Surface sealant for optical semiconductor, method for manufacturing organic EL device, organic EL device and organic EL display panel using the same
To provide a resin composition for sealing an optical semiconductor, which is a raw material for a sealing resin layer having good curability and excellent storage stability; preferably a raw material for a sealing resin layer further having excellent weather resistance. The surface sealant for an optical semiconductor of Embodiment 1 according to the present invention contains epoxy resin (a) having two or more epoxy groups in a molecule, and metal complex (b1) which contains at least one metal ion selected from the group consisting of Zn, Bi, Ca, Al, Cd, La and Zr, a tertiary amine capable of forming a complex with the metal ion and having no N—H bond and an anionic ligand having a molecular weight of 17 to 200, in which the surface sealant has a viscosity of 10 to 10000 mPa·s, as measured by E-type viscometer at 25° C. and 1.0 rpm.
1. A method for manufacturing an organic electroluminescent (EL) device comprising a substrate, an organic EL element, a cured material layer formed of a cured material of a surface sealant and a passivation film laminated in the order presented, comprising:
a first step of forming the organic EL element on a substrate;
a second step of covering the organic EL element with the surface sealant;
a third step of sealing a surface of the organic EL element with the cured material of the surface sealant; and
a fourth step of forming the passivation film on the cured material sealing the surface of the organic EL element, by plasma CVD or sputtering,
wherein the surface sealant comprises:
an epoxy resin (a) having two or more epoxy groups in a molecule thereof; and
a metal complex (b1) which includes: at least one metal ion selected from the group consisting of Zn, Bi, Ca, Al, Cd, La and Zr; a tertiary amine capable of forming a complex with the metal ion and having no N—H bond; and an anionic ligand,
wherein the anionic ligand has two or more atoms selected from the group consisting of O, S and P which are capable of binding to the metal ion, and the anionic ligand is capable of coordinating with the metal ion to form a 3- to 7-membered ring and has a molecular weight of 17 to 200,
wherein the surface sealant has a viscosity of 10 to 10000 mPa·s, as measured by E-type viscometer at 25° C. and 1.0 rpm, and
wherein a cured material layer of the surface sealant after a plasma treatment has a haze value of 30% or less, the plasma treatment being carried out at an oxygen flow rate of 20 mL/minute and an RF power of 500 W for 20 minutes.
2. The method according to claim 1 , wherein a valence of the anionic ligand in the surface sealant is smaller than a valance of the metal ion, and
a radius of the anionic ligand is 2.0 Å or more.
3. The method according to claim 1 , wherein the tertiary amine is a compound represented by any one of the following general formulas (1) to (6):
where R 1 represents a C 1-17 aliphatic hydrocarbon group, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
R 2 , R 3 and R 4 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group, a hydroxy group, an aryl-containing group or a cyanoethyl group;
where RB1, RB3, RB4 and RB5 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group;
RB2 represents a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and a plurality of groups selected from RB1, RB2, RB3, RB4 and RB5 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur;
where RC1, RC3, RC4 and RC5 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group;
RC2 represents a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RC1, RC2, RC3, RC4 and RC5 may be joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur;
where RE1, RE2, RE3, RE4 and RE5 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RE1, RE2, RE3, RE4 and RE5 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur;
where RF1, RF2, RF3, RF4, RF5, RF6 and RF7 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RF1, RF2, RF3, RF4, RF5, RF6 and RF7 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur; and
where RG1, RG2, RG3 and RG4 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RG1, RG2, RG3 and RG4 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur.
4. The method according to claim 3 , wherein the tertiary amine is a compound represented by any one of the general formulas (1) to (3) and the anionic ligand is a carboxylate compound represented by the following general formula (7A):
where RD1 is free or a hydrogen atom and RD2 is a hydrogen group, a C 1-10 hydrocarbon group or a hydroxy group.
5. The method according to claim 1 , wherein among chemical shift peaks in 1 HNMR spectroscopy (in CDCl 3 , 25° C., 270 MHz) of the surface sealant, chemical shift peaks of the tertiary amine include a peak which is shifted by 0.05 ppm or more relative to a chemical shift peak in 1 HNMR spectroscopy (in CDCl 3 , 25° C., 270 MHz) of the tertiary amine alone.
6. The method according to claim 1 , wherein a molar ratio of the tertiary amine to the metal ion is 0.5:1 to 6.0:1.
7. The method according to claim 4 , wherein the carboxylate compound is at least one compound selected from the group consisting of 2-ethylhexanoic acid, formic acid, acetic acid, butanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, benzoic acid and naphthenic acid.
8. The method according to claim 1 , wherein the tertiary amine is at least one compound selected from the group consisting of 1,8-diazobicyclo[5,4,0]undec-7-ene, 1-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-butylimidazole and 1,5-diazobicyclo[4,3,0]non-5-en.
9. The method according to claim 1 , wherein the surface sealant includes the metal complex (b1) so that an equivalent ratio of a tertiary amine active functional group to an epoxy group is in the range of 0.008:1 to 0.3:1.
10. The method according to claim 1 , wherein the surface sealant further comprising an acid anhydride so that an equivalent ratio of an acid anhydride group to an epoxy group is in the range of 0.8:1 to 1.2:1.
11. The method according to claim 1 , wherein the surface sealant has a water content of 0.1 wt % or less.
12. An organic EL device comprising:
an organic EL element;
a cured material layer formed of a cured material of a surface sealant, the cured material layer sealing a surface of the organic EL element while being in contact with the organic EL element; and
a passivation layer in contact with the cured material layer, in the order presented,
wherein the surface sealant comprising:
an epoxy resin (a) having two or more epoxy groups in a molecule thereof: and
a metal complex (b1) which includes: at least one metal ion selected from the group consisting of Zn, Bi, Ca, Al, Cd, La and Zr; a tertiary amine capable of forming a complex with the metal ion and having no N—H bond; and an anionic ligand,
wherein the anionic ligand has two or more atoms selected from the group consisting of O, S and P which are capable of binding to the metal ion, and the anionic ligand is capable of coordinating with the metal ion to form a 3- to 7-membered ring and has a molecular weight of 17 to 200,
wherein the surface sealant has a viscosity of 10 to 10000 mPa·s, as measured by E-type viscometer at 25° C. and 1.0 rpm, and
wherein a cured material layer of the surface sealant after a plasma treatment has a haze value of 30% or less, the plasma treatment being carried out at an oxygen flow rate of 20 mL/minute and an RF power of 500 W for 20 minutes.
13. The organic EL device according to claim 12 , wherein the cured material layer is formed of an epoxy resin composition, and a spectrum of X-ray photoelectron spectroscopy (XPS) of the epoxy resin composition includes a peak derived from at least one metal atom selected from the group consisting of Zn, Bi, Ca, Al, Cd, La and Zr and a peak derived from a nitrogen atom, with a molar ratio of the metal atom to the nitrogen atom being 1:0.5 to 1:6.0, the cured material layer containing the metal atom in an amount of 0.5 to 15 mass %.
14. An organic EL display panel including the organic EL device according to claim 12 .
15. The organic EL device according to claim 12 , wherein a valence of the anionic ligand in the surface sealant is smaller than a valance of the metal ion, and
a radius of the anionic ligand is 2.0 Å or more.
16. The organic EL device according to claim 12 , wherein the tertiary amine is a compound represented by any one of the following general formulas (1) to (6):
where R 1 represents a C 1-17 aliphatic hydrocarbon group, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
R 2 , R 3 and R 4 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group, a hydroxy group, an aryl-containing group or a cyanoethyl group;
where RB1, RB3, RB4 and RB5 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group;
RB2 represents a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RB1, RB2, RB3, RB4 and RB5 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur;
where RC1, RC3, RC4 and RC5 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group;
RC2 represents a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RC1, RC2, RC3, RC4 and RC5 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur;
where RE1, RE2, RE3, RE4 and RE5 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RE1, RE2, RE3, RE4 and RE5 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur;
where RF1, RF2, RF3, RF4, RF5, RF6 and RF7 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RF1, RF2, RF3, RF4, RF5, RF6 and RF7 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur; and
where RG1, RG2, RG3 and RG4 each independently represent a hydrogen group, a C 1-17 aliphatic hydrocarbon group optionally containing a hetero atom, a hydroxy group, an aryl-containing group or a cyanoethyl group; and
a plurality of groups selected from RG1, RG2, RG3 and RG4 optionally joined to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring having a hetero atom selected from oxygen, nitrogen and sulfur.
17. The organic EL device according to claim 16 , wherein the tertiary amine is a compound represented by any one of the general formulas (1) to (3) and the anionic ligand is a carboxylate compound represented by the following general formula (7A):
where RD1 is free or a hydrogen atom and
RD2 is a hydrogen group, a C 1-10 hydrocarbon group or a hydroxy group.
18. The organic EL device according to claim 12 , wherein among chemical shift peaks in 1 HNMR spectroscopy (in CDCl 3 , 25° C., 270 MHz) of the surface sealant, chemical shift peaks of the tertiary amine include a peak which is shifted by 0.05 ppm or more relative to a chemical shift peak in 1 HNMR spectroscopy (in CDCl 3 , 25° C., 270 MHz) of the tertiary amine alone.
19. The organic EL device according to claim 12 , wherein a molar ratio of the tertiary amine to the metal ion is 0.5:1 to 6.0:1.
20. The organic EL device according to claim 17 , wherein the carboxylate compound is at least one compound selected from the group consisting of 2-ethylhexanoic acid, formic acid, acetic acid, butanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, benzoic acid and naphthenic acid.
21. The organic EL device according to claim 12 , wherein the tertiary amine is at least one compound selected from the group consisting of 1,8-diazobicyclo[5,4,0]undec-7-ene, 1-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-butylimidazole and 1,5-diazobicyclo[4,3,0]non-5-en.
22. The organic EL device according to claim 12 , wherein the surface sealant includes the metal complex (b1) so that an equivalent ratio of a tertiary amine active functional group to an epoxy group is in the range of 0.008:1 to 0.3:1.
23. The organic EL device according to claim 12 , wherein the surface sealant further comprising an acid anhydride so that an equivalent ratio of an acid anhydride group to an epoxy group is in the range of 0.8:1 to 1.2:1.
24. The organic EL device according to claim 12 , wherein the surface sealant has a water content of 0.1 wt % or less.