiX _4-k (I)
(Wherein R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, k represents an integer of 0 to 3, and X represents a hydrolyzable group.)
(B) A polyorganosiloxane having an average composition formula represented by the following formula (II) and containing at least a silanol group in the molecule.
R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (II)
Wherein R ⁴ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, respectively. And a + b <4.)
(C) Curing catalyst.

  As the component (A), for example, one or more hydrolyzable group-containing organosilanes represented by the general formula (I) are added to colloidal silica dispersed in an organic solvent or water. The functional group-containing organosilane is prepared by partial hydrolysis in the presence of water in colloidal silica or separately added water.

In the hydrolyzable group-containing organosilane represented by the general formula (I), R ³ in the general formula (I) represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples include a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; 2-phenylethyl Groups, aralkyl groups such as 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3,3- And halogen-substituted hydrocarbon groups such as trifluoropropyl group; and substituted hydrocarbons such as γ-methacryloxypropyl group and γ-mercaptopropyl group. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable because of easy synthesis or availability. Examples of X that is a hydrolyzable group include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, and an amide group. Among these, an alkoxy group is preferable because it is easily available and a silica-dispersed oligomer solution is easily prepared.

  Examples of the hydrolyzable group-containing organosilane represented by the general formula (I) include monofunctional (k = 3), bifunctional (k = 2), trifunctional (k = 1), and Examples include tetrafunctional (k = 0) alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, and amidosilanes. Among these, alkoxysilanes are preferred because they are easily available and silica-dispersed organosilane oligomer solutions are easily prepared. Among the alkoxysilanes, examples of the tetraalkoxysilane (k = 0) include tetramethoxysilane and tetraethoxysilane, and examples of the organotrialkoxysilane (k = 1) include methyltrimethoxysilane, methyltriethoxysilane, and methyl. Examples include triisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxylane and the like. Examples of the diorganodialkoxysilane (k = 2) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Triorganoalkoxysilane (k = 3) ) Is exemplified by trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylisobutylmethoxysila and the like. Furthermore, organosilane compounds generally called silane coupling agents are also included in the alkoxysilanes.

  In the component (A), the proportion of the trifunctional (k = 1) compound in the entire hydrolyzable group-containing organosilane represented by the general formula (I) is preferably 50 mol% or more. If it is more than mol%, it is still more preferable, and it is most preferable if it is 70 mol% or more. In this case, the coating film hardness of the silicone composition becomes sufficiently high, and the silicone composition becomes excellent in dry curability.

  The hardness of the cured film formed from the silicone composition is improved by the colloidal silica in the component (A), and the smoothness and crack resistance of the cured film are improved. Examples of the colloidal silica include colloidal silica having water dispersibility and colloidal silica having dispersibility of a non-aqueous organic solvent such as alcohol. In general, such colloidal silica contains 20 to 50% by mass of silica as a solid content. When water-dispersible colloidal silica is used, the water in the water-dispersible colloidal silica can function as a curing agent as will be described later. Water dispersible colloidal silica is usually prepared from water glass. Commercial products are easily obtained as such colloidal silica. The organic solvent-dispersed colloidal silica is easily prepared by replacing the water of the water-dispersible colloidal silica with an organic solvent. As such organic solvent-dispersed colloidal silica, commercially available products are easily obtained. Examples of the organic solvent in the organic solvent-dispersed colloidal silica include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol And ethylene glycol derivatives such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether, and diacetone alcohol. Only one of these organic solvents can be used, or two or more can be used in combination. In addition to these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, and the like may be used in combination.

  In the component (A), the colloidal silica is preferably contained in the range of 5 to 95% by mass as the silica solid content, more preferably 10 to 90% by mass, and most preferably in the range of 20 to 85% by mass. It is. For example, if the content is less than 5% by mass, the desired film hardness cannot be obtained, and if it exceeds 95% by mass, the uniform dispersion of silica becomes difficult and the (A) component gels. There is.

  The silica-dispersed oligomer in component (A) is usually obtained by partially hydrolyzing a hydrolyzable group-containing organosilane in the presence of colloidal silica. The amount of water used for partially hydrolyzing the hydrolyzable organosilane is preferably in the range of 0.001 to 0.5 mol of water with respect to 1 mol equivalent of the hydrolyzable group (X). For example, if the amount of water used is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate becomes poor. The method of partial hydrolysis is not particularly limited, and a hydrolyzable organoalkoxysilane and colloidal silica may be mixed and added with a necessary amount of water. At this time, the partial hydrolysis reaction proceeds at room temperature. . In addition, in order to accelerate | stimulate partial hydrolysis reaction, you may heat at 60-100 degreeC, and also in order to accelerate | stimulate partial hydrolysis reaction, hydrochloric acid, an acetic acid, halogenated silane, chloroacetic acid, a citric acid, a benzoic acid, Organic acids and inorganic acids such as dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid may be used as the catalyst.

  In order to obtain the component (A) stably in the long term, the pH of the liquid is 2.0 to 7.0, preferably 2.5 to 6.5, more preferably 3.0 to 6.0. It is good to. When the pH is outside this range, the amount of water used is 0.3 mol or more with respect to 1 mole equivalent of the substituent X in the formula (I), and the long-term performance deterioration of the component (A) is remarkable. When the pH of the component (A) is outside this range, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if it is more acidic than this range. Adjustment may be performed using an acidic reagent such as acetic acid. The adjustment method is not particularly limited.

Next, the component (B) will be described. As described above, the component (B) has an average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (wherein R ⁴ is the same or different substituted or unsubstituted carbon number of 1). A monovalent hydrocarbon group of ˜8, wherein a and b are numbers satisfying the relations 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b <4, respectively. It is a polyorganosiloxane containing silanol groups.

In the formula, as R ⁴ , the same as R ³ in the above formula (I) is exemplified, but preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a γ-glycidoxypropyl group, Substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-aminopropyl group and 3,3,3-trifluoropropyl group, more preferably methyl group and phenyl group. Further, a and b in the formula (II) are numbers satisfying the above relationship, respectively, and when a is less than 0.2 or b is more than 3, there is a disadvantage such as a crack in the cured film. When it is more than 2 and 4 or less, or when b is less than 0.0001, curing does not proceed well. Such a silanol group-containing polyorganosiloxane can be prepared by a known method using a large amount of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or a mixture of one or more of the corresponding alkoxysilanes. It can be obtained by hydrolysis with water. When a silanol group-containing polyorganosiloxane is obtained and hydrolyzed by a known method using alkoxysilane, an unhydrolyzed alkoxy group may remain in a trace amount. In other words, a polyorganosiloxane in which a silanol group and a trace amount of alkoxy group coexist may be obtained, but such a polyorganosiloxane may be used.

  The curing catalyst which is the component (C) accelerates the condensation reaction between the component (A) and the component (B) and cures the coating as described above. Such catalysts include metal salts of carboxylic acids such as alkyl titanates, tin octylate and dibutyltin dilaurate, dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine Amine salts such as acetate; quaternary ammonium salts of carboxylic acid such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl Amine amine silane coupling agents such as γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali catalysts such as potassium hydroxide; tetra Isopropyl titane And titanium compounds such as tetrabutyl titanate and titanium tetraacetylacetonate, and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane. In addition to these, (A) component and (B) There is no particular limitation as long as it is effective for the condensation reaction of the components.

  The blending ratio of the component (A) and the component (B) is 99 to 1 part by weight of the component (B) with respect to 1 to 99 parts by weight of the component (A), more preferably 5 to 95 parts by weight of the component (A). The component (B) is 95 to 5 parts by mass, and most preferably the component (B) is 90 to 10 parts by mass with respect to the component (A) 10 to 90 parts by mass. When the component (A) is less than 1 part by mass, the room temperature curability is inferior and sufficient film hardness cannot be obtained. On the other hand, when it exceeds 99 parts by mass, the curability is unstable and a good coating film may not be obtained.

  Further, the addition amount of the curing catalyst as the component (C) is preferably 0.0001 to 10% by mass with respect to the total amount of the component (A) and the component (B) as 100, more preferably 0.00. It is 0005-8 mass%, Most preferably, it is 0.0007-5 mass%. If it is less than 0.0001% by mass, it does not cure at room temperature. Moreover, when it exceeds 10 mass%, heat resistance and a weather resistance will worsen.

  The hydrolyzable group contained in the silica dispersion oligomer of component (A) and the silanol group of component (B) undergo a condensation reaction by heating at room temperature or low temperature in the presence of the curing catalyst of component (C). To form a cured coating. Therefore, this silicone composition is hardly affected by humidity even when cured at room temperature. Moreover, a condensation reaction can be accelerated | stimulated by heat processing and a hardened film can be formed.

  This silicone composition can be diluted with various organic solvents for ease of handling. The type of organic solvent used at this time can be selected according to the type of monovalent hydrocarbon group or the molecular weight of component (A) or component (B). Lower aliphatic alcohols such as ethanol, ethanol, isopropanol, n-butanol, isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, etc. Derivatives of diethylene glycol such as diethylene glycol and diethylene glycol monobutyl ether and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol -You can list It can be used more than one or two selected from the group consisting.

It is also preferred that the silicone composition further contains a linear polysiloxane diol having an average composition represented by the following formula (VI).
H (R ⁷ ₂ SiO) _m OH (VI)
M in the formula (VI) is m ≧ 3, preferably 10-100. R ⁷ in the formula represents the same as R ³ . Since this linear polysiloxane diol has no reactive group other than the terminal OH group, it is a molecule with relatively poor reactivity. For this reason, the linear polysiloxane diol blended in the silicone composition lacks complete compatibility in the coating material and is dispersed as ultrafine particles. In the end, the terminal OH group undergoes a condensation reaction with the bulk resin to be immobilized on the coating film surface. As a result, there is an effect that it is localized on the surface of the R ⁷ group and improves the peelability from the first coat layer. Those having a relatively small m in the formula are excellent in compatibility, and thus not only form a layer on the surface of the coating film, but also add flexibility to the coating film by being incorporated into the bulk, leading to a crack prevention effect. It is preferable that content of the said linear polysiloxane diol is 0.1-100 mass% with respect to the sum of the mass which converted silicone as a condensed silicon compound, and the mass of silica in a silicone composition. This is because if the content of the linear polysiloxane diol is less than 0.1% by mass, the release property is weak, and if it exceeds 100% by mass, the coating may be inhibited from being cured.

The silicone composition is represented by the following general formula (VII), and at least one first (meth) acrylic acid ester in which R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms. And at least one second (meth) acrylic acid ester represented by the following general formula (VII) and R ⁹ is an epoxy group, a glycidyl group or a hydrocarbon group containing them, and the following general formula (VII And at least one third acrylic ester or methacrylic ester in which R ⁹ is a hydrocarbon group containing an alkoxysilyl group or a halogenated silyl group. It is also preferable to further contain a polymer. This acrylic resin copolymer exhibits the effect of improving the toughness of the coating film of the silicone composition.
CH ₂ = CR ⁸ (COOR ⁹ ) (VII)
(In the formula, R ⁸ represents a hydrogen atom or a methyl group.)
As described above, this acrylic resin copolymer is a copolymer of the first, second and third (meth) acrylic acid esters. In the first (meth) acrylic acid ester, R ⁹ in the formula (VII) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. Alkyl groups such as i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group; cyclopentyl group, cyclohexyl group, etc. Cycloalkyl group; aralkyl group such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl group such as phenyl group and tolyl group; chloromethyl group, γ-chloropropyl group, 3, 3 , 3-trifluoropropyl group and other halogenated hydrocarbon groups; 2-hydroxyethyl group and other hydroxy hydrocarbon groups; It is. In addition, the second (meth) acrylic acid ester has at least R ⁹ in the formula (VII) in which R ⁹ is an epoxy group, a glycidyl group or a hydrocarbon group containing them, for example, a γ-glycidoxypropyl group. One type. The third (meth) acrylic acid ester is a hydrocarbon group in which R ⁹ in the formula (VII) contains an alkoxysilyl group or a halogenated silyl group, such as trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethyl At least one of silylpropyl, ethoxydimethylsilylpropyl, trichlorosilylpropyl, dichloromethylsilylpropyl, and chlorodimethylsilylpropyl. This acrylic copolymer is a copolymer of (meth) acrylic acid ester containing at least one kind and a total of at least three or more kinds in the first, second and third (meth) acrylic acid esters, One or more kinds selected from the first, second and third (meth) acrylic acid esters, or one or two or more kinds selected from other (meth) acrylic acid esters other than the above. It may be a copolymer containing.

The first (meth) acrylic acid ester improves the toughness of the coating film of the silicone composition. For this purpose, the substituted or unsubstituted hydrocarbon group of R ⁹ desirably has a volume of a certain level or more, and preferably has 2 or more carbon atoms. When the third (meth) acrylic acid ester is used, it is chemically bonded between the acrylic resin copolymer, the component (A) and the component (B) at the time of curing the coating film. The copolymer is immobilized in the coating film. The third (meth) acrylic acid ester also has an effect of improving the compatibility between the components constituting the silicone composition.

  The molecular weight of this acrylic resin copolymer is greatly related to the compatibility with the component (A) and the component (B). When the polystyrene-reduced average molecular weight of the acrylic resin copolymer exceeds 50,000, phase separation may occur and the coating film may be whitened. Therefore, it is desirable that this acrylic resin copolymer has an average molecular weight in terms of polystyrene of 50,000 or less. The lower limit of the polystyrene-reduced average molecular weight of the acrylic resin copolymer is desirably 1000. If the molecular weight is less than 1000, the toughness of the coating film tends to decrease and cracks tend to occur, which is not preferable. The third (meth) acrylic acid ester having an alkoxysilyl group or a halogenated silyl group is desirably in the range of 2 to 50% by mass in terms of the monomer molar ratio in the copolymer. If it is less than 2 mass%, the compatibility of this acrylic resin copolymer with the component (A) and the component (B) is poor, and the coating film may be whitened. On the other hand, when the content exceeds 50% by mass, the bond density between the acrylic resin copolymer, the component (A) and the component (B) becomes too high, and the improvement in toughness due to the addition of the acrylic resin copolymer is sufficiently exhibited. Not. As a method for synthesizing this acrylic resin copolymer, a solution polymerization in a known organic solvent, an emulsion polymerization, a radical polymerization method by suspension polymerization, an anionic polymerization method, a cationic polymerization method and the like can be employed.

  The content of the acrylic copolymer is preferably 0.1 to 100% by mass with respect to the sum of the mass of silica converted to a condensed silicon compound and the mass of silica in the silicone composition. This is because if it is less than 0.1% by mass, the toughness is weakly expressed, and if it exceeds 100% by mass, the coating is hardened.

  The release layer 7 is formed by applying and drying a silicone composition on the donor substrate 6. The application method of the silicone composition is not particularly limited. For example, a gravure roll coater, a gravure offset roll coater, a micro gravure roll coater, a drawing roll coater, an air knife coater, a reverse roll coater, a bar coater, a die coater, and a fountain. Various coating methods such as coater, commar, spray, dipping, and flow can be selected. At this time, a leveling agent may be added to the silicone composition as necessary. The drying conditions may be appropriately determined depending on the heat-resistant temperature of the donor substrate 6, and may be room temperature drying, for example. The thickness of the release layer 7 is not particularly limited, but is, for example, in the range of 0.1 to 20 μm, and the release layer 7 can follow the deformation of the transfer member 9 during transfer without causing cracks. In order to do so, 0.1-15 micrometers is desirable. In addition, when the silicone composition contains the above-mentioned linear polysiloxane diol or acrylic resin copolymer in order to improve the peelability, crack prevention property and flexibility, the thickness of the release layer 7 is compared. For example, in order that the release layer 7 can follow the deformation of the transfer member 9 during transfer without causing cracks, for example, the thickness may be in the range of 0.1 to 50 μm. 0.1-30 micrometers is more desirable.

  The contact angle of water on the surface of the release layer 7 is preferably 90 ° or more. In this case, the organic layer 4 formed on the release layer 7 is more easily peeled off from the release layer 7 during transfer. If the release layer 7 is formed of the silicone composition as described above and the reaction of the silicone composition is sufficiently advanced when the release layer 7 is formed, the contact angle of water on the surface of the release layer 7 Is easily 90 ° or more.

  Further, in order to set the contact angle of water on the surface of the release layer 7 to 90 ° or more, an appropriate hydrophilic treatment may be performed on the surface of the donor substrate 6 in advance before forming the release layer 7. preferable. In this case, when the release layer 7 is formed on the surface of the donor substrate 6 that has been subjected to the hydrophilic treatment, the hydrophilic groups in the molecules constituting the release layer 7 and the surface of the donor substrate 6 that has been subjected to the hydrophilic treatment are obtained. At the same time, the density of hydrophilic groups decreases and the density of hydrophobic groups increases on the surface side in the release layer 7, thereby improving the hydrophobicity of the surface of the release layer 7 and increasing its water content. The contact angle increases.

  Further, in order to set the contact angle of water on the surface of the release layer 7 to 90 ° or more, when the release layer 7 is formed, a silicone composition is applied onto the donor substrate 6 and dried to form a coating film. It is also preferable to form the release layer 7 by allowing the reaction of the silicone composition to proceed while exposing the coating film to an atmosphere containing an organic solvent. The organic solvent contained in the atmosphere is preferably the same as the organic solvent in the silicone composition used for forming the release layer 7. In this case, the reaction of the silicone composition is promoted, thereby improving the hydrophobicity of the surface of the release layer 7 and increasing the contact angle of water.

  When the organic layer 4 in the organic device 1 is formed by a transfer method, the organic layer 4 is first formed on the release layer 7 of the transfer member 9. The thickness of the organic layer 4 is appropriately set according to the material and function of the organic layer 4.

  In forming the organic layer 4, first, a coating solution 10 containing an organic material that constitutes the organic layer 4 and a solvent that dissolves the organic material and has an affinity for the release layer 7 is prepared.

  The solvent having an affinity for the release layer 7 while the organic material is dissolved is a mixed solvent including a first solvent in which the organic material is dissolved and a second solvent having an affinity for the release layer 7. It is preferable that In this case, the solubility of the organic material and the affinity for the release layer 7 in the solvent having the affinity for the release layer 7 as well as the dissolution of the organic material can be easily adjusted.

  The first solvent in which the organic material used for the preparation of the mixed solvent dissolves depends on the type of the organic material and is not particularly limited, but preferred specific examples thereof include chloroform, 1,2-dichloromethane, Examples thereof include halogen solvents such as chlorobenzene and dichlorobenzene, and furan solvents such as tetrahydrofuran.

  The second solvent having an affinity for the release layer 7 used for the preparation of the mixed solvent depends on the composition of the release layer 7 and is not particularly limited. Preferable examples of the second solvent when formed from the material include alcohols, ketones, lower alkyl acetates, fluorine-based solvents and the like.

  Furthermore, the difference in boiling point between the first solvent and the second solvent is preferably small, and the difference in boiling point is particularly preferably within 20 ° C. In this case, as described later, the film formability of the organic layer 4 is improved.

  It is also preferred that the solubility parameter of the first solvent and the solubility parameter of the second solvent are both 10 or less. In this case, the compatibility of the first solvent and the second solvent is increased, and a highly uniform mixed solvent can be obtained. For this reason, this mixed solvent exhibits the solubility of the organic material and the affinity for the release layer over the entire mixed solvent, thereby further improving the film formability of the organic layer 4.

  As a particularly preferable example of the mixed solvent, chloroform (boiling point 61.0 ° C., solubility parameter 9.3) is contained as the first solvent, and acetone (boiling point 56.1 ° C., solubility parameter 10.0) is contained as the second solvent. A mixed solvent containing chloroform, chloroform (boiling point 61.0 ° C., solubility parameter 9.3) as the first solvent, and ethyl acetate (boiling point 79.5 ° C., solubility parameter 9.0) as the second solvent. Contains mixed solvent, first solvent as chloroform (boiling point 61.0 ° C., solubility parameter 9.3) and second solvent as methyl ethyl ketone (boiling point 79.5 ° C., solubility parameter 9.3) Containing a mixed solvent, tetrahydrofuran (boiling point 66.0 ° C., solubility parameter 9.1) as the first solvent, Mixed solvent containing acetone (boiling point 56.1 ° C., solubility parameter 10.0), dichloromethane as first solvent (boiling point 40.0 ° C., solubility parameter 9.7) and acetone as second solvent And a mixed solvent containing (boiling point 56.1 ° C., solubility parameter 10.0).

  The ratio of the first solvent and the second solvent in the mixed solvent is not particularly limited, but the volume ratio of the former to the latter is preferably in the range of 2: 1 to 1: 2, and 1: 1 to 1: A range of 2 is more preferable.

  The content of the organic material in the coating liquid 10 is not particularly limited, and is appropriately set so that the organic material is uniformly dissolved in the coating liquid 10 and the film forming property of the organic layer 4 is improved.

  A coating film (wet coating film) is formed by applying the coating solution 10 onto the release layer 7. The coating method of the coating liquid 10 on the release layer 7 is not particularly limited, and is an inkjet printing method, a screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a dispenser printing method, a slit coating method, a die coating method, An appropriate method such as a doctor blade coating method or a wire bar coating method may be employed.

  The organic layer 4 is formed by volatilizing the solvent from the wet coating film formed on the release layer 7. In this case, the solvent may be volatilized from the wet coating film at room temperature, or the solvent may be volatilized from the wet coating film by heating the wet coating film. The heating conditions such as the heating temperature when heating the wet coating are appropriately set according to the type of solvent, etc. For example, the second solvent contains chloroform (boiling point 61.0 ° C.) as the first solvent. When a mixed solvent containing acetone (boiling point 56.1 ° C.) is used as the solvent, it is preferably heated at 60 to 100 ° C. for 0.5 to 3 minutes.

  When the organic layer 4 is formed on the release layer 7 in this way, when the wet coating film is formed on the release layer 7, the solvent in the coating solution 10 dissolves the organic material and Since it has an affinity for the release layer 7, a wet coating film with little unevenness and high uniformity can be formed. When the solvent is volatilized from the wet coating film, the organic layer 4 with less unevenness and high uniformity is formed on the release layer 7.

  When the solvent in the coating solution 10 is a mixed solvent containing the first solvent and the second solvent, it is preferable that the boiling points of the first solvent and the second solvent are close to each other. The difference is preferably within 20 ° C. In this case, in the process of volatilization of the solvent from the wet coating film, the second solvent is volatilized excessively compared to the first solvent, so that the wet coating film is repelled from the release layer 7, Aggregation of the organic material due to excessive volatilization of the first solvent compared to the solvent is suppressed. Thereby, the unevenness of the organic layer 4 formed on the release layer 7 is further suppressed, and the uniformity of the organic layer 4 is further improved.

  While forming the organic layer 4 on a transfer member as mentioned above, the intermediate member 8 which comprises some organic devices 1 is also prepared. The organic layer 4 on the transfer member 9 is transferred to the intermediate member 8.

  The intermediate member 8 is a member constituting a part of the organic device 1 and may have a structure in which the organic layer 4 on the transfer member 9 is to be laminated. As the intermediate member 8, for example, a member including a base material 2 and a first electrode 3 stacked on the base material 2; a base material 2, a first electrode stacked on the base material 2 3 and a member comprising one or a plurality of organic layers 4 (an organic layer 4 different from the organic layer 4 on the transfer member 9) overlaid on the first electrode 3; A member comprising a second electrode 5 superimposed on the material 2; a base material 2, a second electrode 5 superimposed on the base material 2, and a second electrode 5 Examples thereof include a member provided with one or a plurality of organic layers 4 (an organic layer 4 different from the organic layer 4 on the transfer member 9). When the organic device 1 does not include the base material 2 and the second electrode 5 exhibits a function of supporting a layer laminated on the second electrode 5, the intermediate member 8 is the second electrode. A member including only the second electrode 5 and a single layer or a plurality of layers of the organic layer 4 (an organic layer 4 different from the organic layer 4 on the transfer member 9). May be.

  In the embodiment shown in FIG. 1, the intermediate member 8 is a member including the base material 2 and the first electrode 3 stacked on the base material 2.

  The organic layer 4 on the transfer member 9 (hole injection layer 41 in the embodiment shown in FIG. 1) is superimposed on the intermediate member 8 and pressed, so that the organic layer 4 on the transfer member 9 is intermediate. Transferred onto the member 8. At this time, in order to promote the transfer of the organic layer 4, the transfer member 9 is maintained at an appropriate temperature so that the organic layer 4 can be easily separated from the transfer member 9, and the intermediate member 8 is It is preferable that the temperature be maintained at an appropriate temperature that allows the organic layer 4 to be in close contact with the intermediate member 8. The preferable temperature of the intermediate member 8 and the transfer member 9 at the time of transfer depends on the structure of these members and the organic layer 4, but the temperature of the transfer member 9 is preferably higher than the intermediate member 8, for example, It is preferable that the intermediate member 8 is held at 140 ° C. and the transfer member 9 is held at 80 ° C., respectively.

  Thus, when the organic layer 4 on the transfer member 9 is transferred onto the intermediate member 8, at least one of the base material 2 and the donor base material 6 is a flexible film-like or sheet-like member. When formed, at least one of the intermediate member 8 and the transfer member 9 can be pressed while being curved. Therefore, the organic layer 4 on the transfer member 9 is further easily transferred onto the intermediate member 8.

  The intermediate member 8 on which the hole injection layer 41 is laminated is further laminated thereon with a hole transport layer 42, a light emitting layer 43, an electron transport layer 44, etc., which are the organic layers 4, and further on the second electrode 5. Are superimposed. Thereby, the organic electroluminescent element 1 as shown in FIG. 3A is obtained. When another organic layer 4 is stacked on the organic layer 4 (for example, when the hole transport layer 42 is stacked on the hole injection layer 41), the member is constituted by the organic layer 4 being stacked on the intermediate member 8. May be regarded as a new intermediate member 8, and the above-described method may be repeated using the new intermediate member 8.

In the embodiment shown in FIG. 2, the electron transport layer 44 is formed as the organic layer 4 on the surface of the release layer 7 in the transfer member 9 including the donor substrate 6 and the release layer 7 similar to the case shown in FIG. 1. It is formed by the same method as described above. ,
On the other hand, the intermediate member 8 is composed of only the second electrode 5. In this case, the second electrode 5 exhibits a function of supporting a layer laminated thereon, and is composed of, for example, a conductive metal plate, metal foil, metal film, or the like.

  Also in this case, the organic layer 4 on the transfer member 9 (electron transport layer 44 in the embodiment shown in FIG. 2) is superimposed on the intermediate member 8 and pressed, so that the organic layer 4 on the transfer member 9 is Transferred onto the intermediate member 8. At this time, in order to facilitate the transfer of the organic layer 4 as in the case shown in FIG. 1, the transfer member 9 is maintained at an appropriate temperature so that the organic layer 4 can be easily separated from the transfer member 9. At the same time, it is preferable that the intermediate member 8 is maintained at an appropriate temperature so that the organic layer 4 can easily adhere to the intermediate member 8.

  The intermediate member 8 on which the electron transport layer 44 is laminated is further laminated thereon with a light emitting layer 43, which is the organic layer 4, a hole transport layer 42, a hole injection layer 41, and the like, and further on the first electrode 3. Are superimposed. Thereby, the organic electroluminescent element 1 as shown in FIG. 3C is obtained. When another organic layer 4 is stacked on the organic layer 4 (for example, when the light emitting layer 43 is stacked on the electron transport layer 44), a member constituted by the organic layer 4 being stacked on the intermediate member 8 is formed. The above-described method may be repeated using the new intermediate member 8 as a new intermediate member 8.

  The one or more organic layers 4 in the organic device 1 are formed by the above-described method. When the organic device 1 includes a plurality of organic layers 4, some of the organic layers 4 may be formed by the above-described method, or all the organic layers 4 may be formed by the above-described method. That is, for example, when the electron transport layer 44, the light emitting layer 43, and the hole transport layer 42 are sequentially formed as the organic layer 4 on the first electrode 3 on the substrate 2, a part of these organic layers 4 is formed. The organic layer 4 may be formed by the method described above, or all the organic layers 4 may be formed by the method described above. When some of the organic layers 4 are formed by the above-described method, the remaining organic layers 4 may be formed by a known method such as a vapor deposition method.

  Next, an apparatus for producing the organic device 1 by the above method will be described.

  FIG. 4 shows a schematic configuration of one aspect of the manufacturing apparatus of the organic device 1. This apparatus is configured to apply a coating liquid 10 to a transfer unit (first transfer unit) that transfers a long transfer member 9, a transfer unit (second transfer unit) that transfers an intermediate member 8, and a transfer member 9. A heating part (first heating part 17) for heating the transfer member 9, a heating part (second heating part 18) for heating the intermediate member 8, and the intermediate member 8 on the release layer 7 of the transfer member 9 And a transfer part that transfers the organic layer 4 from the release layer 7 onto the intermediate member 8 by pressing the organic layer 4.

  In this aspect, the first transport unit holds the transfer member 9 in a wound state, and at the same time, feeds the transfer base material 2 and the winding member 11 that winds the transfer member 9 fed from the feed machine 11. A take-up machine 12 and a pressing roll 13 provided on the transfer path of the transfer member 9 between the feeding machine 11 and the wind-up machine 12 are provided. As a result, the transfer member 9 is fed from the feeding machine 11, passes below the pressing roll 13 while being supported by the pressing roll 13, and is further conveyed by the winding machine 12. The transfer member 9 is conveyed so that the surface of the release layer 7 faces downward when the transfer member 9 passes below the pressing roll 13. In addition, the structure of a 1st conveyance part is not restricted to this aspect. For example, the first transport unit may transport the loop-shaped transfer member 9 while rotating it.

  On the other hand, in this aspect, the second transport unit is configured such that the second transport unit transports the long intermediate member 8 so as to pass further below the transfer member 9 below the pressing roll 13. In this embodiment, the second transport unit is configured by the roller conveyor 14. The first transport unit and the second transport unit transport the transfer member 9 and the intermediate member 8 so that their transport speeds are synchronized. In addition, the structure of a 2nd conveyance part is not restricted to this aspect. For example, if the base member 2 in the intermediate member 8 is formed from a flexible film-like or sheet-like member, and the intermediate member 8 has flexibility as a whole, the second conveying portion is the first conveying in this embodiment. The intermediate member 8 may be transported in a roll-to-roll manner in the same manner as the section. Moreover, you may be comprised by the slide drive device which drives so that a 2nd conveyance part may move, hold | maintaining and fixing the intermediate member 8. FIG.

  In this embodiment, the application unit includes an application nozzle 15 and an application roll 16. The application nozzle 15 is configured to supply the application liquid 10 onto the application roll 16. The coating roll 16 is disposed between the feeding machine 11 and the pressing roll 13 so as to face the release layer 7 of the transfer member 9. The coating roll 16 rotates as the transfer member 9 moves, and the coating liquid 10 on the coating roll 16 is applied onto the release layer 7 of the transfer member 9 accordingly.

  In this embodiment, the first heating unit 17 is configured such that the transfer member 9 is heated between the coating roll 16 and the pressing roll 13 by the first heating unit 17. As the 1st heating part 17, suitable heaters, such as an electric heater and an infrared heater, can be adopted, for example. The output of the first heating unit 17 is that the transfer member 9 is heated by the first heating unit 17, whereby the solvent is volatilized from the coating solution 10 on the transfer member 9 to form the organic layer 4, or Further, the temperature of the transfer member 9 is adjusted as appropriate so that the temperature of the transfer member 9 is heated to a temperature suitable for the transfer of the organic layer 4.

  In this embodiment, the second heating unit 18 is configured such that the intermediate member 8 before passing below the pressing roll 13 is heated by the second heating unit 18. As the second heating unit 18, for example, an appropriate heater such as an electric heater or an infrared heater can be adopted. The output of the second heating unit 18 is appropriately adjusted such that the intermediate member 8 is heated to a temperature suitable for the transfer of the organic layer 4 by the second heating unit 18.

  In this embodiment, the transfer unit is constituted by the pressing roll 13 in the first transport unit. An appropriate interval is provided between the pressing roll 13 and the intermediate member 8 conveyed by the second conveying unit, and the organic layer 4 on the transfer member supported by the pressing roll 13 is thereby formed on the intermediate member 8. To be transferred onto the intermediate member 8. At this time, in order to transfer the organic layer 4 with a high yield, it is preferable that a surface pressure having a certain width is applied from the pressure roll 13 to the intermediate member 8 instead of a linear pressure. It is preferable to have flexibility. For this reason, it is preferable that the outer peripheral surface of the press roll 13 is formed from flexible materials, such as an elastomer.

  When the organic device 1 is manufactured using the apparatus configured as described above, first, a long intermediate member 8 and a long transfer member 9 are prepared. In this aspect, the intermediate member 8 includes a long base material 2 and a plurality of first electrodes 3 formed on the base material 2. The first electrodes 3 are formed so as to be aligned along the longitudinal direction of the substrate 2. The first electrode 3 is formed by an appropriate method such as a coating method or a vapor deposition method. The long transfer member 9 includes a long donor substrate 6 formed of a flexible film or sheet member, and a release layer formed on the donor substrate 6. 7 and has flexibility as a whole.

  The transfer member 9 is set in the first conveyance unit and the intermediate member 8 is set in the second conveyance unit. The first conveyance unit conveys the transfer member 9 and the second conveyance unit conveys the intermediate member 8. To do.

  On the release layer 7 of the transfer member 9 conveyed by the first conveyance unit, the coating liquid 10 is applied by the application unit to form a wet coating film. At this time, the coating liquid 10 is intermittently supplied from the coating nozzle 15 to the coating roll 16, so that wet coating films are formed on the intermediate member 8 at a plurality of locations along the longitudinal direction at intervals. . Subsequently, the transfer member 9 is heated by the first heating unit 17, whereby the solvent in the wet coating film is volatilized, whereby the organic layer 4 is formed. Furthermore, the transfer member 9 is heated to a temperature suitable for the transfer of the organic layer 4 by being heated by the first heating unit 17.

  On the other hand, the intermediate member 8 conveyed by the second conveyance unit is heated to a temperature suitable for the transfer of the organic layer 4 by the second heating unit 18 and then passes below the pressing roll 13.

  When the transfer member 9 passes below the pressing roll 13, the organic layer 4 on the transfer member 9 is pressed onto the intermediate member 8 by the pressing force applied from the pressing roll 13. As a result, the organic layer 4 is transferred onto the intermediate member 8. At this time, the transfer timing and speed of the transfer member 9 and the transfer timing and speed of the intermediate member 8 are synchronized so that the organic layer 4 is transferred onto the first electrode 3 of the intermediate member 8.

  The intermediate member 8 to which the organic layer 4 has been transferred is further transported by the first transport unit and sent to the next process. In the next step, the second electrode 5 is stacked on the organic layer 4 transferred according to this embodiment, or one or more organic layers 4 are stacked on the organic layer 4 and then the second electrode 5 is further stacked. The electrodes 5 are stacked. Thereby, the organic device 1 is obtained.

  In this embodiment, the intermediate member 8 includes the long base 2 and the plurality of first electrodes 3. For example, the intermediate member 8 further includes one or more organic layers 4 (this embodiment) on the first electrode 3. An organic layer 4) different from the organic layer 4 to be transferred may be provided. Further, the intermediate member 8 may include the long base material 2 and a plurality of second electrodes 5, and further, a single layer or a plurality of organic layers 4 (transferred by this embodiment) on the second electrode 5. An organic layer 4) different from the organic layer 4 may be provided. Further, the intermediate member 8 may be a member that does not include the base material 2 and is formed only of the long second electrode 5. Further, the intermediate member 8 does not include the base material 2, the long second electrode 5, and one or a plurality of organic layers 4 stacked on the second electrode 5 (the organic layer 4 transferred by this embodiment is Different organic layers 4) may be provided.

  In the present embodiment, the organic electroluminescence element is particularly described as an organic device. However, the object of the present invention is not limited to the organic electroluminescence element, and may be a single layer or a plurality of organic layers. Organic devices such as various light emitting elements and power generation elements are targeted.

(Formation of hole injection layer)
As the donor substrate 6, a polyimide film having a thickness of 200 μm was prepared. A release layer 7 having a thickness of 2 μm was formed on the donor substrate 6 by the following method, whereby a transfer member 9 was obtained.

(Preparation of A-1 solution)
In a flask equipped with a stirrer, heating jacket, condenser and thermometer, IPA-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-ST, particle size 10-20 nm, solid content 30%, moisture content) 0.5%)), 100 parts by weight of methyltrimethoxysilane, 68 parts by weight of methyltrimethoxysilane, and 10.8 parts by weight of water and stirred for about 5 hours at 65 ° C. with stirring And cooled to obtain component (A). This had a solid content of 36% when left at room temperature for 48 hours. The component (A) obtained here is referred to as (A-1). The preparation conditions of (A-1) are as follows.
-Number of moles of water to 0.4 equivalent of methyltrimethoxysilane with 1 equivalent of hydrolyzable group.
-Silica moisture content in solid content of component (A)--47.3 mass%.
-Mol% of hydrolyzable organosilane with n = 1--100 mol%.

(Preparation of B-1 solution)
In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer, 220 parts by mass (1 mol) of methyltriisopropoxysilane and 150 parts by mass of toluene are weighed, and 1 1 Methyl triisopropoxysilane was hydrolyzed by adding dropwise 108 parts by mass of an aqueous hydrochloric acid solution over 20 minutes. Stirring was stopped 40 minutes after the completion of dropping, and the reaction solution was transferred to a separatory funnel and allowed to stand to separate two layers. The lower layer water / isopropyl alcohol mixture containing hydrochloric acid was removed by separation, then the remaining hydrochloric acid in the toluene resin solution was washed away with water, and further removed under reduced pressure in toluene. Dilution was carried out to obtain a 40 mass% isopropyl alcohol solution of silanol group-containing polyorganosiloxane having an average molecular weight (Mw) of about 2000. The component (B) obtained here is referred to as (B-1).

(Preparation of silicone coating material and formation of release layer)
(A) 70 parts by mass of component (A-1), (B) 30 parts by mass of component (B-1), (C) N-β-aminoethyl-γ-aminopropylmethyldimethoxy as component One part of silane was mixed to obtain a silicone coating material. This silicone coating material was applied onto the donor substrate 6 with a bar coater coater so that the cured coating thickness was 2 μm, and then cured at 150 ° C. for 30 minutes. Thus, a transfer member 9 was obtained.

  The contact angle of water on the surface of the release layer 7 in the transfer member 9 was measured by the θ / 2 method using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) and found to be 95 °.

  Further, N4, N4 '-(biphenyl-4,4'-diyl) bis (N4, N4', Coating solution 10 was prepared by dissolving N4′-triphenylbiphenyl-4,4′-diamine) (TPT1) at a rate of 5 mg / ml.

  While the transfer member 9 is heated to 80 ° C. in a glove box having a dew point of −76 ° C. or less and an oxygen concentration of 1 ppm or less and a dry nitrogen atmosphere, the coating solution 10 is formed on the release layer 7 so that the film thickness becomes 30 nm. The organic layer 4 (hole injection layer 41) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  On the other hand, a polyethylene naphthalate film (Teonex Q65FA made by Teijin DuPont Film) having a thickness of 200 μm was prepared as the substrate 2. Sputtering was performed on the base material 2 using an ITO target (manufactured by Tosoh Corp.), followed by annealing at 150 ° C. for 2 hours in an argon atmosphere. Thus, an intermediate member 8 (first intermediate member 8) including the base material 2 and the first electrode 3 having a sheet resistance of 18Ω / □ made of an ITO film (tin-doped indium oxide) having a thickness of 300 nm was obtained.

  The hole injection layer 41 on the transfer member 9 was overlaid on the first electrode 3 of the first intermediate member 8 in the same glove box having the same dry nitrogen atmosphere as described above. Further, by passing the first intermediate member 8 and the transfer member 9 between a pair of heating rollers, the first intermediate member 8 was pressurized while being heated to 80 ° C. and the transfer member 9 to 150 ° C. . Thus, the hole injection layer 41 on the transfer member 9 was transferred onto the first intermediate member 8 without remaining on the transfer member 9. A member constituted by the hole injection layer 41 and the first intermediate member 8 was used as the second intermediate member 8.

(Formation of hole transport layer)
A transfer member 9 having the same structure as that for forming the hole injection layer 41 was prepared. In addition, a mixed solvent obtained by mixing chloroform and acetone in a volume ratio of 1: 2 was mixed with 2,2′-bis (4- (carbazol-9-yl) phenyl) -biphenyl (BCBP), which is a hole transport material. ) Was dissolved to a concentration of 2 mg / ml to prepare a coating solution 10.

  While the transfer member 9 is heated to 80 ° C. in a glove box having the same dry nitrogen atmosphere as the hole injection layer 41 is formed, the coating solution 10 is formed on the release layer 7 so that the film thickness becomes 30 nm. The organic layer 4 (hole transport layer 42) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  The hole transport layer 42 on the transfer member 9 is overlaid on the hole injection layer 41 of the second intermediate member 8 in the glove box having the same dry nitrogen atmosphere as described above, and the second intermediate member 8 and the transfer member 9 are further stacked. Were pressed between the pair of heating rollers while heating the second intermediate member 8 to 70 ° C. and the transfer member 9 to 140 ° C. As a result, the hole transport layer 42 on the transfer member 9 was transferred onto the second intermediate member 8 without remaining on the transfer member 9. A member constituted by the hole transport layer 42 and the second intermediate member 8 was defined as a third intermediate member 8.

(Formation of light emitting layer)
A transfer member 9 having the same structure as that for forming the hole injection layer 41 was prepared. The host material 2,2'-bis (4- (carbazol-9-yl) phenyl) -biphenyl (BCBP) and the guest material Tris [2- (p-tolyl) pyridine] iridium (III) ( A light emitting layer material composed of Ir (mppy) 3) was prepared. The ratio of the guest material to the entire light emitting layer material was 6% by mass. A coating solution 10 was prepared by dissolving the light emitting layer material in a mixed solvent obtained by mixing dichloromethane and acetone in a volume ratio of 1: 1 so as to have a concentration of 2.5 mg / ml.

  While the transfer member 9 is heated to 80 ° C. in a glove box having the same dry nitrogen atmosphere as the hole injection layer 41 is formed, the coating solution 10 is formed on the release layer 7 so that the film thickness becomes 30 nm. The organic layer 4 (light emitting layer 43) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  The light emitting layer 43 on the transfer member 9 is overlaid on the hole transport layer 42 of the third intermediate member 8 in the same glove box having the same dry nitrogen atmosphere as described above, and the third intermediate member 8 and the transfer member 9 are further stacked. By passing between the pair of heating rollers, the third intermediate member 8 was pressurized while being heated to 83 ° C. and the transfer member 9 to 138 ° C. As a result, the hole transport layer 42 on the transfer member 9 was transferred onto the third intermediate member 8 without remaining on the transfer member 9. A member constituted by the hole transport layer 42 and the third intermediate member 8 was defined as a fourth intermediate member 8.

(Formation of electron transport layer)
A transfer member 9 having the same structure as that for forming the hole injection layer 41 was prepared. In addition, to a mixed solvent obtained by mixing dichloromethane and acetone in a volume ratio of 1: 1, 2,2 ', 2 "-(1,3,5-Benzinetriyl) -tris (1- A coating solution 10 was prepared by dissolving phenyl-1-H-benzimidazole (TPBi) at a rate of 5 mg / ml.

  While the transfer member 9 is heated to 80 ° C. in a glove box having the same dry nitrogen atmosphere as the hole injection layer 41 is formed, the coating solution 10 is formed on the release layer 7 so that the film thickness becomes 30 nm. The organic layer 4 (electron transport layer 44) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  The electron transport layer 44 on the transfer member 9 is overlaid on the light emitting layer 43 of the fourth intermediate member 8 in the same glove box having the dry nitrogen atmosphere as described above, and the fourth intermediate member 8 and the transfer member 9 are further stacked. The fourth intermediate member 8 was pressurized while being heated to 82 ° C. and the transfer member 9 to 140 ° C. by passing between the pair of heating rollers. Thus, the electron transport layer 44 on the transfer member 9 was transferred onto the fourth intermediate member 8 without remaining on the transfer member 9.

(Formation of electron injection layer and second electrode)
An electron injection layer was formed on the electron transport layer 44 by depositing lithium fluoride by a vacuum deposition method. Furthermore, the second electrode 5 having a thickness of 80 nm was formed by depositing aluminum on the electron injection layer by vacuum deposition.

  Thereby, the organic device 1 (organic electroluminescent element) with favorable light emission characteristics was obtained with a good yield.

(Formation of electron transport layer)
To a mixed solvent obtained by mixing dichloromethane and acetone in a volume ratio of 1: 1, 2,2 ', 2 "-(1,3,5-Benzinetriyl) -tris (1-phenyl- A coating solution 10 was prepared by dissolving 1-H-benzimidazole (TPBi) to a concentration of 5 mg / ml.

  A transfer member 9 was produced by the same method and conditions as in Example 1. While the transfer member 9 is heated to 80 ° C. in a glove box having a dew point of −76 ° C. or less and an oxygen concentration of 1 ppm or less, the coating solution 10 is formed on the release layer 7 with a film thickness of 30 nm. Thus, the organic layer 4 (electron transport layer 44) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  On the other hand, a copper sheet having a thickness of 200 μm was prepared as the second electrode 5. This second electrode 5 was used as an intermediate member 8 (first intermediate member 8).

  The electron transport layer 44 on the transfer member 9 is overlaid on the second electrode 5 of the first intermediate member 8 in the same dry nitrogen atmosphere glove box as described above, and the first intermediate member 8 and the transfer member are further stacked. By passing 9 between a pair of heating rollers, the first intermediate member 8 was pressurized while being heated to 83 ° C. and the transfer member 9 to 139 ° C. As a result, the electron transport layer 44 on the transfer member 9 was transferred onto the first intermediate member 8 without remaining on the transfer member 9. A member constituted by the electron transport layer 44 and the first intermediate member 8 was used as the second intermediate member 8.

(Formation of light emitting layer)
A transfer member 9 having the same structure as that for forming the electron transport layer 44 was prepared. The host material bis (4- (N-carbazolyl) phenyl) phenylphosphine oxide (BCPO) and the guest material Tris [2- (p-tolyl) pyridine] iridium (III) (Ir (mppy) 3) A light emitting layer material consisting of: The ratio of the guest material to the entire light emitting layer material was 1% by mass. The light emitting layer material was dissolved in a mixed solvent obtained by mixing dichloromethane and acetone in a volume ratio of 1: 1 at a ratio of 7.5 mg / ml, thereby preparing a coating solution 10.

  While the transfer member 9 is heated to 80 ° C. in a glove box having the same dry nitrogen atmosphere as the electron transport layer 44 is formed, the coating solution 10 is formed on the release layer 7 so that the film thickness becomes 30 nm. The organic layer 4 (light emitting layer 43) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  The light emitting layer 43 on the transfer member 9 is stacked on the electron transport layer 44 of the second intermediate member 8 in the same glove box having the same dry nitrogen atmosphere as described above, and the second intermediate member 8 and the transfer member 9 are further stacked. By passing between the pair of heating rollers, the second intermediate member 8 was pressurized while being heated to 81 ° C. and the transfer member 9 to 140 ° C. Thereby, the light emitting layer 43 on the transfer member 9 was transferred onto the second intermediate member 8 without remaining on the transfer member 9. A member constituted by the light emitting layer 43 and the second intermediate member 8 was defined as a third intermediate member 8.

(Formation of hole transport layer)
A transfer member 9 having the same structure as that for forming the electron transport layer 44 was prepared. In addition, a mixed solvent obtained by mixing chloroform and acetone in a volume ratio of 1: 2 was mixed with 2,2′-bis (4- (carbazol-9-yl) phenyl) -biphenyl (BCBP), which is a hole transport material. ) Was dissolved to a concentration of 2 mg / ml to prepare a coating solution 10.

  While the transfer member 9 is heated to 80 ° C. in a glove box having the same dry nitrogen atmosphere as the electron transport layer 44 is formed, the coating solution 10 is formed on the release layer 7 so that the film thickness becomes 30 nm. The organic layer 4 (hole transport layer 42) was formed by applying with a bar coater and further drying at 80 ° C. for 1 minute.

  The hole transport layer 42 on the transfer member 9 is overlaid on the light emitting layer 43 of the third intermediate member 8 in the glove box having the same dry nitrogen atmosphere as described above, and the third intermediate member 8 and the transfer member 9 are further stacked. The third intermediate member 8 was pressed while being heated to 75 ° C. and the transfer member 9 was heated to 142 ° C. by passing between a pair of heating rollers. As a result, the hole transport layer 42 on the transfer member 9 was transferred onto the third intermediate member 8 without remaining on the transfer member 9.

(Formation of hole injection layer and first electrode)
A hole injection layer 41 was formed on the hole transport layer 42 by depositing molybdenum oxide by a vacuum deposition method. Further, the first electrode 3 having a thickness of 20 nm was formed by depositing gold on the hole injection layer 41 by vacuum vapor deposition.

  Thereby, the organic device 1 (organic electroluminescent element) with favorable light emission characteristics was obtained with a good yield.

DESCRIPTION OF SYMBOLS 1 Organic device 4 Organic layer 7 Release layer 8 Intermediate member 9 Transfer member 10 Coating liquid 17 Heating part (first heating part)

Claims (5)

A method for producing an organic device comprising the following steps;
Providing an intermediate member forming part of the organic device;
Providing a transfer member comprising a release layer;
An organic material, a first solvent in which the organic material is dissolved, and a second solvent having affinity for the release layer, and the first solvent and the second solvent Preparing a coating liquid having a volume ratio of 1: 1 to 1: 2; and coating the coating liquid on the release layer of the transfer member to form an organic layer on the release layer. Forming and subsequently transferring the organic layer from the release layer onto the intermediate member. 2. The method for producing an organic device according to claim 1, wherein the boiling point of the first solvent is 66.0 ° C. or lower, and the boiling point of the second solvent is 79.5 ° C. or lower. Both the solubility parameter of the first solvent and the solubility parameter of the second solvent are 10 or less,
The method for producing an organic device according to claim 1 or 2, wherein a difference in boiling points between the first solvent and the second solvent is within 20 ° C. The manufacturing method of the organic device as described in any one of Claims 1 thru | or 3 with which the said mold release layer is formed from the silicone type material. The method for producing an organic device according to any one of claims 1 to 4, wherein a contact angle of water on the surface of the release layer is 90 ° or more.

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