TW202137434A - Electronic device, sulfidation inhibitor, and sealant - Google Patents

Abstract

The present invention addresses the problem of providing an electronic device in which the sulfidation of metal by gas containing sulfur compounds, such as hydrogen sulfide, or sulfur allotropes is inhibited. The present invention also addresses the problem of providing a sulfidation inhibitor and a sealant for this purpose. The electronic device of the present invention is characterized by comprising at least a metal-containing member layer and a layer containing a compound (1) having a structure represented by general formula (1) below. (In the formula, R1 and R2 each independently represent an acid group, -ORa, -SRb, or -NRcRd. Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent. R3 represents a nitrogen-containing ligand. Me represents copper (Cu) or zinc (Zn).).

Description

Electronic components, anti-vulcanization agents and sealing materials

The present invention relates to electronic components, anti-vulcanization agents and sealing materials. More specifically, it relates to electronic components that prevent the sulfidation of metals due to gases containing sulfur compounds such as hydrogen sulfide or sulfur allotropes.

In light emitting diode (light emitting diode: hereinafter referred to as "LED") elements, organic electroluminescence elements (also known as "organic EL elements". EL: electroluminescence), photoelectric conversion elements and other electronic elements, silver or Metals such as copper are used in lead frames or electrodes. For example, silver is used as a plating material for lead frames for light-emitting diodes because of its high reflectivity of visible light. In addition, since silver has high conductivity, it is also used as a material for electrical wiring or electrodes.

However, it is known that in the presence of a gas containing sulfur compounds such as hydrogen sulfide or sulfur allotropes, most metals other than gold and platinum react with sulfur to form sulfides, especially by contact with silver or copper. The reaction proceeds even at room temperature to produce black silver sulfide or copper sulfide, which is the cause of the deterioration of the function of electronic components.

For example, in recent years, in the vicinity of blue LED elements, there have been developed white LED devices equipped with YAG phosphors that emit yellow fluorescent elements, or white LED elements that emit red, green, and blue light in combination. LED device. Such white LED devices are widely used as substitutes for conventional fluorescent lamps or incandescent lamps, and are required to maintain high light extraction efficiency for a long period of time.

However, one of the main reasons for the low light extraction efficiency of the conventional light-emitting device is the deterioration of the electrode or the light-emitting element included in the light-emitting device. The deterioration of the electrode or the light-emitting element is caused by, for example, hydrogen sulfide gas or moisture contained in the use environment of the light-emitting device.

Accordingly, as a strategy to prevent deterioration due to vulcanization of lead frames, electrodes, etc., techniques using sulfide-based gas sorbents or silver discoloration prevention agents have been introduced (for example, refer to Patent Document 1 and Patent Document 2).

In addition, as the use of these anti-vulcanizing agents, there are known (1) a solution containing an anti-vulcanizing agent is applied to the electrode, and (2) a solution containing an anti-vulcanizing agent is added to the sealing material and combined There are two types of coating, but there is a problem in the solubility of the anti-vulcanizing agent in the solvent, so there is also a problem that it cannot be coated well.

On the other hand, in recent years, instead of epoxy resins used as sealing materials in the past, the use of silicone resins with excellent light resistance and heat resistance is increasing. However, compared with epoxy resin, silicone resin has very high gas permeability, and it can easily permeate the sulfur-based gas that discolors the aforementioned silver. The permeated gas discolors the silver-plated part inside the seal, so the reflectance of the silver-plated part is reduced. As a result, the illuminance is reduced. Therefore, as a problem of the sealing by the silicone resin of the silver-plated frame, it is pointed out that the illuminance is low or the durability is low. Moreover, when the electrode and the sealing material are subjected to thermal shock, there is also a problem of so-called adhesion that is easy to peel off.

Accordingly, when silicone resin is used as a sealing material, it is desirable to have a technology that prevents the discoloration of silver and can ensure the durability of its reflectance. However, the performance degradation caused by metal vulcanization as described above has become a problem not only in LED devices, but also in other electronic devices such as photoelectric conversion devices. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6555933 [Patent Document 2] JP 2015-79991 A

[The problem to be solved by the invention]

The present invention has been accomplished in view of the above-mentioned problems and conditions, and the problem to be solved is to provide an electronic component that prevents the sulfidation of metals caused by gases containing sulfur compounds such as hydrogen sulfide or sulfur allotropes. Moreover, for this purpose, an anti-vulcanization agent and a sealing material are provided. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors discovered that during the process of studying the causes of the above-mentioned problems, there is an interaction with metals such as silver or copper, and the interaction with materials such as polysiloxane used in the sealing material is also strong. , The metal complexes with nitrogen-containing ligands are effective for solving the problem, and finally the present invention is completed.

That is, the above-mentioned problems related to the present invention are solved by the following means.

1. An electronic component characterized by having at least a layer containing a metal member and a layer containing a compound (1) having a structure represented by the following general formula (1).

(In the formula, R ₁ and R ₂ each independently represent an acid group, -ORa, -SRb, or -NRcRd. Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent. R ₃ represents a nitrogen-containing ligand. Me Represents copper (Cu) or zinc (Zn)).

2. The electronic component according to item 1, wherein the aforementioned R ₁ and R ₂ in the aforementioned general formula (1) represent an acid group.

3. The electronic component according to item 1 or 2, wherein the acid group is a carboxylic acid group or an inorganic acid group.

4. The electronic component according to any one of items 1 to 3, wherein the metal-containing member layer contains silver (Ag) or copper (Cu).

5. The electronic component described in any one of items 1 to 4, wherein the layer containing the aforementioned compound (1) contains a resin or a resin precursor, and The content of the aforementioned compound (1) is in the range of 1 to 50% by mass.

6. The electronic component according to any one of items 1 to 5, wherein the layer containing the aforementioned compound (1) contains an organic solvent having a boiling point of 150°C or higher.

7. The electronic element according to any one of items 1 to 6, wherein the electronic element is a light-emitting diode, a photoelectric conversion element, or an organic electroluminescence element.

8. An anti-vulcanizing agent characterized by containing at least a compound (1) having a structure represented by the following general formula (1).

(In the formula, R ₁ and R ₂ each independently represent an acid group, -ORa, -SRb, or -NRcRd. Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent. R ₃ represents a nitrogen-containing ligand. Me Represents copper (Cu) or zinc (Zn)).

9. A sealing material characterized by containing at least the anti-vulcanization agent as described in item 8. [Effects of the invention]

By the above-mentioned means of the present invention, it is possible to provide an electronic component that prevents metal sulfidation caused by a gas containing sulfur compounds such as hydrogen sulfide or sulfur allotropes. In addition, for this purpose, an anti-vulcanization agent and a sealing material can be provided. Although the mechanism for expressing or acting on the effect of the present invention has not been clarified yet, it is presumed to be as follows.

The aforementioned compound (1) having the structure represented by the general formula (1) is a metal complex with a nitrogen-containing ligand. In addition, since the central metal Me is copper (Cu) or zinc (Zn), it is combined with silver or copper The interaction of other metals is strong, and the interaction with materials such as polysiloxane used in the sealing material is also strong. Based on this, it is estimated that by preventing the reaction of sulfur compounds such as hydrogen sulfide or sulfur compounds in the sulfur allotrope with silver or copper, and preventing the generation of metal sulfides such as silver sulfide or copper sulfide, The problem related to the present invention can be solved.

The electronic component of the present invention is characterized by having at least a layer containing a metal-containing member layer and the aforementioned compound (1) having a structure represented by the general formula (1). This feature is a feature common to or corresponding to each embodiment described below.

As an embodiment of the present invention, from the viewpoint of expressing the effects of the present invention, it is preferable that the aforementioned R ₁ and R ₂ in the aforementioned general formula (1) represent an acid group. Furthermore, the aforementioned acid group is preferably a carboxylic acid group or an inorganic acid group. Furthermore, the aforementioned metal-containing member layer preferably contains silver (Ag) or copper (Cu).

As an embodiment of the present invention, from the viewpoint of the effect of preventing the vulcanization of metals due to gases containing sulfur compounds such as hydrogen sulfide or sulfur allotropes, the layer containing the aforementioned compound (1) contains a resin or a resin precursor The content of the aforementioned compound (1) is also preferably within the range of 1-50% by mass. Furthermore, from the same viewpoint, it is preferable that the layer containing the aforementioned compound (1) contains an organic solvent having a boiling point of 150°C or higher.

Although the electronic element of the present invention is a light-emitting diode, a photoelectric conversion element, or an organic electroluminescence element, it is preferable from the viewpoint of expressing the effects of the present invention.

At least the aforementioned compound (1) having the structure represented by the general formula (1) can be suitably used as an anti-vulcanizing agent. In addition, it can also be suitably used as a sealing material. Hereinafter, the present invention, its constituent elements, and the modes and aspects for implementing the present invention will be described in detail. Still, in this case, "~" is used in the meaning that the numerical value described before and after it is included as the lower limit and the upper limit.

1. Outline of the electronic component of the present invention The electronic component of the present invention is characterized by having at least a layer containing a metal member and a layer containing a compound (1) having a structure represented by the following general formula (1).

Here, the so-called "electronic components" in a narrow sense refers to components that use the motion energy and position energy of electrons to generate, amplify, transform, or control electrical signals. For example, active elements such as light-emitting diode elements, organic electroluminescence elements, photoelectric conversion elements, and transistors can be cited. Furthermore, in the present invention, passive components that perform passive operations such as "resistance" and "storage" from other ways, such as resistors, capacitors, etc., are also included in electronic components.

In addition, in a broad sense, the so-called "electronic components" refers to light-emitting devices and display devices that also include the above-mentioned narrowly defined "electronic components". In the present invention, although the term "electronic component" is used in accordance with the main and broad definition, for the convenience of description, the term "electronic component" in the narrower definition is also suitable for use.

As an embodiment of the present invention, from the viewpoint of expressing the effects of the present invention, it is preferable that the following R ₁ and R ₂ in the following general formula (1) represent an acid group. Furthermore, the aforementioned acid group is preferably a carboxylic acid group or an inorganic acid group. Furthermore, the aforementioned metal-containing member layer preferably contains silver (Ag) or copper (Cu).

(1.1) Layer containing metal components In the present invention, the "metal-containing member layer" refers to a layer including metal-containing members constituting electronic components. For example, it refers to metal-containing electrodes or lead frames. Still, the so-called "lead frame" refers to a metal sheet used in semiconductor packages such as ICs or LSIs to support and fix IC chips and become the connection terminals when mounted on a printed wiring board.

The effect of the present invention is characterized in that electronic components having a metal-containing member layer containing silver (Ag) or copper (Cu) become prominent.

(1.2) Compounds with the structure represented by general formula (1) (1) The electronic device of the present invention is characterized by having a layer containing a compound (1) having a structure represented by the following general formula (1).

(In the formula, R ₁ and R ₂ each independently represent an acid group, -ORa, -SRb, or -NRcRd. Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent. R ₃ represents a nitrogen-containing ligand. Me Represents copper (Cu) or zinc (Zn)).

_{R 1} and R ₂ in the above general formula (1) preferably represent an acid group. Furthermore, the aforementioned acid group is preferably a carboxylic acid group or an inorganic acid group. Here, the so-called "acid group" refers to the removal of more than one remaining atom or group of atoms that can ionize the hydrogen atom as a hydrogen ion from the molecules of various inorganic or organic acids. For example, in the case of carboxylic acid R-COOH, R-COO- is an acid group (also called a "carboxylic acid group").

Examples of carboxylic acid groups include formic acid groups, acetate groups, propionic acid groups, butyric acid groups, valeric acid groups, hexanoic acid groups, heptanoic acid groups, octanoic acid groups, 2-ethylhexanoic acid groups, and neodecanoic acid groups. , Lauric acid (dodecanoic acid) group, stearic acid (octadecanoic acid), methacrylic acid group, undecylenic acid group and other aliphatic monocarboxylic acid groups.

In addition, aliphatic polycarboxylic acid groups such as an oxalic acid group, a malonic acid group, a succinic acid group, a glutaric acid group, and an adipic acid group can be cited. Furthermore, aromatic polycarbonates such as aromatic monocarboxylic acid groups such as benzoic acid group and toluic acid group, phthalic acid group, isophthalic acid group, terephthalic acid group, and nitrophthalic acid group can be cited. Carboxylic acid group and so on.

Examples of inorganic acid groups include hydrochloric acid groups, chloric acid groups, chlorite groups, and hypochlorous acid groups, such as chloric acid groups, hydrobromide acid groups, perbromic acid groups, bromic acid groups, and bromine acid groups. , Hypobromite, etc. Bromate, hydrogen iodide, periodic acid, iodate, iodite, hypoiodic acid, etc., iodate, sulfate, disulfate, thio Sulfate groups, sulfamic acid groups, sulfite groups, disulfite groups, thiosulfite groups, such as sulfate groups, nitrate groups, nitrite groups, hyponitrite groups, Nitroxyl acid groups, etc. The nitrous acid group, orthophosphoric acid group, phosphite group, hypophosphorous acid group, phosphinic acid (Phosphinous acid) group, phosphenic acid (phosphenic acid) group, phosphinic acid (Subphosphenic acid) group, diphosphate group, three Phosphoric acid, orthoboric, metaboric, perboric, hypoboric, boronic, borinic acid, boric acid, bicarbonate, and carbonate. Other examples include phenolsulfonic acid groups.

Among the above acid groups, acetate group, 2-ethylhexanoic acid group, neodecanoic acid group, lauric acid (dodecanoic acid) group, stearic acid (octadecanoic acid), methacrylic acid group, undecanoic acid group The present invention has improved the stability of the compound (1), that is, the metal complex, which has the structure represented by the general formula (1). From the viewpoint of the size of the effect, it is better. Still, these acid groups can be used as a combination of two or more kinds.

In addition, R ₁ and R ₂ as groups other than the aforementioned acid groups each independently represent -ORa, -SRb, or -NRcRd. Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent. Here, when Ra, Rb, Rc, and Rd each independently represent a substituent, the following examples of substituents can be cited.

That is, as substituents that can be used in the present invention, for example, alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl , Tridecyl, tetradecyl, pentadecyl, etc.), cycloalkyl (e.g. cyclopentyl, cyclohexyl, etc.), alkenyl (e.g. vinyl, allyl, etc.), alkynyl (e.g. acetylene Group, propargyl, etc.) and so on.

In addition, aromatic hydrocarbon groups (also called aromatic carbocyclic groups, aryl groups, etc.), for example, phenyl, p-chlorophenyl, mesityl, tolyl, xylyl, naphthyl, anthracenyl, etc. , Azulenyl, dihydroacenaphthyl, stilbene, phenanthryl, indenyl, pyrenyl, biphenylyl, etc.). Furthermore, aromatic heterocyclic groups (for example, furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, Carbazolyl, Carbolinyl, Diazacarbazolyl (representing any one of the carbon atoms constituting the Carboline ring of the aforementioned carboline group is substituted with a nitrogen atom), Phthalazinyl Etc.), heterocyclic groups (e.g. pyrrolidinyl, imidazolidinyl, morpholinyl, oxazolidinyl, etc.).

In addition, sulfasulfonyl groups (e.g., sulfasulfonyl, methylsulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexyl) can be cited. Aminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc. ), acyl groups (e.g. acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl , Pyridylcarbonyl, etc.).

In addition, amide groups (for example, methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethyl Hexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl (e.g., aminocarbonyl, methylamino, etc.) Carbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, Phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), ureido groups (e.g. methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, etc.) , Dodecylureido, phenylureidonaphthylureido, 2-pyridylaminoureido, etc.).

Furthermore, sulfinyl groups (for example, methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, twelve Alkylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfinyl (e.g., methylsulfinyl, ethylsulfinyl, etc.) , Butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, etc.), arylsulfonyl or heteroarylsulfonyl (e.g. phenylsulfonyl Group, naphthylsulfonyl, 2-pyridylsulfonyl, etc.).

In addition, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), fluorinated hydrocarbon groups (for example, fluoromethyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl, etc.), cyano groups, and nitro groups can be cited. , Hydroxyl, mercapto, silyl group (e.g. trimethylsilyl, triisopropylsilyl, triphenylsilyl, phenyldiethylsilyl, etc.), phosphate group (e.g. dihexylphosphoryl, etc.) , Phosphite group (for example, diphenylphosphino etc.), Phosphono group and the like.

As Ra of -ORa, an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a heterocyclic group, etc. are preferable. As Rb of -SRb, an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a heterocyclic group, etc. are preferable. As Rc and Rd of -NRcRd, an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a heterocyclic group, etc. are preferable.

R ₃ represents a nitrogen-containing ligand. Although the nitrogen-containing ligand is not specifically limited in structure, it is preferably a ligand coordinated to copper (Cu) or zinc (Zn).

As nitrogen-containing ligands suitable for use in the present invention, 2-aminoethanol (monoethanolamine), diethanolamine, triethanolamine, triethylenetetramine, tetramethylenediamine, 4-(2-amino) Ethyl)pyridine, 2,2'-bipyridyl, ethylenediaminetetraacetic acid, 5,5'-bis(triisopropoxysilyl)-2,2'-bipyridine, hexylamine, dodecane Amine, 3-aminopropyl triethoxysilane, etc.

The aforementioned compound (1) having the structure represented by the general formula (1) is a metal complex with a nitrogen-containing ligand. In addition, since the central metal Me is copper (Cu) or zinc (Zn), it is combined with silver or copper The interaction between other metals is strong, and the interaction with materials such as silicone used in the sealing material is also strong. Accordingly, the reaction of sulfur compounds in the gas containing sulfur compounds such as hydrogen sulfide or sulfur allotropes with silver or copper is prevented, and the generation of metal sulfides such as silver sulfide or copper sulfide is prevented.

Specific examples of the compound (1) having the structure represented by the general formula (1) (referred to as "exemplary compounds" as appropriate) are shown in the following Table I and Table II. In addition, the compound (1) related to the present invention is not limited to the following examples.

[Table I] Compound No. R ₁ R ₂ R ₃ Me 1 2 -ethylhexanoate 2 -ethylhexanoate 2 - aminoethanol ( monoethanolamine) Zn 2 2 -ethylhexanoate 2 -ethylhexanoate Diethanolamine Zn 3 2 -ethylhexanoate 2 -ethylhexanoate Triethanolamine Zn 4 Neodecanoic acid Neodecanoic acid Triethylenetetramine Zn 5 Neodecanoic acid Neodecanoic acid Tetramethylene diamine Zn 6 Neodecanoic acid Neodecanoic acid 4-(2 -aminoethyl ) pyridine Zn 7 Lauric acid group Lauric acid group 2,2' -Bipyridyl Zn 8 Lauric acid group Lauric acid group Ethylenediaminetetraacetic acid Zn 9 Stearic acid group Stearic acid group 5,5' -bis ( triisopropoxysilyl )-2,2' -bipyridine Zn 10 Stearic acid group Stearic acid group Hexylamine Zn 11 Undecylenic acid group Undecylenic acid group Dodecylamine Zn 12 Acetate Acetate 3 -aminopropyl triethoxysilane Zn 13 Acetate Acetate 2 - aminoethanol ( monoethanolamine) Zn 14 Acetate Acetate Diethanolamine Zn 15 Acetate Acetate Triethanolamine Zn 16 Acetate Acetate Triethylenetetramine Zn 17 Acetate Acetate Tetramethylene diamine Zn 18 Acetate Acetate 4-(2 -aminoethyl ) pyridine Zn 19 Acetate Acetate 2,2' -Bipyridyl Zn 20 Acetate Acetate Ethylenediaminetetraacetic acid Zn twenty one Acetate Acetate 5,5' -bis ( triisopropoxysilyl )-2,2' -bipyridine Zn twenty two Acetate Acetate Hexylamine Zn twenty three Acetate Acetate Dodecylamine Zn twenty four Benzoic acid group Benzoic acid group Triethanolamine Zn 25 Benzoic acid group Benzoic acid group Triethylenetetramine Zn 26 Benzoic acid group Benzoic acid group Tetramethylene diamine Zn 27 Phenol sulfonate Phenol sulfonate 4-(2 -aminoethyl ) pyridine Zn 28 Phenol sulfonate Phenol sulfonate 2,2' -Bipyridyl Zn 29 Methacrylate Methacrylate Ethylenediaminetetraacetic acid Zn 30 Methacrylate Methacrylate 5,5' -bis ( triisopropoxysilyl )-2,2' -bipyridine Zn 31 Nitrate Nitrate Hexylamine Zn 32 Nitrate Nitrate Dodecylamine Zn 33 Nitrate Nitrate 2 - aminoethanol ( monoethanolamine) Zn 34 Nitrate Nitrate Diethanolamine Zn 35 Nitrate Nitrate Triethanolamine Zn 36 Sulfate Sulfate 4-(2 -aminoethyl ) pyridine Zn 37 Sulfate Sulfate 2,2' -Bipyridyl Zn 38 Sulfate Sulfate Ethylenediaminetetraacetic acid Zn

[Table II] Compound No. R ₁ R ₂ R ₃ Me 39 Sulfate Sulfate 5,5' -Bis ( triisopropoxysilyl )-2,2' -bipyridine Zn 40 Sulfate Sulfate 2 - aminoethanol ( monoethanolamine) Zn 41 Sulfate Sulfate Diethanolamine Zn 42 Sulfate Sulfate Triethanolamine Zn 43 Trifluoromethanesulfonic acid group Trifluoromethanesulfonic acid group 5,5' -Bis ( triisopropoxysilyl )-2,2' -bipyridine Zn 44 Trifluoromethanesulfonic acid group Trifluoromethanesulfonic acid group 2 - aminoethanol ( monoethanolamine) Zn 45 Trifluoromethanesulfonic acid group Trifluoromethanesulfonic acid group Diethanolamine Zn 46 Trifluoromethanesulfonic acid group Trifluoromethanesulfonic acid group Triethanolamine Zn 47 Acetate 2 -ethylhexanoate 2 - aminoethanol ( monoethanolamine) Zn 48 Acetate Neodecanoic acid Diethanolamine Zn 49 Acetate Lauric acid group Triethanolamine Zn 50 Acetate Benzoic acid group 2,2' -Bipyridyl Zn 51 Acetate Phenol sulfonate Ethylenediaminetetraacetic acid Zn 52 Acetate Methacrylate 4-(2 -aminoethyl ) pyridine Zn 53 Acetate Nitrate 5,5' -Bis ( triisopropoxysilyl )-2,2' -bipyridine Zn 54 Acetate Sulfate Hexylamine Zn 55 Acetate Trifluoromethanesulfonic acid group 3 -aminopropyl triethoxysilane Zn 56 2 -ethylhexanoate 2 -ethylhexanoate 2 - aminoethanol ( monoethanolamine) Cu 57 Neodecanoic acid Neodecanoic acid Diethanolamine Cu 58 Lauric acid group Lauric acid group Triethanolamine Cu 59 Stearic acid group Stearic acid group 4-(2 -aminoethyl ) pyridine Cu 60 Undecylenic acid group Undecylenic acid group Hexylamine Cu 61 Acetate Acetate Dodecylamine Cu 62 Benzoic acid group Benzoic acid group Diethanolamine Cu 63 Phenol sulfonate Phenol sulfonate Triethanolamine Cu 64 Methacrylate Methacrylate 4-(2 -aminoethyl ) pyridine Cu 65 Nitrate Nitrate Hexylamine Cu 66 Sulfate Sulfate Dodecylamine Cu 67 Trifluoromethanesulfonic acid group Trifluoromethanesulfonic acid group Diethanolamine Cu 68 Acetate Acetate Triethanolamine Cu 69 Acetate Acetate 4-(2 -aminoethyl ) pyridine Cu 70 Acetate Acetate Hexylamine Cu 71 Nitrate Nitrate 3 -aminopropyl triethoxysilane Cu 72 Nitrate Nitrate 5,5' -bis ( triisopropoxysilyl )-2,2' -bipyridine Cu 73 Nitrate Nitrate Diethanolamine Cu 74 Sulfate Sulfate Triethanolamine Cu 75 Sulfate Sulfate 4-(2 -aminoethyl ) pyridine Cu 76 Sulfate Sulfate 5,5' -bis ( triisopropoxysilyl )-2,2' -bipyridine Cu

(1.3) Anti-vulcanizing agent The anti-vulcanization agent of the present invention is characterized by containing the aforementioned compound (1) having the structure represented by the general formula (1). The anti-sulfurizing agent is particularly characterized by preventing the sulfidation of metals due to gases containing sulfur compounds such as hydrogen sulfide or sulfur allotropes. Still, there are cases where it has an effect on anti-sulfurization of substances other than metals.

The anti-vulcanizing agent may contain other kinds of compounds according to the purpose within a range that does not hinder the effect of the present invention. In addition, the content of the compound (1) having the structure represented by the general formula (1) in the anti-vulcanizing agent is preferably 60% by mass or more.

The method of use of the anti-vulcanizing agent is not particularly limited. The compound can be used as a coating liquid dissolved or dispersed in a solvent, coated on a metal member of an electronic component, and a medium containing a resin constituting the sealing material described later is also preferable. .

As an organic solvent that can be used if necessary when preparing the coating liquid, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, or aliphatic ethers or alicyclic ethers can be suitably used. Ethers, etc.

Although the concentration of the compound (1) of the present invention in the coating liquid varies depending on the intended thickness or the shelf life of the coating liquid, it is preferably about 0.2 to 35% by mass.

The prepared coating liquid can include spray coating method, spin coating method, knife coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, etc. by coating methods, including Wet forming methods such as inkjet printing methods such as printing methods by patterning methods can be used according to the material. Among these, the inkjet printing method is preferred. The inkjet printing method is not particularly limited, and a known method can be used.

(1.4) Sealing material In the present invention, the so-called "sealing material" refers to a functional member that coats the aforementioned metal-containing member, that is, the metal contained in electronic components, and prevents the metal from being caused by gases containing sulfur compounds such as hydrogen sulfide or sulfur allotropes. The vulcanization and protection of the film or layered components as the purpose. Still, it is also good to have the function of preventing the influence of moisture or oxygen.

In the present invention, the aforementioned anti-vulcanizing agent may be applied to the metal-containing member and covered, and then the sealing material may be covered to protect the metal-containing member. In addition, the aforementioned anti-vulcanization agent may be contained in the sealing material (see FIGS. 1A and 1B).

The materials constituting the sealing material are not particularly limited, and various materials can be used, but preferred materials include, for example, thermoplastic resins, thermosetting resins, and photocuring resins. Specifically, the following resins can be exemplified.

For example, polysiloxane resins, epoxy resins, polyethylene, polypropylene, polybutene and copolymers of these, polyolefin resins such as cyclic polyolefins, alkyd resins, guanamine resins, Fluoroplastic resins such as phenol resin, tetrafluoroethylene (PTFE), fluorinated ethylene polypropylene copolymer (FEP), polyacrylonitrile resin, polystyrene resin, polyacetal resin, nylon 6, 11 ( Polyimide resins such as meth)acrylate resins, thermoplastic polyimides, polyetherimides, polyetheretherketone resins, polyoxyethylene (Polyethylene oxide) resins, and polyterephthalic acid Polyester resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl ether resins such as ethylene glycol (PET), polybutylene terephthalate (PBT) and copolymers of these Polyphenylene ether (Polyphenylene ether) resin, polyphenylene oxide resin, polymethylpentene resin, polyurethane resin, melamine resin, urea resin, polycarbonate resin, furan Series resins, silicon series resins, ionomer series resins, polyisocyanate series resins, polyterpene series resins and copolymers of these.

Among these, preferred are silicone resins, epoxy resins, cyclic polyolefin resins, polyacrylonitrile resins, polystyrene resins, polyamide resins, (meth)acrylate resins, The polyetheretherketone resin, polyester resin, polycarbonate resin, and copolymers of these may be resins modified to impart specific properties. Moreover, these resins can also be used individually or in mixture of 2 or more types.

(1.5) Sealing material containing anti-vulcanizing agent As mentioned above, it is also preferable that the sealing material of the present invention contains the aforementioned anti-vulcanizing agent. The sealing material can be formed by preparing a coating liquid containing the aforementioned anti-vulcanizing agent, coating it on an electronic component, and forming a film while sintering or irradiating it with ultraviolet rays to cause condensation. In addition, sealing materials made by other methods can also be used.

As the material when the sealing material is formed by coating, a thermosetting or UV curing type solvent-free monomer is preferable, and a curing type silicone monomer is particularly preferable. After coating the solvent-free monomer, the solid film is formed by thermal curing and/or UV curing to form a sealing material layer. Still, a compound that absorbs moisture and oxygen can be mixed with the sealing material. The solvent and coating method at the time of applying the coating liquid to form the sealing material layer can be the same as those in the case of the aforementioned anti-vulcanizing agent.

The thickness of the sealing material layer is in the range of 10 nm to 100 μm for the dry film, more preferably in the range of 0.1 to 1 μm, and it is more preferable in terms of the anti-vulcanization effect.

The sealing material preferably contains polysiloxane resin from the viewpoint of exhibiting the anti-vulcanization effect of the metal. As the polysiloxane resin, polydimethylsiloxane, polymethylphenylsiloxane, and polysiloxane can be used. Diphenylsiloxane etc. Furthermore, siloxanes containing fluorine atoms can also be suitably used.

The silicone resin used as the sealing material layer of the present invention may be a low-molecular body or a high-molecular body. Particularly preferred are oligomers or polymers. Specifically, polysiloxane derivatives such as polysiloxane-based compounds, polydimethylsiloxane-based compounds, and polydimethylsiloxane-based copolymers can be cited. Things. In addition, it may be a combination of these compounds.

For the coating film after immobilization, it is better to use plasma or ozone or ultraviolet light that can be used for low-temperature polymerization reaction. Among ultraviolet light, vacuum ultraviolet treatment (called VUV) is used, which improves the smoothness of the film surface. .

As the means for generating ultraviolet rays in vacuum ultraviolet treatment, for example, metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, UV light lasers, etc. can be cited, but they are not particularly limited. Preferably, an excimer lamp is used.

The sealing material of the present invention contains an organic solvent having a boiling point of 150°C or higher, and it is preferable from the viewpoint of enhancing the effect of the present invention. Examples of solvents with a boiling point of 150°C or higher include cyclohexanone, N-methylpyrrolidone, cycloheptanone, anisole, tetralin (Tetralin), cyclohexylbenzene, methyl anisole, and phenoxytoluene. , Methyl naphthalene, butyl benzoate, diphenyl ether, N,N-dimethylformamide, dimethyl sulfide, N,N-dimethylacetamide, ethylene glycol, glycerin, etc.

2. Electronic components Although the anti-sulfurizing agent of the present invention and the sealing material containing it can be applied to various electronic components, in this specification, it is directed to LED components, photoelectric conversion components, and organic electroluminescence components, as well as light-emitting devices and solar cells using them And the organic EL display device will be described.

(2.1) Light-emitting devices using light-emitting diode (LED) components, etc. The light-emitting device according to the present invention, as shown in FIG. 2, includes a substrate 11 having an electrode 15, a light-emitting element 12 electrically connected to the electrode 15, and a sealing material layer 13 that covers the electrode 15 and the light-emitting element 12. The light-emitting device 100 may include a wavelength conversion layer 14 covering the light-emitting element 12 or the sealing material layer 13 if necessary.

Here, the type of the light-emitting element 12 included in the light-emitting device 100 of the present invention is not particularly limited, and may be a semiconductor laser element, a light emitting diode (LED) element, an organic EL element, and the like. In the following, first, a case where the light-emitting element is an LED element is taken as an example, and the light-emitting device according to the present invention will be described.

(2.1.1) Substrate In FIG. 2, the substrate 11 is a member for supporting the LED element 12. An electrode 15 made of metal is formed on the substrate 11, and the electrode 15 has a function of supplying electricity to the LED element 12 from a power source (not shown) arranged outside the substrate 11. In addition, the electrode 15 may further have a function of reflecting the light emitted by the LED element 12 on the light extraction surface side of the light emitting device 100. The shape of the electrode 15 is not particularly limited, and it can be appropriately selected according to the type and application of the light-emitting device 100.

The substrate 11 may be a flat plate, and may have a cavity (recess) as shown in FIG. 2. When the substrate 11 has a cavity, the shape of the cavity is not particularly limited. For example, it may be a truncated cone shape, a truncated cone shape, a cylindrical shape, a prismatic shape, or the like.

The substrate 11 preferably has insulation and heat resistance, and is preferably made of ceramic resin or heat-resistant resin. Examples of heat-resistant resins include liquid crystal polymer, polyphenylene sulfide, aromatic nylon, epoxy resin, rigid silicone resin, polyphthalamide, and the like.

In addition, the substrate 11 may contain an inorganic filler. The inorganic filler can be titanium oxide, zinc oxide, aluminum oxide, silicon dioxide, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, boron nitride, glass fiber, and the like.

The manufacturing method of the substrate 11 with the electrode 15 is not particularly limited. Generally, it can be obtained by integrally molding a lead frame of a desired shape and a resin.

(2.1.2) LED components The LED element 12 is an element that is electrically connected to the electrode 15 formed on the substrate 11 and emits light of a specific wavelength. The wavelength of the light emitted by the LED element 12 is not particularly limited. The LED element 12 may be, for example, an element that emits blue light (light of about 420-485 nm), or an element that emits ultraviolet light. Furthermore, it may be an element that emits green light, red light, or the like.

The configuration of the LED element 12 is not particularly limited. When the LED element 12 is an element emitting blue light, the LED element 12 may be an n-GaN compound semiconductor layer (cladding layer), an InGaN compound semiconductor layer (light emitting layer), and a p-GaN compound semiconductor layer (cladding layer). Coating), laminates with transparent electrode layers, etc.

In addition, the shape of the LED element 12 is not particularly limited. For example, it may have a light-emitting surface of (200-300) μm×(200-300) μm. In addition, the height of the LED element 12 is usually about 50 to 200 μm. The LED element 12 is not only the upper surface, but also the one that takes out light from the side surface or the bottom surface. In the light-emitting device 100 shown in FIG. 2, although only one LED element 12 is arranged on the substrate 11, a plurality of LED elements 12 may be arranged on the substrate 11.

The connection method of the LED element 12 and the aforementioned electrode 15 is not particularly limited. For example, as shown in FIG. 2, the LED element 12 and the electrode 15 can be connected through a metal wire 16. In addition, the LED element 12 and the electrode 15 can be connected through a protruding electrode (not shown). The state where the LED element 12 and the electrode 15 are connected through a metal wire is called a wire bonding type. On the other hand, the aspect in which the LED element 12 and the electrode 15 are connected through the protruding electrode is called a flip-chip bonding type.

In the flip-chip bonding type light emitting device 100, an underfill material (not shown) can be filled in the gap between the LED element 12 and the substrate 11. The underfill material may be a member containing silicone resin, epoxy resin, the same material as the sealing material layer 13 described later, or the like.

(2.1.3) Sealing material layer The sealing material layer 13 is a layer covering the aforementioned LED element 12 or electrode 15, and is a layer that protects the LED element 12 or electrode 15 from humidity or hydrogen sulfide gas outside the light-emitting device. The formation area of the sealing material layer 13 is not particularly limited, and the sealing material layer 13 may be a layer covering only the LED element 12 and the electrode 15. In addition, not only the LED element 12 or the electrode 15 but also a layer that completely covers the substrate 11 on the side where the LED element 12 is arranged.

The sealing material layer 13 may contain polysiloxane and the compound (1) related to the present invention. The thickness of the sealing material layer 13 is in the range of 0.1-15 micrometers, Preferably it is in the range of 0.3-4 micrometers. If the thickness of the sealing material layer is 15 μm or less, the sealing material layer 3 is unlikely to be deformed and cracked during film formation.

On the other hand, when the thickness of the sealing material layer 13 is 0.1 μm or more, it is easy to sufficiently improve the gas barrier properties of the sealing material layer 3 and sufficiently protect the LED elements 12 and electrodes 15 from humidity and sulfurization components outside the light-emitting device 100. The thickness of the sealing material layer 13 is determined to be the maximum thickness of the sealing material layer 13 arranged on the upper surface (light emitting surface) of the LED element 12. In addition, the thickness of the layer was measured using a laser micrometer.

(2.1.4) Wavelength conversion layer The light-emitting device related to the present invention may include a wavelength conversion layer 14. The wavelength conversion layer 14 is a layer that converts light of a specific wavelength emitted by the LED element 12 to light of other specific wavelengths. The wavelength conversion layer 14 may be a layer in which phosphor particles are dispersed in epoxy resin, silicone resin, or the like.

If the phosphor particles contained in the wavelength conversion layer 14 are excited by the light emitted from the LED element 12 and emit fluorescence of a different wavelength from the emitted light from the LED element 12. For example, in the case of phosphor particles that emit yellow fluorescence, there are YAG (yttrium, aluminum, and garnet) phosphors. The YAG fluorescent system receives blue light (with a wavelength in the range of 420-485nm) emitted from a blue LED element, and emits yellow fluorescent light (with a wavelength in the range of 550-650nm).

For example, (a) the phosphor particles are mixed with a mixed raw material having a predetermined composition, an appropriate amount of flux (fluoride such as ammonium fluoride) is mixed and pressurized to form a compact. (b) The obtained molded body is placed in a crucible and fired in the air at a temperature range of 1350 to 1450°C for 2 to 5 hours to obtain a sintered body.

The mixed raw materials with the specified composition are obtained by fully mixing the oxides of Y, Gd, Ce, Sm, Al, La, Ga, etc. at a stoichiometric ratio, or compounds that easily become oxides at high temperatures. In addition, the mixed raw material system with a specified composition (a) mixes and dissolves rare earth elements such as Y, Gd, Ce, and Sm in an acid solution and oxalic acid at a chemical ratio to obtain a co-precipitated oxide. (b) It can also be obtained by mixing this co-precipitated oxide with alumina or gallium oxide. The type of phosphor is not limited to YAG phosphors, and may be, for example, other phosphors such as non-garnet-based phosphors that do not contain Ce.

The average particle diameter of the phosphor particles is preferably in the range of 1 to 50 μm, more preferably 10 μm or less. The larger the particle size of the phosphor particles, the more the luminous efficiency (wavelength conversion efficiency) is improved. On the other hand, when the particle size of the phosphor particles is too large, the gap generated at the interface between the phosphor particles and the resin increases. This makes it easy to reduce the strength of the wavelength conversion layer 14. The average particle size of the phosphor particles refers to the value of D50 measured by a laser diffraction particle size distribution meter. Examples of laser diffraction particle size distribution measuring devices include the laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation. The amount of phosphor particles contained in the wavelength conversion layer 14 is usually in the range of 5 to 15% by mass relative to the total mass of the wavelength conversion layer 14.

The thickness of the wavelength conversion layer 14 is preferably about 25 μm to 5 mm. When the thickness of the wavelength conversion layer 14 is too thick, the concentration of the phosphor particles may be excessively reduced, and the phosphor particles may not be uniformly dispersed. The thickness of the wavelength conversion layer 14 means the maximum thickness of the wavelength conversion layer 14 formed as a film on the light-emitting surface of the LED element 12. The thickness of the wavelength conversion layer 14 can be measured with a laser micrometer.

(2.1.5) Supplement to the basic composition of LED light-emitting devices As the basic structure of the LED light emitting device of the present invention, the surface mount type (SMT type) LED light emitting device described below, the CSP type with different chip sizes of the packaging method, and the TFT type using TFT can be cited.

The so-called surface mount type (SMT type, Surface Mount Technology) LED light-emitting device is a mounting in which LED components are mounted on a substrate with metal terminals (lead frame), and the LED components and electrodes are connected by bonding wires Way.

In addition, the so-called CSP (Chip Size Package) LED light-emitting devices with different chip sizes with different packaging methods are implemented in which the LED elements themselves have metalized anodes and cathodes and are directly soldered to the circuit board.

In addition, the so-called TFT-type LED light-emitting device is a method of controlling the light emission of the LED with TFT.

3 shows a schematic cross-sectional view of an example of an SMT-type LED light emitting device containing the aforementioned compound (1) related to the anti-vulcanizing agent of the present invention. The LED light-emitting device 200 shown in FIG. 3 shows a surface-mounting type (SMT type) LED light-emitting device. On an insulating substrate 20 constituting a packaging substrate P, a lead frame 21 and an LED element 25 as electrodes pass through a connection terminal 24 Connect and connect with the lead frame 21 through the welding 26 and the welding wire 27 provided on the surface of the LED element 25.

A sealing material layer 28 is provided in this configuration of the LED element 25, the coated bonding wire 27, the lead frame 21, etc., and the sealing material layer 28 together with the phosphor particles 29a is the anti-vulcanization agent related to the present invention, that is, contains the compound (1 ) The composition of 29b.

In the configuration of FIG. 3, a reflective layer 23 is further formed on the periphery of the sealing material layer 28. The reflective layer 23 may or may not be present. The reflective layer 23 is preferably Ag with high reflectivity. In addition to Ag, metals such as Al, Ni, and Ti can also be used.

In the LED light-emitting device 200 shown in FIG. 3, the anti-sulfurizing agent-containing particles 29b present in a dispersed state due to the sealing material layer 28 containing the phosphor 29a and the vulcanization invaded from the outside of the LED light-emitting device 200 Hydrogen reacts, and capturing the hydrogen sulfide can effectively prevent the corrosion of the metal components such as the constituent materials of the LED element or the silver constituting the reflective layer.

(2.1.6) Manufacturing method of light-emitting device The aforementioned method of manufacturing the light-emitting device can be a method having the following three steps. (1) Steps to prepare the substrate for mounting LED components (2) The step of coating the sealing composition to coat the LED elements and electrodes (3) Steps to harden the sealing composition

In the manufacturing method of the light-emitting device, if necessary, it may have (4) the step of forming a wavelength conversion layer containing phosphor particles on the sealing material layer.

[1] LED component preparation steps In the LED component preparation step, the substrate for connecting the LED component and the electrode is prepared. For example, it may be a step of preparing a substrate having the aforementioned electrodes, fixing the LED element to the substrate, and connecting the electrode of the substrate, and the cathode electrode and the anode electrode of the LED element. The method of connecting the LED element and the electrode, or the method of fixing the LED element to the substrate is not particularly limited, and may be the same method as the conventionally known method.

[2] Step of coating composition for sealing The step of applying the sealing composition may be a step of applying the aforementioned coating solution containing the anti-sulfurizing agent so as to cover the electrode and the LED element. The coating solution contains metal anti-sulfurization, polysiloxane precursor, sulfhydryl-containing silane coupling agent and solvent.

The coating method of the sealing composition is not particularly limited, and may be known coating methods such as blade coating, spin coating, dispenser coating, and spray coating.

[3] Steps to harden the coating film of the sealing material The step of curing the coating film of the sealing material may be a step of heating the coating film. In this coating film hardening step, the solvent of the sealing material coating film is removed, and the polysiloxane precursor is dehydrated and condensed as polysiloxane to harden the sealing material coating film.

The temperature at the time of curing the seal coating film is preferably 100°C or higher, more preferably in the range of 150 to 300°C. When the heating temperature is less than 100°C, the dehydration condensation of the polysiloxane precursor may not be sufficiently performed, and the strength of the sealing material layer may not be sufficiently improved in some cases. In addition, water and the like generated during dehydration and condensation of the polysiloxane precursor cannot be sufficiently removed, and there is a possibility that the light resistance of the sealing material layer, etc., may be reduced.

[4] Steps for forming wavelength conversion layer The step of forming the wavelength conversion layer may be a step of coating the composition for the wavelength conversion layer contained in the phosphor particles and the resin or its precursor on the aforementioned sealing material layer, and then hardening it. The composition for the wavelength conversion layer may contain a solvent if necessary. The solvent contained in the composition for the wavelength conversion layer is not particularly limited as long as it can dissolve or disperse the aforementioned resin or its precursor. Solvents can be hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl acetate, etc. The esters and so on.

In addition, the mixing of the composition for the wavelength conversion layer can be performed by, for example, a stirring mill, a blade kneading stirring device, a film rotating type disperser, or the like. By adjusting the stirring conditions, the sedimentation of the phosphor particles in the composition for the wavelength conversion layer is suppressed.

The coating method of the composition for the wavelength conversion layer can be appropriately selected, such as dispenser coating. In addition, after coating the composition for the wavelength conversion layer, it is cured. The curing method and curing conditions of the composition for the wavelength conversion layer can be appropriately selected according to the type of resin. As an example of the hardening method, heat hardening can be cited.

(2.2) Photoelectric conversion elements and solar cells The anti-vulcanization agent of the present invention is preferably, for example, a sealing material layer suitable for an organic functional layer of a photoelectric conversion element. 4 is a cross-sectional view showing an example of a solar cell of a single configuration (a configuration in which the bulk heterojunction layer is a single layer) including a bulk heterojunction type organic photoelectric conversion element.

In FIG. 4, the bulk heterojunction organic photoelectric conversion element 300 is on one side of the substrate 31, and the photoelectric conversion part of the transparent electrode (anode 32), the hole transport layer 33, and the bulk heterojunction layer are sequentially laminated 34. The electron transport layer (or also called the buffer layer) 35 and the counter electrode (cathode 36).

The substrate 31 is a member that holds the transparent electrode 32, the photoelectric conversion portion 34, and the counter electrode 36 laminated in this order. In this embodiment, it is preferable that the photoelectrically converted light is incident from the substrate 31 side, so that the substrate 31 can transmit the photoelectrically converted light, that is, it is a transparent member with respect to the wavelength of the photoelectrically converted light. For the substrate 31, for example, a glass substrate, a resin substrate, or the like is used. The substrate 31 is not essential. For example, by forming the transparent electrode 32 and the counter electrode 36 on both sides of the photoelectric conversion portion 34, a bulk heterojunction organic photoelectric conversion element 300 can be constructed.

The photoelectric conversion part 34 is a layer that converts light energy into electrical energy, and is composed of a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material is relatively used as an electron donor (Donner), and the n-type semiconductor material is relatively used as an electron acceptor (Acceptor). Here, the electron donor and electron acceptor system "when absorbing light, move electrons from the electron donor to the electron acceptor to form a pair of holes and electrons (charge separation state). For example, the electrode only supplies or accommodates electrons, but uses light reaction to supply or accommodate electrons.

In FIG. 4, the light incident from the transparent electrode 32 through the substrate 31 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion portion 34, and the electron is moved from the electron donor to the electron acceptor to form a hole Pair with electrons (charge separation state). The charge generated is in the internal electric field. For example, when the work functions of the transparent electrode 32 and the counter electrode 36 are different, the electrons pass between the electron acceptors by the potential difference between the transparent electrode 32 and the counter electrode 36, and the holes are supplied by the electrons. Different electrodes are transported between the bodies, and the photocurrent is detected.

For example, when the work function of the transparent electrode 32 is greater than the work function of the counter electrode 36, electrons are transmitted to the transparent electrode 32, and holes are transmitted to the counter electrode 36. Still, if the size of the work function is reversed, electrons and holes are transferred in the opposite direction. In addition, applying a potential between the transparent electrode 32 and the counter electrode 36 can also control the transmission direction of electrons and holes.

Although not described in FIG. 4, it may have other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer.

In addition, for the purpose of further improving the solar light utilization efficiency (photoelectric conversion efficiency), a tandem structure (a structure having a plurality of heterojunction layers) in which such photoelectric conversion elements are laminated may be used.

Examples of materials that can be used in the above-mentioned layers include n-type semiconductor materials and p-type semiconductor materials described in paragraphs 0045 to 0113 of JP 2015-149483 A.

(Method of forming bulk heterojunction layer) As a method of forming a bulk heterojunction layer of a mixed electron acceptor and an electron donor, a vapor deposition method, a coating method (including a casting method and a spin coating method), etc. can be exemplified. Among them, in order to increase the area of the interface between the aforementioned holes and electrons in order to separate the charges, and to produce an element with high photoelectric conversion efficiency, the coating method is preferred. In addition, the coating method is also excellent in production speed.

In the present invention, the n-type semiconductor material and the p-type semiconductor material constituting the bulk heterojunction layer can be used as the organic material for electronic components of the present invention. That is, it is preferable to form the bulk heterojunction layer by coating a solution containing the n-type semiconductor material and the p-type semiconductor material, an organic solvent, and cellulose nanofibers, and the n-type semiconductor material and The coating solution of p-type semiconductor material, organic solvent, and cellulose nanofiber is preferably set at 50°C or less, the concentration of carbon dioxide dissolved in the organic solvent under atmospheric pressure is 1 ppm to the saturation of the aforementioned organic solvent concentration.

As a means for setting the concentration of dissolved carbon dioxide in the above range, as mentioned above, a method of bubbling carbon dioxide in a solution containing n-type semiconductor material and p-type semiconductor material, an organic solvent, and cellulose nanofiber, or Supercritical chromatography using supercritical fluids containing organic solvents and carbon dioxide.

After coating, it is preferable to perform heating in order to cause the removal of residual solvent, moisture, and gas, and to increase the mobility of the semiconductor material by crystallization and absorption of long waves. In the manufacturing process, when an annealing treatment is performed at a predetermined temperature, microscopically, a part of the arrangement or crystallization can be promoted, and the bulk heterojunction layer can be made into an appropriate phase separation structure. As a result, it is performed in such a way that the carrier mobility of the bulk heterojunction layer can be improved and high efficiency can be obtained.

Although the photoelectric conversion portion (bulk heterojunction layer) 34, the electron acceptor and the electron donor may be uniformly mixed in a single layer structure, it is also possible to change the mixing ratio of the electron acceptor and the electron donor to a multiple layer structure.

Next, the electrodes constituting the organic photoelectric conversion element will be described.

The organic photoelectric conversion element uses the positive and negative charges generated by the bulk heterojunction layer to pass through the p-type organic semiconductor material and the n-type organic semiconductor material, and is taken out from the transparent electrode and the counter electrode, respectively, to function as a battery. In individual electrodes, the characteristics suitable for the carrier passing the electrode are sought.

(Opposite) In the present invention, the so-called counter electrode (cathode) is preferably an electrode that takes out electrons. For example, when used as a cathode, although it may be a separate layer of a conductive material, in addition to conductive materials, resins that hold these can also be used in combination.

As a counter electrode material, it is sought to have sufficient conductivity, and when joined with the aforementioned n-type semiconductor material, it has a work function close to the extent that a Schottky barrier is not formed and does not deteriorate. That is, it is preferable to use a metal having a work function of 0 to 0.3 eV, preferably a work function of 4.0 to 5.1 eV, than the LUMO of the n-type semiconductor material used in the bulk heterojunction layer.

On the other hand, since the work function is smaller (deeper) than the transparent electrode (anode) that takes out the holes, it is not good, and the metal with a larger (shallow) work function than the n-type semiconductor material produces interlayer resistance, so It is preferably a metal that actually has a work function of 4.2 to 4.8 eV. Accordingly, materials based on oxides such as aluminum, gold, silver, copper, indium, zinc oxide, ITO, and titanium oxide are also preferable. Aluminum, silver, and copper are more preferable, and silver is still more preferable. Moreover, the work function of these metals can also be measured by ultraviolet photoelectron spectroscopy (UPS).

Still, it can be alloyed if necessary, for example, suitable for magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al ₂ O ₃ ) mixture, lithium/aluminum mixture, aluminum and the like. The counter electrode can be produced by forming a thin film of these electrode materials by evaporation or sputtering. In addition, the film thickness is usually in the range of 10 nm to 5 μm, and preferably selected in the range of 50 to 200 nm.

In addition, when making the counter electrode side light-transmissive, for example, it can be made by thinning a conductive material suitable for the counter electrode such as aluminum and aluminum alloys, silver and silver compounds, to a thickness of about 1-20 nm. , Set up a film of conductive light-transmitting material to become a light-transmitting counter electrode.

(Transparent electrode) In the present invention, the transparent electrode is preferably an electrode for taking out holes. For example, when used as an anode, it is preferably an electrode that transmits light in the range of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ , and ZnO, metal thin films such as gold, silver, and platinum, metal nanowires, carbon nanotubes, etc. can be used.

In addition, it is also possible to use selected from polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisobenzothiophene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene , Polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene derivatives in the group of conductive polymers, etc. In addition, a plurality of these conductive compounds may be combined to form a transparent electrode.

(Middle electrode) In addition, as a material for the intermediate electrode that is necessary in the case of a series configuration, it is preferable to use a layer of a compound that has both transparency and conductivity. The material used for the aforementioned transparent electrode (ITO, AZO, FTO, oxide Transparent metal oxides such as titanium, Ag, Al, Au, etc. containing very thin metal layers or layers of nano-particles and nanowires, PEDOT: conductive polymer materials such as PSS, polyaniline, etc.).

Furthermore, among the aforementioned hole transport layer and electron transport layer, they are laminated by appropriate combinations, and there are also combinations used as intermediate electrodes. In such a configuration, it is preferable to omit the step of forming one layer. Next, the materials other than the electrodes and bulk heterojunction layers are described.

(Hole transport layer and electron blocking layer) Since the organic photoelectric conversion element can more efficiently extract the charges generated in the bulk heterojunction layer, it is preferable to have a hole transport layer and an electron blocking layer between the bulk heterojunction layer and the transparent electrode.

As a material constituting these layers, for example, as a hole transport layer, PEDOT manufactured by Heraeus Corporation, Clevious, etc., polyaniline and its dopant materials, cyanide compounds described in WO2006/019270, etc. can be used.

Furthermore, in a hole transport layer with a LUMO level that is shallower than the LUMO level of the n-type semiconductor material used in the bulk heterojunction layer, the electrons generated in the bulk heterojunction layer will not flow to the transparent electrode side. The electronic blocking function of the rectifying effect. For such a hole transport layer, it is preferable to use a hole transport layer with such a function, which is also called an electron blocking layer.

As such a material, triarylamine compounds described in JP 5-271166 A and the like can be used, and metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used. In addition, a layer composed of a single p-type semiconductor material used in the bulk heterojunction layer can also be used. As a means for forming these layers, although either a vacuum vapor deposition method or a solution coating method may be used, the solution coating method is preferred. Before the bulk heterojunction layer is formed, when the coating film is formed in the lower layer, since it has the effect of leveling the coating surface and reducing the effects of leakage and the like, it is preferable.

(Electron transport layer, hole blocking layer and buffer layer) The organic photoelectric conversion element is formed by forming an electron transport layer, a hole blocking layer, and a buffer layer between the bulk heterojunction layer and the opposite electrode. Since it is possible to more efficiently extract the charges generated in the bulk heterojunction layer, it is preferable To have such layers.

In addition, as the electron transport layer, octaazaporphyrins, p-type semiconductor perfluoro compounds (perfluoropentacene or perfluorophthalocyanine, etc.) can be used, but in the same way, it is used for layers with relatively bulk heterojunctions. The electron transport layer of the HOMO level of the p-type semiconductor material with a deeper HOMO level imparts a hole blocking function with a rectifying effect that does not flow to the opposite side to the holes generated in the bulk heterojunction layer. For such an electron transport layer, it is preferable to use an electron transport layer with such a function, which is also called a hole blocking layer.

As the material for the electron transport layer, phenanthrene compounds such as bathocuproine, naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, etc. can also be used N-type semiconductor materials and n-type inorganic oxides such as titanium oxide, zinc oxide, gallium oxide, etc., and a layer composed of single n-type semiconductor materials used in bulk heterojunction layers, etc.

In addition, alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.

Among these, it is preferable to use an alkali metal compound that is further doped with organic semiconductor molecules and also has the function of improving the circuit connection with the aforementioned metal electrode (cathode). In the case of an alkali metal compound layer, in particular, it is also called a buffer layer.

(Other layers) For the purpose of improving the energy conversion efficiency or the life of the device, various intermediate layers can be included in the device. Examples of the intermediate layer include a hole blocking layer, an electron blocking layer, a hole injection layer, an electron injection layer, an exciton blocking layer, a UV absorption layer, a light reflection layer, a wavelength conversion layer, and the like.

(Substrate) When the photoelectrically converted light is incident from the substrate side, the substrate is preferably a member that can transmit the photoelectrically converted light, that is, a member that is transparent to the wavelength of the photoelectrically converted light. For the substrate, for example, a glass substrate or a resin substrate is suitable, but from the viewpoint of lightness and flexibility, it is desirable to use a transparent resin film.

The transparent resin film that can be preferably used as a transparent substrate in the present invention is not particularly limited, and its material, shape, structure, thickness, etc. can be appropriately selected from known ones. Examples include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), modified polyester, etc., polyethylene (PE) resin film, polypropylene (PP) ) Resin film, polystyrene resin film, polyolefin resin film such as cyclic olefin resin, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, Poly (PSF) resin film, polyether (PES) resin film, polycarbonate (PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, three Acetyl cellulose (TAC) resin film, etc., but it is particularly preferred if it is a resin film with a transmittance of 80% or more in the wavelength of the visible light region (380-800nm). Among them, from the viewpoints of transparency, heat resistance, ease of handling, strength, and cost, biaxially stretched polyethylene terephthalate film, biaxially stretched polyethylene naphthalate film, and polyethylene terephthalate film are preferred. Ether turpentine film, polycarbonate film, more preferably biaxially stretched polyethylene terephthalate film, biaxially stretched polyethylene naphthalate film.

For the transparent substrate used in the present invention, in order to ensure the wettability or adhesion of the coating liquid, surface treatment or an easy-to-bond layer may be provided. For surface treatment or easy bonding layer, conventionally known techniques can be used. For example, the surface treatment includes surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Moreover, as the easy-to-adhesive layer, polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylene copolymer, etc. , Epoxy copolymers, etc.

In addition, for the purpose of suppressing the permeation of oxygen and water vapor, a barrier coating layer can be formed by phosphorescence in advance on the transparent substrate.

(Optical Function Layer) The organic photoelectric conversion element aims to receive sunlight more efficiently, and may have various optical function layers. As the optical function layer, a light-collecting layer such as an anti-reflection film, a microlens array, etc. can be provided, such as a light-diffusion layer that scatters light reflected by the opposite pole and can be incident on the bulk heterojunction layer again.

As the anti-reflection layer, although various known anti-reflection layers can be provided, for example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy-adhesive layer adjacent to the film is determined by It is within the range of 1.57 to 1.63, since it can reduce the reflection at the interface between the thin film substrate and the easy-to-bond layer and increase the transmittance, so it is better. As a method of adjusting the refractive index, it can be implemented by appropriately adjusting the ratio of a relatively high refractive index oxide sol such as tin oxide sol or cerium oxide sol to a binder resin. Although the easy-adhesive layer may be a single layer, in order to improve adhesiveness, it may have a structure of two or more layers.

As the light-collecting layer, for example, it can be processed by a structure in which a microlens array is arranged on the sunlight-receiving side of the support substrate, or combined with a so-called light-collecting sheet, which can increase the amount of light received from a specific direction, or vice versa. Dependence of the incident angle of sunlight.

As an example of the microlens array, on the light extraction side of the substrate, one side is arranged in 30μm2 dimensions and the apex angle becomes a quadrangular pyramid of 90 degrees. One side is preferably in the range of 10 to 100 μm. If it is smaller than this, it will be colored due to the effect of diffraction.

In addition, as the light scattering layer, various anti-glare layers, metals or various inorganic oxides, etc., include a layer in which nanoparticles and nanowires are dispersed in a colorless and transparent polymer.

(Graphical) The method or manufacturing process for patterning the foregoing electrode, power generation layer, hole transport layer, electron transport layer, etc. is not particularly limited, and known methods can be appropriately applied.

If it is a soluble material such as a bulk heterojunction layer, a transmission layer, etc., only unnecessary parts can be wiped after the mold coating, dip coating, etc. are completely coated. Inkjet printing or screen printing can be used. , Direct patterning during coating.

In the case of insoluble materials such as electrode materials, mask vapor deposition may be performed during vacuum deposition of the electrodes, or patterning may be performed by known methods such as etching or lift-off. In addition, patterns can also be formed by transferring patterns formed on other substrates.

(seal) In addition, in order to manufacture the organic photoelectric conversion element in the environment without degradation of oxygen, moisture, etc., it is also preferable to use methods other than the sealing material of the present invention. For example, a method of sealing a lid made of alumina or glass with an adhesive is used, and a plastic film forming a gas barrier layer of aluminum, silica, alumina, etc., and an organic photoelectric conversion element are used The method of adhesive bonding, the method of spin-coating organic polymer materials with high gas barrier properties (polyvinyl alcohol, etc.), the method of applying inorganic films with high gas barrier properties (silica, alumina, etc.) or organic films (poly Toluene (Parylene, etc.) is stacked under vacuum, and composite lamination methods, etc.

(2.3) Display devices using organic EL elements (2.3.1) Organic EL display device Fig. 5 is a schematic cross-sectional view showing an example of the structure of an organic EL element. In the organic EL display device 400, a cathode 45, an organic functional layer group 46, and a transparent electrode (anode 47) are laminated on a substrate 41 to form an organic EL element 40. As an aspect of the sealing in the present invention, the anti-sulfurization layer 49 is formed so as to cover the organic EL element 40 described above. In addition, the anti-vulcanization layer 49 is coated on the sealing material layer 48. Still, it may be a form in which an anti-vulcanizing agent is contained in the sealing material layer. In the following, the elements constituting the organic EL display device will be described.

(Substrate) The substrate (hereinafter, also referred to as substrate, support substrate, base material, support, etc.) that can be used in organic EL devices is not particularly limited. Glass substrates, plastic substrates, etc. can be used, and they can be transparent or opaque. When taking out the light from the substrate side, the substrate is preferably transparent. As the transparent substrate preferably used, glass, quartz, and transparent plastic substrates can be cited.

In addition, as a substrate, in order to prevent the intrusion of oxygen or water from the substrate side, in a test based on JIS Z-0208, it is preferable that the thickness is 1μm or more, and the water vapor permeability is 1g/(m ² ･24h･atm ) (25℃) or less.

As a glass substrate, specifically, an alkali-free glass, low alkali glass, soda lime glass, etc. are mentioned, for example. From the viewpoint of low moisture absorption, alkali-free glass is preferred, but any of these can be used if sufficient drying is performed.

In recent years, plastic substrates have attracted attention for reasons such as high flexibility, light weight, and resistance to breakage, and the possibility of further thinning of organic EL devices.

The resin film used as the base material of the plastic substrate is not particularly limited. Examples include polyester, polyethylene, and polyethylene such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Acrylic, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate Cellulose esters such as formates, cellulose nitrates, or their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyvinyl vinyl alcohol, syndiotactic polystyrene, polycarbonate, and Bornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfide (PES), polyphenylene sulfide, polysulfide, polyether imine, polyether ketone imine, polyether Amine, fluororesin, nylon, polymethacrylate, acrylic or polyarylate, organic-inorganic composite (Hybrid) resin, etc.

Examples of the organic-inorganic composite resin include those obtained by combining an organic resin and an inorganic polymer (for example, silica, alumina, titania, zirconia, etc.) obtained by sol-gel reaction. Among these, ARTON (manufactured by JSR Co., Ltd.) or Apelle (manufactured by Mitsui Chemicals Co., Ltd.) so-called norbornene (or cycloolefin-based) resin is particularly preferred.

Generally, the produced plastic substrates have relatively high moisture permeability, and there are cases where moisture is contained inside the substrates. Therefore, when using such a plastic substrate, it is better to install a barrier film (also called "gas barrier film" or "water vapor sealing film") on the resin film to prevent the intrusion of water vapor or oxygen as a gas barrier. Film those.

The material constituting the barrier film is not particularly limited, and a coating film of an inorganic substance, an organic substance, or a combination of the two is used. Preferably, a film can be formed, and the water vapor transmission rate (25±0.5°C, relative humidity (90±2)%RH) measured in accordance with JIS K 7129-1992 is 0.01g/(m ² ･24h) or less The barrier film of JIS K 7126-1987 is more preferably an oxygen permeability of 1×10 ^-3 mL/(m ² ･24h･atm) or less, and a water vapor permeability of 1×10 ^{-as measured by the method of JIS K 7126-1987} High barrier film below ⁵ g/(m ^{2 ･24h).}

The material constituting the barrier film is not particularly limited as long as it has a function of suppressing the infiltration of those that cause element deterioration such as moisture or oxygen. For example, metal oxides, metal oxynitrides, or metal nitrides can be used. Inorganic, organic or a composite of the two, etc.

Examples of metal oxides, metal oxynitrides or metal nitrides include silicon oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), aluminum oxide and other metal oxides, silicon nitride, etc. Metal oxynitrides such as metal nitrides, silicon oxynitride, titanium oxynitride, etc.

Furthermore, in order to improve the fragility of the film, it is more preferable to have a laminated structure including these inorganic layers and organic materials. The lamination order of the inorganic layer and the organic layer is not particularly limited, but it is preferable to alternately laminate both layers multiple times.

The method of providing a barrier film on the aforementioned resin film is not particularly limited. Although any method can be used, for example, vacuum evaporation, sputtering, reactive sputtering, molecular wire epitaxy, cluster ion beam, ion Plating method, plasma polymerization method, atmospheric piezoelectric plasma polymerization method, CVD method (such as plasma CVD method, laser CVD method, thermal CVD method, etc.), coating method, sol/gel method, etc. Among these, from the viewpoint of a dense film that can be formed, a method of plasma CVD treatment by atmospheric pressure or near atmospheric pressure is preferable.

Examples of opaque substrates include metal plates, thin films, opaque resin substrates, ceramic substrates, and the like of aluminum oxide and stainless steel.

(anode) As the anode of the organic EL element, it is preferable to use a metal, alloy, conductive compound of metal with a large work function (4 eV or more), or a mixture of these as the electrode material.

Here, the so-called "conductive compound of metal" refers to a compound of metal and other substances that has conductivity, specifically, it refers to a conductive compound such as metal oxides and halides.

Specific examples of such electrode materials include metals such as Au, CuI, indium/tin oxide (ITO), SnO ₂ , ZnO, and other conductive transparent materials. The anode can be produced by forming a thin film containing these electrode materials on the substrate by a known method such as vapor deposition or sputtering.

In addition, the thin film can be used to form a pattern of a desired shape by photolithography. In addition, when too much pattern accuracy is not required (about 100μm or more), it can pass through the vapor deposition or sputtering of the above-mentioned electrode material. The mask of the desired shape is patterned.

In the case of taking out the light emission from the anode, it is desirable that the light transmittance is greater than 10%. In addition, the sheet resistance as the anode is preferably several hundred Ω/sq. or less. Furthermore, although the film thickness of the anode differs depending on the constituent material, it is usually in the range of 10 nm to 1 μm, and preferably selected in the range of 10 to 200 nm.

(Organic functional layer) Although the organic functional layer (also referred to as "organic EL layer" or "organic compound layer") contains at least a light-emitting layer, the so-called light-emitting layer in a broad sense refers to an electrode consisting of a cathode and an anode when current flows The light-emitting layer, specifically, refers to a layer containing an organic compound that emits light when a current flows through an electrode composed of a cathode and an anode.

If necessary, the organic EL device used in the present invention may have a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer in addition to the light-emitting layer. These layers are sandwiched between the cathode and the anode. structure.

Specifically, one can cite (i) Anode/light emitting layer/cathode (ii) Anode/hole injection layer/light emitting layer/cathode (iii) Anode/light emitting layer/electron injection layer/cathode (iv) Anode/hole injection layer/light-emitting layer/electron injection layer/cathode (v) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode (vi) Anode/hole transport layer/light emitting layer/electron transport layer/cathode And other structures.

Furthermore, a cathode buffer layer (for example, lithium fluoride, etc.) may be inserted between the electron injection layer and the cathode, or an anode buffer layer (for example, copper phthalocyanine, etc.) may be inserted between the anode and the hole injection layer.

(Light-emitting layer) The light-emitting layer is a layer that combines the electrons and holes injected from the electrode or the electron transport layer and the hole transport layer to emit light. The light-emitting part can be in the layer of the light-emitting layer or the interface between the light-emitting layer and the adjacent layer. . The light-emitting layer may be a layer having a single composition, or may be a laminated structure including a plurality of layers having the same or different compositions.

The light-emitting layer itself can be endowed with functions such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. That is, the light-emitting layer can be given (1) when an electric field is applied, holes can be injected through the anode or hole injection layer, and electrons can be injected by the cathode or electron injection layer, and (2) the electric field can be used to inject electrons. At least one of the luminous functions that the injected electric charges (electrons and holes) move, and (3) the recombination field of electrons and holes is provided to the inside of the light-emitting layer, and the light-emitting function is connected to the light. Furthermore, the light-emitting layer may differ in the ease of injection of holes and the ease of injection of electrons. Moreover, although the transport function represented by the mobility of holes and electrons may be large or small, it is preferable to have at least either one The function of charge movement.

The type of the light-emitting material used in the light-emitting layer is not particularly limited, and those known in the past as light-emitting materials in organic EL devices can be used. Such light-emitting materials are mainly organic compounds, depending on the desired hue. For example, the compounds described in Macromol.Symp. 125, pages 17 to 26 can be cited. In addition, the luminescent material can be a polymer material such as p-polyphenylene vinylene or polytetrafluoroethylene, and then a polymer material with the aforementioned luminescent material introduced into the side chain can be used, or the aforementioned luminescent material can be used as the main chain of the polymer. Molecular materials. Furthermore, as mentioned above, in addition to the light-emitting performance, since the luminescent material can also have a hole injection function or an electron injection function, almost all of the hole injection material or electron injection material described later can also be used as a luminescent material.

When the layer constituting the organic EL element is composed of two or more organic compounds, the main component can be called the host, and the other components are called the dopant. In the light-emitting layer, when the host and the dopant are used together, the The mixing ratio of the dopant of the light-emitting layer of the host compound of the component (hereinafter also referred to as the light-emitting dopant) is preferably within the range of 0.1-30% by mass.

The dopants used in the light-emitting layer can be roughly divided into two types: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescence.

Representative examples of fluorescent dopants include coumarin-based pigments, pyran-based pigments, cyanine-based pigments, crotonium-based pigments, square cyanine (Squarylium)-based pigments, and oxabenzene Anthracene (Oxobenzanthracene) dyes, luciferin dyes, rhodamine dyes, pyridinium dyes, perylene dyes, stilbene dyes, polythiophene dyes or rare earth complex phosphors, other known Fluorescent compounds, etc.

In the present invention, it is preferable that at least one light-emitting layer contains a phosphorescent compound.

In the present invention, the so-called phosphorescent compound is a compound that is observed to emit light from an excited triplet state, and has a phosphorescent quantum yield of 0.001 or more at 25°C.

The phosphorescence quantum yield is preferably 0.01 or more, and more preferably 0.1 or more. The above-mentioned phosphorescence quantum yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopy II of Lecture 7 of Experimental Chemistry, 4th Edition. Although the phosphorescent quantum yield in the solution can be measured using various solvents, the phosphorescent compound used in the present invention can achieve the above-mentioned phosphorescent quantum yield in any solvent.

The phosphorescent dopant is a phosphorescent compound. As a representative example, it is preferably a complex compound containing metals of groups 8 to 10 in the periodic table of the elements, and more preferably an iridium compound, an osmium compound, and a rhodium compound , Palladium compounds or platinum compounds (platinum complex compounds), of which iridium compounds, rhodium compounds, platinum compounds are preferred, and iridium compounds are most preferred.

Examples of dopants include compounds described in the following documents or patent gazettes. J. Am. Chem. Soc. 123 Volume 4304～4312, International Publication No. 2000/70655, Same as 2001/93642, Same as 2002/02714, Same as 2002/15645, Same as 2002/44189, Same as 2002/ No. 081488, Japanese Patent Application Publication No. 2002-280178, Same as 2001-181616, Same as 2002-280179, Same as 2001-181617, Same as 2002-280180, Same as 2001-247859, Same as 2002- Bulletin 299060, Bulletin 2001-313178, Bulletin 2002-302671, Bulletin 2001-345183, Bulletin 2002-324679, Bulletin 2002-332291, Bulletin 2002-50484, Bulletin 2002-332292 Bulletin No. 2002-83684, JP 2002-540572 Bulletin, JP 2002-117978 Bulletin, 2002-338588 Bulletin, 2002-170684 Bulletin, 2002-352960, JP 2002-50483, same 2002-100476, same 2002-173674, same 2002-359082, same 2002-175884, same 2002-363552, same 2002-184582, same 2003 -7469, Japanese Special Form 2002-525808, Japanese Special Publication 2003-7471, Japanese Special Publication 2002-525833, Japanese Special Publication 2003-31366, Same 2002-226495, Same 2002 -234894, same as 2002-235076, same as 2002-241751, same as 2001-319779, same as 2001-319780, same as 2002-62824, same as 2002-100474, same as 2002- Bulletin No. 203679, the same bulletin 2002-343572, the same bulletin 2002-203678, etc.

Only one type of light-emitting dopant may be used, or multiple types may be used. By taking out the light emission from these dopants at the same time, a light-emitting element having a plurality of emission maximum wavelengths may also be constructed. In addition, for example, both phosphorescent dopants and fluorescent dopants may be added. When a plurality of light-emitting layers are laminated to constitute an organic EL device, the light-emitting dopants contained in the individual layers may be the same or different, and may be of a single type or of plural types.

Furthermore, a polymer material in which the aforementioned light-emitting dopant is introduced into the polymer chain or the aforementioned light-emitting dopant is used as the main chain of the polymer can be used.

As the above-mentioned host compound, for example, carbazole derivatives, triarylamine derivatives, aromatic borane derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligo-arylene compounds, etc. have a basic skeleton Furthermore, the electron transport materials and hole transport materials described later are also listed as corresponding examples.

Suitable for blue or white light-emitting elements, display devices and lighting devices, it is preferable that the maximum fluorescence wavelength of the host compound is 415nm or less, and when phosphorescent dopants are used, it is even more preferable for the host compound The 0-0 band (Band) of phosphorescence is 450 nm or less. As the light-emitting host, it is preferable to use a compound that has hole-transporting ability and electron-transporting ability, prevents the long-wavelength of light emission, and has a high Tg (glass transition temperature).

As a specific example of the light-emitting host, for example, the compounds described in the following documents are suitable.

JP 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860 , Same as 2002-334787, same 2002-15871, same 2002-334788, same 2002-43056, same 2002-334789, same 2002-75645, same 2002-338579, same Same as 2002-105445, same 2002-343568, same 2002-141173, same 2002-352957, same 2002-203683, same 2002-363227, same 2002-231453, same 2003-3165, same 2002-234888, same 2003-27048, same 2002-255934, same 2002-260861, same 2002-280183, same 2002-299060, same 2002 -Bulletin No.302516, the same bulletin 2002-305083, the same bulletin 2002-305084, the same bulletin 2002-308837, etc.

The light-emitting dopant may be dispersed throughout the layer containing the host compound, or may be partially dispersed. Compounds with other functions can be further added to the light-emitting layer.

By using the above-mentioned materials, for example, the vapor deposition method, spin coating method, casting method, LB method (Langmuir-Blodgett (Langmuir-Blodgett) method), inkjet printing method, printing method, etc. are known The method for thinning, although the light-emitting layer can be formed, but the light-emitting layer formed is particularly preferably a molecular deposition film.

Here, the so-called molecular deposition film refers to a thin film formed from the deposition of the above-mentioned compound in the gas phase state, or a film formed from the solidification of the compound in the molten state or the liquid state. Generally, the molecular accumulation film and the thin film (molecular accumulation film) formed by the LB method can be distinguished by the difference of the aggregation structure, the higher-order structure, or the difference in the function due to it.

In the present invention, it is preferable to use the phosphorescent dopant and host compound as the above-mentioned luminescent material as the organic material for electronic devices of the present invention. That is, a solution containing the phosphorescent dopant and host compound, an organic solvent, and cellulose nanofibers (composition for manufacturing electronic components) is applied by spin coating, casting, inkjet, and spray methods. The light-emitting layer can be formed by coating by a printing method, a slot-type coating method, etc., since it can form a light-emitting layer including a molecular deposition film. Among them, the inkjet printing method is preferred from the viewpoints that it is easy to obtain a homogeneous film and that it is difficult to generate pinholes.

Furthermore, the coating solution containing the phosphorescent dopant and host compound, an organic solvent, and cellulose nanofibers is preferably 50°C or less, and the concentration of dissolved carbon dioxide relative to the organic solvent under atmospheric pressure is set to 1ppm to the saturation concentration of the aforementioned organic solvent. As a means for setting the concentration of dissolved carbon dioxide in the above range, there can be mentioned a solution containing phosphorescent dopant and host compound, and an organic solvent, a method of bubbling carbon dioxide, or a supercritical fluid containing an organic solvent and carbon dioxide. Supercritical chromatography.

(Hole injection layer and hole transmission layer) The hole injection material used in the hole injection layer has any of hole injection and electron barrier properties. In addition, the hole-transporting material used in the hole-transporting layer has an electron barrier property and has an agent that transmits holes to the light-emitting layer. Accordingly, in the present invention, the hole transport layer is included in the hole injection layer.

These hole injection materials and hole transport materials can be either organic or inorganic. Specifically, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, Phenylenediamine derivatives , Arylamine derivatives, amine substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, quinone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline Conductive polymer oligomers such as copolymers, porphyrin compounds, and thiophene oligomers. Among these, arylamine derivatives and porphyrin compounds are preferred.

Among the arylamine derivatives, aromatic tertiary amine compounds and styryl amine compounds are preferred, and aromatic tertiary amine compounds are more preferred.

Representative examples of the above-mentioned aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl; N,N' -Diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD); 2,2-bis(4-di -p-tolylaminophenyl)propane; 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane; N,N,N',N'-tetra-p-toluene -4,4'-diaminobiphenyl; 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane; bis(4-dimethylamino) -2-methylphenyl)phenylmethane; bis(4-di-p-tolylaminophenyl)phenylmethane; N,N'-diphenyl-N,N'-bis(4-methyl (Oxyphenyl)-4,4'-diaminobiphenyl; N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (Diphenylamino)biphenyl; N,N,N-tris(p-tolyl)amine; 4-(di-p-tolylamino)-4'-[4-(di-p-toluene Amino) styryl] stilbene; 4-N,N-diphenylamino-(2-diphenylvinyl)benzene; 3-methoxy-4'-N,N-diphenyl Amino stilbene; N-phenylcarbazole, and further include those having two condensed aromatic rings described in the specification of U.S. Patent No. 5061569, such as 4,4'-bis[N-(1 -Naphthyl)-N-phenylamino]biphenyl (hereinafter referred to as α-NPD), the triphenylamine unit described in JP 4-308688 A and three starbursts are connected Of 4,4',4”-[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA), etc. Also, p-type-Si, p-type-SiC, etc. The inorganic compound can also be used as a hole injection material.

Furthermore, in the present invention, the hole transport material of the hole transport layer preferably has a maximum fluorescence wavelength below 415 nm. That is, the hole-transporting material is preferably a compound that has hole-transporting energy, prevents the long wavelength of light emission, and is still a high Tg compound.

The hole injection layer and the hole transport layer can be made of the above hole injection material and hole transport material, for example, vacuum evaporation method, spin coating method, casting method, LB method, inkjet method, printing method, printing It is formed by thin-filming in well-known methods such as law.

In the present invention, it is preferable to use the above-mentioned hole injection material and hole transport material as the organic material for electronic devices of the present invention. Furthermore, it is preferable to apply a solution (composition for manufacturing electronic components) containing the above-mentioned hole injection material and hole transport material, an organic solvent, and cellulose nanofibers by spin coating, casting, or inkjet It can be formed by coating method, spray method, printing method, slot-type coating method, etc. Among them, the inkjet printing method is preferred from the viewpoints that it is easy to obtain a homogeneous film and that it is difficult to generate pinholes.

The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually about 5 nm to 5 μm. Furthermore, the hole injection layer and the hole transport layer may each have a one-layer structure including one or more of the above-mentioned materials, or a laminated structure including multiple layers of the same composition or different compositions. . In addition, when both the hole injection layer and the hole transport layer are provided, among the above-mentioned materials, although different materials are usually used, the same material may be used.

(Electron injection layer and electron transport layer) As long as the electron injection layer has a function of transferring electrons injected from the cathode to the light emitting layer, any material can be selected from conventionally known compounds.

Examples of materials used in this electron injection layer (hereinafter also referred to as electron injection materials) include nitro-substituted quinone derivatives, diphenylquinone derivatives, Thiopyrandioxide derivatives, naphthylene perylene, etc. Heterocyclic tetracarboxylic anhydride, carbodiimide, pyrimidine derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, etc.

In addition, a series of electron-transporting compounds described in Japanese Patent Application Laid-Open No. 59-194393 were disclosed in the publication as a material for forming a light-emitting layer, but as a result of research by the present inventors, it was found that it can be used as an electron injection material. Furthermore, in the above-mentioned oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring, which are known as electron attracting groups, are also Can be used as an electron injection material.

In addition, metal complexes of 8-hydroxyquinoline derivatives, such as ginseng (8-hydroxyquinoline) aluminum (abbreviated as Alq ₃ ), ginseng (5,7-dichloro-8-hydroxyquinoline) aluminum, ginseng (5,7-Dibromo-8-hydroxyquinoline) aluminum, ginseng (2-methyl-8-hydroxyquinoline) aluminum, ginseng (5-methyl-8-hydroxyquinoline) aluminum, bis(8- Hydroxyquinoline) zinc (Znq), etc., and the central metal of these metal complexes are replaced with metal complexes of In, Mg, Cu, Ca, Sn, Ga or Pb, which can also be used as electron injection materials.

In addition, metal-free or metal phthalocyanine or those whose ends are substituted with alkyl groups or sulfonic acid groups can also be preferably used as electron injection materials. Also, like the hole injection layer, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as electron injection materials.

The preferred compound used in the electron transport layer preferably has a maximum fluorescence wavelength below 415 nm. That is, the compound used in the electron transport layer is preferably a compound that has electron transport energy, prevents the long wavelength of light emission, and is high Tg.

The electron injection layer can be formed by thinning the above-mentioned electron injection material by a known method such as vacuum evaporation, spin coating, casting, LB method, inkjet method, printing method, and printing method. .

In the present invention, it is preferable to use the above-mentioned electron injection material as the organic material for electronic devices of the present invention. Furthermore, it is preferable to apply a solution (composition for manufacturing electronic components) containing the above-mentioned electron injection material, an organic solvent, and cellulose nanofibers by spin coating, casting, inkjet, spray, or printing. It can be formed by coating method, slot type coating method, etc. Among them, the inkjet method is preferred from the viewpoints that it is easy to obtain a homogeneous film and that it is difficult to generate pinholes.

In addition, the thickness of the electron injection layer is not particularly limited, but it is usually selected within the range of 5 nm to 5 μm. The electron injection layer may have a one-layer structure including one or two or more of these electron injection materials, or may have a laminated structure including a plurality of layers of the same composition or different compositions.

In this specification, among the aforementioned electron injection layers, when the ionization energy is larger than that of the light-emitting layer, it is particularly called an electron transport layer. Accordingly, in this specification, the electron transport layer is included in the electron injection layer.

The above-mentioned electron transport layer is also called a hole blocking layer (hole blocking layer), for example, International Publication No. 2000/70655, Japanese Patent Application Publication No. 2001-313178, Japanese Patent Application Publication No. 11-204258, and the same 11- Bulletin No. 204359, and "Organic EL Devices and the Forefront of Industrialization (issued by NTS Corporation on November 30, 1998)" on page 237, etc. In particular, a so-called "phosphorescent light-emitting device" using ortho-metal complex dopants in the light-emitting layer is preferably a structure having an electron transport layer (hole blocking layer) as described in (v) and (vi).

(buffer layer) A buffer layer (electrode interface layer) may exist between the anode and the light-emitting layer or hole injection layer, and between the cathode and the light-emitting layer or electron injection layer.

The so-called buffer layer is a layer provided between the electrode and the organic layer in order to reduce the driving voltage or increase the luminous efficiency. The details are described in "Organic EL Devices and the Forefront of Industrialization (issued by NTS Corporation on November 30, 1998)" No. 2 In Chapter 2 "Electrode Materials" (pages 123 to 166), there are anode buffer layers and cathode buffer layers.

The anode buffer layer is described in Japanese Patent Laid-open No. 9-45479, No. 9-260062, No. 8-288069, etc., and its details are also described. As specific examples, the use of a phthalocyanine buffer layer represented by copper phthalocyanine and vanadium oxide The representative oxide buffer layer, amorphous carbon buffer layer, polyaniline (Emeraldine) or polythiophene and other conductive polymer buffer layer, etc.

The cathode buffer layer is described in Japanese Patent Laid-open No. 6-325871, No. 9-17574, No. 10-74586, etc. The details are also described. Specifically, metal buffer layers represented by strontium or aluminum, and lithium fluoride Representative alkali metal compound buffer layer, alkaline earth metal compound buffer layer represented by magnesium fluoride, oxide buffer layer represented by alumina, etc.

The above-mentioned buffer layer is desirably a very thin film. Although it depends on the material, its thickness is preferably in the range of 0.1-100 nm. Furthermore, in addition to the basic constituent layers described above, if necessary, layers having other functions can be appropriately laminated.

(cathode) As mentioned above, as the cathode of the organic EL device, generally speaking, a metal with a small work function (less than 4eV) (hereinafter, also referred to as electron injecting metal), alloy, conductive compound of metal, or a mixture of these is used as Those who use electrode material.

Specific examples of such electrode materials include sodium, magnesium, lithium, aluminum, indium, rare earth metals, sodium-potassium alloys, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures , Aluminum/alumina (Al ₂ O ₃ ) mixture, lithium/aluminum mixture, etc.

In the present invention, although those listed above can be used as the electrode material of the cathode, it is preferable that the cathode contains a Group 13 metal element. That is, in the present invention, as described later, by oxidizing the surface of the cathode with oxygen in a plasma state, an oxide film is formed on the surface of the cathode, which can prevent the oxidation of the above cathode and improve the durability of the cathode.

Accordingly, the electrode material of the cathode is preferably a metal that has better electron injection properties required by the cathode and can form a dense oxide film.

As the electrode material of the cathode containing the aforementioned Group 13 metal element, specifically, for example, aluminum, indium, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al ₂ O ₃ ) mixture, lithium /Aluminum mixture, etc. In addition, although the mixing ratio of each component of the said mixture may be a conventionally well-known ratio as a cathode of an organic electroluminescent element, it is not specifically limited to this. The above-mentioned cathode can be produced by forming a thin film of the above-mentioned electrode material on the above-mentioned organic compound layer (organic EL layer) by a method such as vapor deposition or sputtering.

In addition, the sheet resistance of the cathode is preferably several hundred Ω/sq. or less, and the film thickness is usually in the range of 10 nm to 1 μm, and preferably selected in the range of 50 to 200 nm. Furthermore, in order to transmit the luminous light, it is better to make either the anode or the cathode of the organic EL element transparent or semi-transparent, so as to improve the luminous efficiency.

[Manufacturing method of organic EL device] As an example of a method of manufacturing an organic EL device, a method of manufacturing an organic EL device including an anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode will be described.

First, on a suitable substrate, a desired electrode material, such as a thin film containing an anode material, is made to have a thickness of 1 μm or less, preferably in the range of 10 to 200 nm, by vapor deposition or The anode is formed by sputtering and other methods. Next, an organic compound thin film (organic thin film) of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole stop layer of the device material is formed on this.

As the method of thinning of these organic thin films, as mentioned above, although spin coating method, casting method, inkjet printing method, spray method, vapor deposition method, printing method, slit coating method, etc. are available, it is easy to obtain In view of the homogeneous film and the fact that it is difficult to generate pinholes and the like, and in the present invention, the composition for manufacturing electronic components of the present invention can be used, and the inkjet printing method is preferred.

However, different film forming methods for each layer can be applied. When vapor deposition film-forming method, deposition conditions for use, although depending on the type of compound and the like, but generally, in the range of a desired boat heating temperature of 50 ~ 450 ℃, vacuum degree of 10 ^-6 to 10 ^{- It} is appropriately selected within the range of 2 Pa, the vapor deposition rate in the range of 0.01-50 nm/sec, the substrate temperature in the range of -50 to 300°C, and the thickness in the range of 0.1 nm to 5 μm.

After these layers are formed, the thin film containing the cathode material is made to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, by methods such as vapor deposition or sputtering. The cathode is formed, and the desired organic EL device is obtained. Although the production of this organic EL device is preferably performed by a single vacuum from the hole injection layer to the cathode, it is fine to extract and perform different film forming methods on the way. At this time, it is necessary to worry about working in a dry inert gas environment.

[Sealing of organic EL elements] Although the method of sealing the organic EL element is not particularly limited, for example, a method of arranging the sealing member so as to cover the light-emitting area of the organic EL element after sealing the outer periphery of the organic EL element with a sealing adhesive can be cited.

Examples of adhesives for sealing include acrylic oligomers, methacrylic oligomers, light-curing and thermosetting adhesives with reactive vinyl groups, and moisture-curing adhesives such as 2-cyanoacrylate. And so on the adhesive. In addition, thermal and chemical curing types (two-component mixing) such as epoxy-based systems can be cited. In addition, hot-melt polyamides, polyesters, and polyolefins can be cited. In addition, a cationic curing type ultraviolet curing type epoxy resin adhesive can be cited.

As the sealing member, a polymer film and a metal film can be preferably used from the viewpoint of thinning an organic EL element. In the case of a polymer film, it is preferable to impart the aforementioned gas barrier properties.

Examples of the sealing structure include a structure in which the organic EL element and the sealing member can be hollow, or a filling and sealing structure in which a sealing material such as an adhesive is filled between the organic EL element and the sealing member.

In the gap between the sealing member and the light-emitting area of the organic EL element, in addition to the sealing adhesive, inert gas such as nitrogen and argon or inert gas such as fluorinated hydrocarbon and silicone oil can be injected into the gas and liquid phases. Inert liquid. In addition, the gap between the sealing member and the display area of the organic EL element may be a vacuum, or an inert gas may be enclosed in the gap, or a desiccant may be arranged.

[Organic EL display device] For the organic EL display device (hereinafter, simply referred to as "display device") using the above-mentioned organic EL element, if only a shadow mask is provided when the light-emitting layer is formed, and the other layers are common, the pattern of the shadow mask, etc. If not, a film can be formed on one side by vapor deposition, casting, spin coating, inkjet, printing, etc.

When only the light-emitting layer is patterned, it is not limited to the method, but the vapor deposition method, the inkjet printing method, and the printing method are preferable. In the case of using the vapor deposition method, it is preferable to use the patterning of the shadow mask.

In addition, it is also possible to reverse the production order and produce in the order of the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode.

When a DC voltage is applied to the display device obtained in this way, the anode is set as + and the cathode is set as the polarity, and when the applied voltage is in the range of about 2-40V, light emission can be observed. Moreover, even if the voltage is applied with the opposite polarity, the current does not flow, and no light emission occurs at all. Furthermore, when an AC voltage is applied, light is emitted only when the anode is + and the cathode is -. Still, the waveform of the applied AC can be arbitrary.

The display device can be used as a display device, a display, and various luminous light sources. In display devices and displays, the use of blue, red, and green light-emitting organic EL elements makes full-color display possible.

Examples of display devices and displays include televisions, personal computers, mobile devices, AV equipment, text broadcast displays, and information displays in automobiles. In particular, it can be used as a display device for reproducing still images or movie images, and as a driving method when used as a display device for movie reproduction, even if it is a simple matrix (passive matrix) method or an active matrix method.

As the luminous light source, it can include household lighting, car interior lighting, backlight for clocks or liquid crystals, billboard advertisements, signals, light sources for optical storage media, light sources for electrophotographic copiers, light sources for optical communication processors, and light sensors. The light source, etc. are not limited to this.

In addition, it can be used as an organic EL element having a resonator structure in the organic EL element of the present invention.

The purpose of use of organic EL elements having such a resonator structure includes light sources for optical storage media, light sources for electrophotographic copiers, light sources for optical communication processors, light sources for optical sensors, etc., but they are not limited to this. Wait. In addition, it can be used for the above-mentioned purposes by causing the laser to vibrate.

The organic EL element of the present invention can be used as a lamp such as a light source for illumination or exposure, and can also be used as a projection device for projecting images, or a display device (display) for directly viewing still images or video images. . When used as a display device for video reproduction, the driving method can be a simple matrix (passive matrix) method or an active matrix method. Or, a full-color display device can be produced by using two or more organic EL devices of the present invention with different luminous colors. [Example]

Hereinafter, although the present invention will be specifically described with reference to examples, the present invention is not limited to these. However, in the examples, the expression "parts" or "%" is used, unless otherwise specified, it means "parts by mass" or "% by mass".

[Example 1] (Production of LED components (1-1)) In the center of the accommodating part of the circular package (opening diameter 3mm, bottom diameter 2mm, wall angle 60°), a blue LED element (rectangular parallelepiped shape; 200μm×300μm×100μm) is mounted on the flip chip. The circular package is shown in Fig. 2 and uses a silver electrode 15 with a thickness of 100 nm. To coat the LED element and the electrode, a solution in which the exemplary compound 13 (1.0 g) was dissolved in 100 ml of ethanol was spray-coated, and the solution was heated at 150° C. and cured for 10 minutes.

Next, a polysiloxane resin (OE6630, manufactured by Dow Toray Co., Ltd.) in which 10% by mass of phosphor particles prepared by the following method was dispersed by a dispenser was applied to the circular package and fired at 150°C. When it is small, a wavelength conversion layer is formed. The thickness of the wavelength conversion layer is set to 2.5 mm.

(Preparation of phosphor particles) Y ₂ O ₃ 7.41 g, Gd ₂ O ₃ 4.01 g, CeO ₂ 0.63 g, and Al ₂ O ₃ 7.77 g were thoroughly mixed. An appropriate amount of ammonium fluoride is mixed with this mixture as a flux, and it is filled in a crucible made of alumina. The filler is fired in a reducing environment in which hydrogen-containing nitrogen gas flows in a temperature range of 1350 to 1450°C for 2 to 5 hours to obtain a fired product ((Y _0.72 Gd _0.24 )3Al ₅ O ₁₂ : Ce _0.04 ).

The fired product obtained by crushing, washing, separating, and drying obtains yellow phosphor particles with an average particle size of about 10 μm. When measuring the emission wavelength of the excitation light at a wavelength of 465 nm, it has a peak wavelength at approximately 570 nm.

(Production of LED components (1-2)～(1-19)) Except that the compound and the solvent were changed as shown in Table III, each LED element (light-emitting device) was produced in the same manner as the LED element (1-1).

＜Evaluation＞ The adhesion and vulcanization resistance of each LED element were evaluated by the following methods. The evaluation results are shown in Table III.

(Assessment of Adhesion) After drying each LED element at 150°C for 30 minutes, it was allowed to stand in a constant temperature and humidity chamber at 85°C and a relative humidity of 85% for 24 hours. Then, perform a reflow treatment at a peak of 265°C within 30 minutes to confirm whether the sealing material layer is peeled off. In addition, the total beam was measured with a spectroradiometer (CS-2000, manufactured by Konica Minolta Sensing Co., Ltd.). The evaluation is carried out using the following benchmarks.

◎: The peeling of the non-sealing material layer was observed with a microscope, and the light was turned on when power was applied to the light-emitting device. The microscope confirmed that the total beam value due to the difficult minute peeling was reduced by less than 1% ○: The peeling of the non-sealing material layer was observed with a microscope. Although the light was turned on when the light-emitting device was energized, the microscope confirmed that the total beam value due to the difficult minute peeling was reduced to 1% or more and 3% or less △: Although there is peeling of the sealing material layer observed with a microscope, the light-emitting device is turned on when electricity is applied to it ×: There is peeling of the sealing material layer observed with a microscope, and the light-emitting device is not lighted when power is applied to it

(Evaluation of resistance to vulcanization) According to the JIS standard gas exposure test (JIS C 60068-2-43), the LED device is exposed to an environment of 15 ppm hydrogen sulfide gas, 25° C., and 50% RH for 1000 hours. Perform full beam measurement before and after exposure, and evaluate the vulcanization resistance based on the following criteria. The total beam was measured with a spectroradiometer (CS-2000, manufactured by Konica Minolta Sensing Co., Ltd.). The value of the following comparative compound (1) (also referred to as "comparison 1") element (1-18) (comparative example) after exposure/pre-exposure brightness was taken as 100 and expressed as a relative value. Still, the larger the value, the better the vulcanization resistance. The above evaluation results are shown in Table III below.

[Table III]

From the results shown in Table III, it is clear that the LED device of the present invention has better adhesion and brightness than the comparative example. Furthermore, it was observed that the color of the surface of the silver electrode of the comparative example after the gas exposure test was blackened compared to the color of the surface of the silver electrode of the LED element of the present invention.

[Example 2] (Production of LED components (2-1)) According to the following method, the LED element (2-1) of the LED light-emitting element is produced. The constituent materials used in the manufacture of LED1 are shown below.

･Packaging substrate: A commercial product with an opening diameter of 3mm, a bottom diameter of 2mm, and a wall angle of 60° ･Phosphor 1: YAG 405C205 manufactured by Nemoto Special Chemical Co., Ltd.; particle size distribution D50: 20.5μm ･Resin for resin layer formation 1: Polysiloxane resin: OE6630 manufactured by Dow Corning Toray ･Lead frame: Silver-plated and polished; Model 5050 made by ALFACT Co., Ltd. ･Wire: made of silver alloy, made of Tanaka Precious Metals, SEC type ･LED element: Due to the light source, an InGaN-based LED element that emits blue light with a wavelength of about 460nm is used, and a YAG phosphor is used as the phosphor, and white light is obtained by mixing blue light and yellow light.

＜Realization of LED components＞ After the LED element has formed the contact hole, prepare a rectangular parallelepiped LED element with a length of 200um × a width of 200um × a height of 200um. The packaging substrate is cleaned with plasma to remove organic pollutants, and then the LED components are mounted on the packaging substrate, and the lead frame and the LED terminals are connected and mounted by bonding wires.

＜Formation of sealing material layer＞ For the formation of the sealing material layer, the resin layer forming composition of the following configuration was used.

･Resin 1 for resin layer formation (polysiloxane resin: OE6630 manufactured by Dow Corning Toray) 80 parts by mass ･Phosphor 1: YAG 405C205 manufactured by Nemoto Special Chemical Co., Ltd.; particle size distribution D50: 20.5μm 20 parts by mass ･Anti-vulcanizing agent: Exemplary compound 13 5 parts by mass The resin layer forming resin 1 and the phosphor 1 were stirred at 1500 rpm for 15 minutes using the Yuxing type stirring and degassing device "MAZERUSTAR KK-400" manufactured by Kurashiki Boshoku Co., Ltd. to prepare the resin layer forming composition, and a dispenser was used (MPP-1 manufactured by Musashino Engineering Co., Ltd.), pour into the above-mentioned packaging substrate to which the LED components are connected, heat-treat at 110°C for 30 minutes, and then heat-treat at 150°C for 15 minutes to dry the resin to produce LED components ( 2-1) (Refer to Figure 3).

(Production of LED components (2-2)～(2-19)) Except for changing to the compound and solvent shown in Table IV, the LED element (light-emitting device) was produced in the same manner as in the case of the LED element (2-1).

＜Evaluation＞ The adhesion and vulcanization resistance of each LED element were evaluated by the following methods. The evaluation results are shown in Table IV.

(Assessment of Adhesion) It is evaluated in the same manner as in Example 1. The evaluation is carried out using the following benchmarks. ◎: The peeling of the non-sealing material layer was observed with a microscope, and the light was turned on when power was applied to the light-emitting device. The microscope confirmed that the total beam value due to the difficult minute peeling was reduced by less than 1% ○: The peeling of the non-sealing material layer was observed with a microscope. Although the light was turned on when the light-emitting device was energized, the microscope confirmed that the total beam value due to the difficult minute peeling was reduced to 1% or more and 3% or less △: Although there is peeling of the sealing material layer observed with a microscope, the light-emitting device is turned on when electricity is applied to it ×: There is peeling of the sealing material layer observed with a microscope, and the light-emitting device is not lighted when power is applied to it

(Evaluation of resistance to vulcanization) According to the JIS standard gas exposure test (JIS C 60068-2-43), the LED element (light emitting device) is exposed to an environment of 15 ppm hydrogen sulfide gas, 25° C., and 50% RH for 1000 hours. Perform full beam measurement before and after exposure, and evaluate the vulcanization resistance based on the following criteria. The total beam was measured with a spectroradiometer (CS-2000, manufactured by Konica Minolta Sensing Co., Ltd.). The brightness is the value of the brightness after exposure/the brightness before exposure of the elements 1-18 (comparative example) as 100, which is expressed as a relative value. The larger the displayed value, the better the vulcanization resistance.

(Evaluation of the dispersibility of polysiloxane) Visually judge based on the following criteria. ○: Dissolving. Or become uniformly dispersed ×: A state where there is no mixing at all

[Table IV]

It is clear from the results shown in Table IV that the LED element (light-emitting device) of the present invention is excellent in each evaluation performance. Furthermore, it was observed that the color of the surface of the lead frame and the bonding wire after the gas exposure test was darker than that of the present inventor and the comparative example.

[Example 3] <Preparation of organic photoelectric conversion element (3-1)> The glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen and cleaned with UV ozone, and fixed in a vacuum evaporation device The substrate rack. After decompressing the vacuum degree in the vacuum evaporation device to 1×10 ^-4 Pa, as the anode, 100nm silver was evaporated, and on the anode, copper phthalocyanine (CuPC) and anthracene [9,1,2 -c,d,e: 10,5,6-c',d',e'][bis[benzimidazole[2,1-a]isoquinoline]]-10,21-dione (PTCBI) Co-evaporation was carried out at the ratio of CuCP:PTCBI=1:1, and the bulk heterojunction layer was set with a thickness of 400nm.

Next, as a cathode, a cathode (15 nm) of Mg:Ag=1:9 was vapor-deposited. Next, on the cathode, the sealing material containing the exemplified compound 15 and the sealing material containing the compound of Comparative 1 as a comparative example were bonded through the adhesive to produce an organic photoelectric conversion element (3-1).

(Production of sealing material containing exemplified compound 15) In a glove box, the exemplary compound 15 (1.0 g) was dissolved in 100 ml of ethanol and spray-coated on a polyethylene naphthalate film (PEN: manufactured by Teijin Film Solutions Co., Ltd.) with a thickness of 100 μm, and heated at 150°C ･Cure for 10 minutes.

＜Production of organic photoelectric conversion element (3-2) and (3-3)＞ Except that the kind of anti-sulfurizing agent was changed as follows, the same procedure as the organic photoelectric conversion element (3-1) was carried out to produce organic photoelectric conversion elements (3-2) and (3-3).

Organic photoelectric conversion element (3-2); Comparative compound 1 (manufactured by Nippon Kayaku Co., Ltd.) Organic photoelectric conversion element (3-3); KESMON NS-20C (manufactured by Toagosei Co., Ltd.)

<Evaluation> The obtained organic photoelectric conversion element was exposed to a hydrogen sulfide gas of 15ppm, a temperature of 25°C, and a relative humidity of 50%RH in an environment of 15ppm of hydrogen sulfide gas in accordance with the gas exposure test of JIS standard (JIS C 60068-2-43). Hour. After the exposure, when irradiated with light of ^{an intensity of 100 mW/cm 2} of the solar simulator, the organic photoelectric conversion element of exemplified compound 15 was compared with the organic photoelectric conversion element using comparative compound 1, and the luminous efficiency was higher.

The evaluation criteria are as follows. ○: Relative to the brightness of 90% or more before the vulcanization test △: Relative to the brightness of 75% or more before the vulcanization test ×: The brightness is less than 75% compared to before the vulcanization test

[Table V] Organic photoelectric conversion element No. Compound No. Vulcanization resistance Remark 3-1 15 ○ this invention 3-2 Comparison 1 △ Comparative example 3-3 KESMON NS-20C △ Comparative example

From the results shown in Table V, it is understood that the organic photoelectric conversion element of the present invention has excellent vulcanization resistance in the comparative example. Furthermore, it was observed that the color of the surface of the silver electrode of the comparative example after the gas exposure test was blackened compared with the color of the surface of the silver electrode of the organic photoelectric conversion element of the present invention.

[Example 4] (Production of organic EL element (4-1)) As the anode, a glass substrate made of 100nm ITO (Indium Tin Oxide) film was cleaned with isopropyl alcohol ultrasonic wave, dried with dry nitrogen and cleaned with UV ozone, and fixed on the substrate rack of the vacuum evaporation device.

Next, a 10nm HAT-CN (1,4,5,8,9,12-Hexaazatriphenylene hexacarbonitrile) was vapor-deposited, and a hole injection transport layer was provided.

Next, α-NPD (4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl) was vapor-deposited on the aforementioned hole injection layer, and a hole transmission with a thickness of 40nm was set Floor.

Combine mCP (1,3-bis(N-carbazolyl)benzene) as the host material and Bis[2-(4,6-difluorophenyl) pyridinato-C2,N](picolinato)iridium( III) (FIrpic), co-evaporation is performed so as to be 94% and 6% by volume, respectively, and a light-emitting layer with a thickness of 30 nm is provided.

Then, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) was vapor-deposited to provide an electron transport layer with a thickness of 330 nm. Furthermore, 100 nm of silver was further vapor-deposited, and a cathode was installed.

(Production of sealing material containing exemplified compound 15) In a glove box, the exemplary compound 15 (1.0 g) was dissolved in 100 ml of ethanol and spray-coated on a polyethylene naphthalate film (PEN: manufactured by Teijin Film Solutions Co., Ltd.) with a thickness of 100 μm, and heated at 150°C ･Cure for 10 minutes.

On one side of the produced sealing material film, a thermosetting liquid adhesive (epoxy resin) was formed to have a thickness of 25 μm as a sealing resin layer. Furthermore, the gas barrier film provided with this sealing resin layer is laminated on the aforementioned organic EL element. At this time, the sealing resin layer forming surface of the sealing material film is continuously overlapped on the sealing surface side of the organic EL element so that the ends of the extraction portion of the anode and the cathode protrude outward.

Next, the sample to which the sealing material film was bonded was placed in a decompression device, and pressure was applied at 90°C under a reduced pressure of 0.1 MPa, and kept for 5 minutes. Next, the sample was returned to the atmospheric pressure environment, and further heated at 90°C for 30 minutes to harden the adhesive. Still, the heating is carried out in the glove box using a hot plate.

The above-mentioned sealing step is performed under atmospheric pressure, in a nitrogen environment with a moisture content of 1 ppm or less, in accordance with JIS B 9920, with the measured cleanliness as class 100, and the dew point temperature is below -80°C, and the oxygen concentration is below 0.8 ppm. By the above method, an organic EL device 1 sealed with a sealing material containing compound 15 is produced. A cross-sectional view of the organic EL element (4-1) is shown in FIG. 5.

(Production of organic EL elements (4-2) and (4-3)) Except that the type of anti-vulcanizing agent was changed as follows, the same procedure as the organic EL element (4-1) was carried out to produce organic EL elements (4-2) and (4-3).

Organic EL element (4-2); Comparative compound 1 (2-ethylhexyl zinc (manufactured by Nippon Kayaku Co., Ltd.)) Organic EL element (4-3); KESMON NS-20C (manufactured by Toagosei Co., Ltd.)

＜Evaluation＞ The following evaluations were performed for each of the above-mentioned organic EL devices produced. The evaluation results are shown in Table VI.

[Measurement of injection voltage] The obtained organic EL element was tested in accordance with JIS standard gas exposure test (JIS C 60068-2-43), and the organic EL display device was exposed to 15 ppm hydrogen sulfide gas, temperature 25°C, and relative humidity 50% RH. Expose to the environment for 10 hours. After the exposure, the DC voltage and current source/monitor 6234 manufactured by ADC company were used for each organic EL element, and the voltage when a current of 30 A/m ² was passed was measured, and this was obtained as the injection voltage. Determine the relative value of 100 for the injection voltage of the organic EL element (4-3).

[Measurement of power efficiency] The brightness was measured using a spectroradiometer CS-2000 manufactured by Konica Minolta. According to the following formula, calculate the power efficiency. Calculate the relative value of the power efficiency of the organic EL element (4-3) as 100. Power efficiency = (brightness) × pi / (current density × voltage) (lm/W)

[Measurement of uneven brightness] Using the spectroradiometer CS-2000 manufactured by Konica Minolta, the brightness at 50 points at any position on the light-emitting surface was measured, and the average brightness relative to the measured brightness was based on the following formula: The average of the absolute value of the difference in brightness at each point is obtained as an index Sa, and this is used as a measure of uneven brightness. The relative value of the brightness unevenness of the organic EL element (4-3) as 100 was determined.

[Table VI] Organic EL element No. Compound No. Evaluation result (relative value) Remark Injection voltage Power efficiency Uneven brightness 4-1 15 59 130 69 this invention 4-2 Comparison 1 91 112 91 Comparative example 4-3 KESMON NS-20C 100 100 100 Comparative example

From the above evaluation results, it is believed that the sealing material of the present invention has higher sealing performance than the sealing material of the comparative example, and the performance degradation of the organic EL element is reduced. Furthermore, it was observed that the color of the surface of the silver electrode of the comparative example after the gas exposure test was blackened compared with the color of the surface of the silver electrode of the organic EL device of the present invention. [Industrial availability]

It is possible to provide an electronic component that prevents metal sulfidation caused by gases containing sulfur compounds such as hydrogen sulfide or sulfur allotropes. In addition, for this purpose, an anti-vulcanization agent and a sealing material can be provided.

1: Layer containing metal components 2: Anti-vulcanizing agent layer 3: Sealing material layer (can contain anti-vulcanizing agent) 4: Sealing material layer containing anti-vulcanizing agent 100: Light-emitting device 11: substrate 12: Light-emitting components (LED components, etc.) 13: Sealing layer 14: Wavelength conversion layer 15: Electrode 16: Metal wire 200: LED light emitting device 20: Insulating substrate 21: Lead frame 22: Packaging (also known as Bank) 23: reflective layer 24: Terminal for connection 25: LED components 26: Welding 27: Welding wire 28: Sealing material layer 29a: Phosphor particles 29b: Anti-vulcanizing agent 300: Bulk heterojunction organic photoelectric conversion element 31: substrate 32: Transparent electrode (anode) 33: hole transport layer 34: Photoelectric conversion part (bulk heterojunction layer) 35: electron transport layer 36: Counter electrode (cathode) 400: Organic EL display device 40: Organic EL element 41: substrate 42: Glass cover or gas barrier film 43: Adhesive 45: cathode 46: Organic functional layer group 47: Glass substrate with transparent electrode 48: Sealing material layer (may contain metal vulcanizing agent) 49: Metal vulcanizing agent layer

[Fig. 1A] A conceptual diagram showing an example of protecting a metal-containing member of an electronic component with the sealing material of the present invention [Fig. 1B] A conceptual diagram showing an example of protecting a metal-containing member of an electronic component with the sealing material of the present invention [Fig. 2] A cross-sectional conceptual diagram showing an example of a form of an LED light-emitting device [Fig. 3] A cross-sectional conceptual view showing another example of the LED light-emitting device [Fig. 4] A conceptual cross-sectional view of a solar cell including a bulk-heterojunction type organic photoelectric conversion element [Fig. 5] A conceptual cross-sectional view showing an example of an organic EL element

1: Layer containing metal components

4: Sealing material layer containing anti-vulcanizing agent

Claims (9)

An electronic component characterized by having at least a layer containing a metal member and a layer containing a compound (1) having a structure represented by the following general formula (1),

(In the formula, R ₁ and R ₂ each independently represent an acid group, -ORa, -SRb, or -NRcRd; Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent; R ₃ represents a nitrogen-containing ligand; Me Represents copper (Cu) or zinc (Zn)). The electronic component of claim 1, wherein the aforementioned R ₁ and R ₂ in the aforementioned general formula (1) represent an acid group. The electronic component of claim 1 or claim 2, wherein the aforementioned acid group is a carboxylic acid group or an inorganic acid group. An electronic component according to any one of claim 1 to claim 3, wherein the aforementioned metal-containing member layer contains silver (Ag) or copper (Cu). The electronic component of any one of claims 1 to 4, wherein the layer containing the aforementioned compound (1) contains a resin or a resin precursor, and The content of the aforementioned compound (1) is in the range of 1 to 50% by mass. An electronic component according to any one of claims 1 to 5, wherein the layer containing the aforementioned compound (1) contains an organic solvent having a boiling point of 150°C or higher. An electronic component according to any one of claim 1 to claim 6, wherein the aforementioned electronic component is a light-emitting diode, a photoelectric conversion element, or an organic electroluminescence element. An anti-vulcanizing agent characterized by containing at least a compound (1) having a structure represented by the following general formula (1),

(In the formula, R ₁ and R ₂ each independently represent an acid group, -ORa, -SRb, or -NRcRd; Ra, Rb, Rc, and Rd each independently represent a hydrogen atom or a substituent; R ₃ represents a nitrogen-containing ligand; Me Represents copper (Cu) or zinc (Zn)). A sealing material characterized by containing at least the anti-vulcanization agent as claimed in claim 8.

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