JP6761972B2 - Ultraviolet curable resin composition, manufacturing method of organic EL light emitting device and organic EL light emitting device - Google Patents

Description

The present invention comprises an ultraviolet curable resin composition suitable for producing a sealing material in an organic EL light emitting device, a method for producing an organic EL light emitting device using this ultraviolet curable resin, and an organic EL provided with the sealing material. Regarding the light emitting device.

Organic EL light emitting devices are applied to lighting applications, display applications, etc., and are expected to be widely used in the future.

Among the organic EL light emitting devices, the so-called top emission type has, for example, an organic EL element arranged on a support substrate, a transparent substrate arranged so as to face the support substrate, and transparent between the support substrate and the transparent substrate. It is constructed by filling with a suitable sealing material. In this case, the light emitted by the organic EL element can pass through the sealing material and the transparent substrate and be emitted to the outside.

The sealing material suppresses the invasion of moisture into the organic EL element, thereby suppressing the generation and growth of dark spots in the organic EL element. The dark spot is a portion that does not emit light, which is generated when the organic EL element is deteriorated by moisture.

The encapsulant is prepared from, for example, a composition containing a cationic curable resin and a cationic polymerization initiator (see Patent Documents 1 and 2). In this case, since the composition can be cured by ultraviolet irradiation or the like to produce a sealing material, the sealing material can be produced without applying a heat load to the organic EL element.

Japanese Patent No. 5703429 Japanese Patent No. 5887467

The viscosity of the composition for organic EL encapsulation described in Patent Document 1 and Patent Document 2 is 50 mPa · s or more, so that the viscosity is not required to be so low, and it is assumed that the composition is applied by an inkjet method. Absent.

The subject of the present invention is an ultraviolet curable resin composition capable of lowering the viscosity and thereby being applied by an inkjet method, a method for producing an organic EL light emitting device using this ultraviolet curable resin composition, and an organic EL. It is to provide a light emitting device.

The ultraviolet curable resin composition according to one aspect of the present invention contains a polyfunctional cationically polymerizable compound, a cationic curing catalyst (C), and a monofunctional cationically polymerizable compound (E) having a viscosity of 8 mPa · s or less.

The method for manufacturing an organic EL light emitting device according to one aspect of the present invention is a method for manufacturing an organic EL light emitting device including an organic EL element and a sealing material covering the organic EL element, and the ultraviolet curable resin composition. Is molded by an inkjet method, and then the ultraviolet curable resin composition is irradiated with ultraviolet rays and cured to prepare the sealing material.

The organic EL light emitting device according to one aspect of the present invention includes an organic EL element and a sealing material covering the organic EL element, and the sealing material is a cured product of the ultraviolet curable resin composition.

In one aspect of the present invention, an ultraviolet curable resin composition capable of lowering the viscosity and thereby being applied by an inkjet method, a method for producing an organic EL light emitting device using this ultraviolet curable resin composition, and There is an advantage that an organic EL light emitting device can be provided.

It is a schematic cross-sectional view which shows an example of the organic EL light emitting device.

Hereinafter, an embodiment of the present invention will be described.

An example of the structure of the organic EL light emitting device 1 will be described with reference to FIG. The organic EL light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at intervals, an organic EL element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and a support substrate 2. It includes a sealing material 5 filled between the transparent substrate 3 and the transparent substrate 3. Further, in the example shown in FIG. 1, the organic EL light emitting device 1 includes a surface of the support substrate 2 facing the transparent substrate 3 and a passivation layer 6 covering the organic EL element 4.

The support substrate 2 is made of, for example, a resin material, but is not limited thereto. The transparent substrate 3 is made of a translucent material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The organic EL element 4 is also called an organic light emitting diode. The organic EL element 4 includes, for example, a pair of electrodes and an organic light emitting layer between the electrodes. The passivation layer 6 is preferably made of silicon nitride or silicon oxide.

The encapsulant 5 can be produced from the ultraviolet curable resin composition (hereinafter referred to as composition (X)) according to the present embodiment. That is, the composition (X) is preferably a composition for encapsulating an organic EL element or a composition for manufacturing an organic EL light emitting device.

[Composition (X)]
Hereinafter, the composition (X) will be described.

The composition (X) contains a polyfunctional cationically polymerizable compound, a cationic curing catalyst (C), and a monofunctional cationically polymerizable compound (E) having a viscosity of 8 mPa · s or less. The polyfunctional cationically polymerizable compound may contain either a polyfunctional cationically polymerizable compound (A) having no siloxane skeleton or a polyfunctional cationically polymerizable compound (B) having a siloxane skeleton. It can and can contain both. The UV curable resin composition may contain a hygroscopic agent, but may not.

When the composition (X) is irradiated with ultraviolet rays, the composition (X) is cured by a photocationic polymerization reaction, so that a cured product can be produced. The composition (X) can have a low viscosity by containing the monofunctional cationically polymerizable compound (E). Therefore, the applicability is good when the composition (X) is applied when the sealing material 5 is produced. Therefore, the composition (X) can be applied by a casting method, an inkjet method, or the like, and the composition (X) can also be applied by an inkjet method at room temperature.

Further, the cured product of the composition (X) can have a sufficiently high refractive index suitable as a sealing material 5 in the organic EL light emitting device 1. For example, the cured product can have a refractive index in the range of 1.45 or more and less than 1.55. Therefore, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, it is possible to improve the extraction efficiency of the light transmitted through the sealing material 5 and emitted to the outside.

In addition, the composition (X) can have good cationic polymerization reactivity, so that the cured product can have high strength. Further, it is possible to suppress the occurrence of tack on the cured product.

When the composition (X) contains a hygroscopic agent, the cured product can have hygroscopicity. The average particle size of the hygroscopic agent is not limited. When the hygroscopic agent contains the hygroscopic agent (D) having an average particle size of 100 nm or less, the cured product can also have high transparency. Further, even if the composition (X) contains a hygroscopic agent (D) having a small particle size, it can have a low viscosity by containing the monofunctional cationically polymerizable compound (E).

Further, when the composition (X) contains the polyfunctional cationically polymerizable compound (B), the viscosity is further reduced when the composition (X) contains the hygroscopic agent (D) having an average particle size of 100 nm or less. It's easy.

The viscosity of the composition (X) at 25 ° C. is preferably in the range of 5 to 50 mPa · s. In this case, it is easy to mold the composition (X) into a film or the like, and the composition (X) can be molded by a method such as a casting method or an inkjet method. It is also preferable that the viscosity of the composition (X) at 25 ° C. is in the range of 5 to 20 mPa · s. In this case, since the composition (X) has a particularly low viscosity, it is easy to mold the composition (X) by an inkjet method. It is also preferable that the viscosity of the composition (X) at 50 ° C. is in the range of 5 to 20 mPa · s. In this case, regardless of the viscosity of the composition (X) at room temperature, the viscosity of the composition (X) can be reduced by slightly heating the composition (X). Therefore, the composition (X) can be reduced in viscosity. It is easy to mold by the inkjet method. Such a low viscosity of composition (X) can be achieved by the composition of composition (X) described in detail below.

Hereinafter, the components of the composition (X) will be described in more detail.

As described above, in the second aspect, the components contained in the polyfunctional cationically polymerizable compound in the composition (X) are not particularly limited. The polyfunctional cationically polymerizable compound may contain either or both of the polyfunctional cationically polymerizable compound (A) and the polyfunctional cationically polymerizable compound (B).

The polyfunctional cationically polymerizable compound (A) does not have a siloxane skeleton and has two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (A) is preferably 2 to 4, and more preferably 2 to 3.

The cationically polymerizable functional group is at least one group selected from the group consisting of, for example, an epoxy group, an oxetane group and a vinyl ether group.

The polyfunctional cationic polymerizable compound (A) is, for example, a bifunctional alicyclic epoxy compound as shown in the following formula (1), a trifunctional epoxy compound as shown in the following formula (2), and a representative in the following formula (3). It contains at least one component of such a bifunctional oxetane compound, an alkylene glycol diglycidyl ether as shown in the following formulas (4) to (7), and an alkylene glycol monovinyl monoglycidyl ether as shown in the formula (8). it can.

In the formula (1), R ^{1 to} R ¹⁸ are independently hydrogen atoms, halogen atoms, or hydrocarbon groups, respectively. The hydrocarbon group may contain an oxygen atom or a halogen atom. In formula (1), X is a single bond or divalent organic group, and the organic group is, for example, −CO—O−CH ₂₋ .

Examples of the compound represented by the formula (1) include a compound represented by the following formula (1a) and a compound represented by the following formula (1b).

More specifically, the polyfunctional cationically polymerizable compound (A) includes, for example, celoxide 2021P and celoxide 8010 manufactured by Daicel, TEPIC-VL manufactured by Nissan Chemical Industries, OXT-221 manufactured by Toagosei, and 1, It can contain at least one component selected from the group consisting of 3-PD-DEP, 1,4-BG-DEP, 1,6-HD-DEP, NPG-DEP and butylene glycol monovinyl monoglycidyl ether.

The polyfunctional cationically polymerizable compound (A) preferably has an alicyclic epoxy structure, and particularly preferably contains the compound represented by the formula (1). In this case, the composition (X) can have higher cationic polymerization reactivity.

In particular, the composition (X) preferably contains the compound represented by the formula (1a). In this case, the composition (X) can have a higher cationic polymerization reactivity and a particularly low viscosity.

The amount of the polyfunctional cationically polymerizable compound (A) with respect to the total amount of the resin component is preferably in the range of 5 to 95% by mass. The resin component refers to a compound having cationically polymerizable properties in the composition (X), and includes a polyfunctional cationically polymerizable compound and a monofunctional cationically polymerizable compound (E). If the amount of the polyfunctional cationically polymerizable compound (A) is 5% by mass or more, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product has high strength. Can have. Further, when the amount of the polyfunctional cationically polymerizable compound (A) is 95% by mass or less, especially when the composition (X) contains a hygroscopic agent (D) having an average particle size of 100 nm or less, the composition ( The hygroscopic agent (D) can be easily dispersed particularly uniformly in X). The amount of the polyfunctional cationically polymerizable compound (A) is more preferably 12% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and 25% by mass or more. Is particularly preferable. Further, the amount of the polyfunctional cationically polymerizable compound (A) is more preferably 85% by mass or less, and further preferably 60% by mass or less. For example, the amount of the polyfunctional cationically polymerizable compound (A) is preferably in the range of 20 to 60% by mass.

The polyfunctional cationically polymerizable compound (B) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (B) is preferably 2 to 6, and more preferably 2 to 4. The polyfunctional cationically polymerizable compound (B) can contribute to the improvement of the cationic polymerization reactivity of the composition (X) and the heat-resistant discoloration of the cured product and the encapsulant 5. When the heat-resistant discoloration property of the sealing material 5 is high, it is possible to suppress the time-dependent deterioration of the light emission intensity and the time-dependent change of the light emission color of the organic EL light emitting device 1 provided with the sealing material 5. Further, the polyfunctional cationically polymerizable compound (B) can also contribute to lowering the elastic modulus of the cured product and the encapsulant 5, and therefore, the organic EL light emitting device 1 provided with the encapsulant 5 is made more flexible. It is also possible to give it. Further, the polyfunctional cationically polymerizable compound (B) can contribute to the improvement of the dispersibility of the hygroscopic agent (D) in the composition (X) and the cured product. Therefore, even if the hygroscopic agent (D) is not subjected to a surface treatment for improving dispersibility, the hygroscopic agent (D) can be satisfactorily dispersed in the composition (X) and the cured product. ..

The polyfunctional cationically polymerizable compound (B) is preferably liquid at 25 ° C. In particular, the viscosity of the polyfunctional cationically polymerizable compound (B) at 25 ° C. is preferably in the range of 10 to 300 mPa · s. In this case, the increase in viscosity of the composition (X) can be suppressed.

The cationically polymerizable functional group contained in the polyfunctional cationically polymerizable compound (B) is at least one group selected from the group consisting of, for example, an epoxy group, an oxetane group and a vinyl ether group.

The siloxane skeleton of the polyfunctional cationically polymerizable compound (B) may be linear, branched or cyclic. The number of Si atoms contained in the siloxane skeleton is preferably in the range of 2 to 15. In this case, the composition (X) can have a particularly low viscosity. The number of Si atoms is more preferably in the range of 2 to 10, further preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6.

The polyfunctional cationically polymerizable compound (B) contains, for example, at least one of a compound represented by the formula (10) and a compound represented by the formula (11).

R in each of the formulas (10) and (11) is a single bond or a divalent organic group, preferably an alkylene group. Y is a siloxane skeleton, which may be linear, branched or cyclic, and the number of Si atoms thereof is preferably in the range of 2 to 10, more preferably in the range of 2 to 7. It is more preferable if it is within the range of 3 to 6. n is an integer of 2 or more, preferably in the range of 2-4.

More specifically, for example, the polyfunctional cationically polymerizable compound (B) contains the compound represented by the following formula (10a).

R in the formula (10a) is a single bond or a divalent organic group, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the equation (10a) is an integer of 0 or more. The compound represented by the formula (10a) preferably contains the compound represented by the following formula (100). That is, the polyfunctional cationically polymerizable compound (B) preferably contains the compound represented by the following formula (100).

In the formula (100), n is an integer of 0 or more, preferably in the range of 0 to 8. It is more preferable if n is in the range of 0 to 5, and even more preferably if it is in the range of 1 to 4.

Examples of the compound represented by the formula (100) include the compound represented by the following formula (10a-1).

The polyfunctional cationically polymerizable compound (B) may be used in place of the compound represented by the formula (10a) or together with the compound represented by the formula (10a) in the following formulas (10b) to (10d) and (11a) to (11b). It may contain at least one compound among the compounds shown in.

R in the formula (10d) is a single bond or a divalent organic group, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the equation (10d) is an integer of 0 or more. M in the formula (10d) is an integer of 2 or more.

R in the formula (11a) is a single bond or a divalent organic group, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the formula (11a) is an integer of 0 or more, and is preferably in the range of 8 to 80. M in the formula (11a) is an integer of 2 or more, and is preferably in the range of 2 to 6.

R in the formula (11b) is a single bond or a divalent organic group, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the formula (11b) is an integer of 0 or more, and is preferably in the range of 8 to 80.

More specifically, the polyfunctional cationic polymerizable compound (B) is, for example, product numbers X-40-2669, X-40-2670, X-40-2715, X-40-2732, X manufactured by Shin-Etsu Chemical Co., Ltd. Containing at least one component selected from the group consisting of -22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163, and X-22-163B. Is preferable.

The polyfunctional cationically polymerizable compound (B) preferably has an alicyclic epoxy structure, and it is particularly preferable that the polyfunctional cationically polymerizable compound (B) contains the compound represented by the formula (2). The compound represented by the formula (2) can particularly contribute to the improvement of the cationic polymerization reactivity of the composition (X) and the reduction of the viscosity, and the improvement of the heat-resistant discoloration property and the low elastic modulus of the cured product and the sealing material 5. Can especially contribute to. When the composition (X) contains the hygroscopic agent (D), it can particularly contribute to the improvement of the dispersibility of the hygroscopic agent (D) in the composition (X).

The amount of the polyfunctional cationically polymerizable compound (B) with respect to the total amount of the resin component is preferably in the range of 5 to 95% by mass. When the amount of the polyfunctional cationically polymerizable compound (B) is 5% by mass or more, particularly when the composition (X) contains a hygroscopic agent (D), in the composition (X) and in the cured product. By particularly improving the dispersibility of the hygroscopic agent (D), the transparency of the cured product is particularly improved. Further, when the amount of the polyfunctional cationic polymerizable compound (B) is 95% by mass or less, the composition (X) can have a particularly high photocationic polymerization reactivity, and therefore the cured product has a particularly high strength. be able to. The amount of the polyfunctional cationically polymerizable compound (B) is more preferably 6% by mass or more, more preferably 13% by mass or more, and particularly preferably 20% by mass or more. Further, the amount of the polyfunctional cationically polymerizable compound (B) is more preferably 70% by mass or less, and in this case, the cured product can have a higher refractive index. The amount of the polyfunctional cationically polymerizable compound (B) is more preferably 45% by mass or less. For example, the amount of the polyfunctional cationically polymerizable compound (B) is preferably in the range of 20 to 70% by mass.

The cationic curing catalyst (C) is not particularly limited as long as it is a catalyst that generates protonic acid or Lewis acid by being irradiated with light. The cationic curing catalyst (C) can contain at least one of an ionic photoacid generating type cationic curing catalyst and a nonionic photoacid generator cationic curing catalyst.

The ionic photoacid generation type cationic curing catalyst can contain at least one of an onium salt and an organometallic complex. Examples of onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts. Examples of organometallic complexes include iron-allene complexes, titanosen complexes, and arylsilanol-aluminum complexes. The ionic photoacid generation type cationic curing catalyst can contain at least one of these components.

The cationic curing catalyst of the nonionic photoacid generator is at least one selected from the group consisting of, for example, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide phosphonate. Can contain the components of.

More specific examples of the cation curing catalyst (C) are DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, 109, etc.), BBI series manufactured by Midori Chemical Co., Ltd. (101, 102, 103, 105, 106, 109, 110, 200, 210, 300, 301, etc.), TSP series (102, 103, 105, 106, 109, 200, 300, 1000, etc.), HDS-109, MDS series (103, 105, 109, 203, 205, 209, etc.), BDS-109, MNPS-109, DTS series (102, 103, 105, 200, etc.), NDS series (103, 105, 155, 165, etc.) , DAM series (101, 102, 103, 105, 201, etc.), SI series (105, 106, etc.), PI-106, NDI series (105, 106, 109, 1001, 1004, etc.), PAI series (01, 101, etc.) , 106, 1001, 1002, 1003, 1004, etc.), MBZ-101, PYR-100, NB series (101, 201, etc.), NAI series (100, 1002, 1003, 1004, 101, 105, 106, 109, etc.) , TAZ series (100, 101, 102, 103, 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC-101, TPS-Actate, DTS-Actate, Di-Boc Bisphinol A, tert-Butyl lithocholate, tert-Butyl deoxycholate, tert-Butyl chocolate, BX, BC-2, MPI-103, BDS-105, TPS-103, NAT-103, B , And TMS-105;
Union Carbide, USA Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950;
BASF's Irgacure 250, Irgacure 261 and Irgacure 264;
CG-24-61 manufactured by Ciba Geigy Co., Ltd .;
ADEKA Corporation ADEKA OPTMER SP-150, ADEKA OPTMER SP-151, ADEKA OPTMER SP-170 and ADEKA OPTMER SP-171;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd .;
CI-2064, CI-2369, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682; manufactured by Nippon Soda Co., Ltd.
PI-2074, a tetrakis (pentafluorophenyl) borate tolulikmiliodonium salt manufactured by Rhodia;
3M FFC509;
CD-1010, CD-1011 and CD-1012 manufactured by Sartomer, USA;
Includes CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S from Sun Appro Co., Ltd .; and UVI-6992 and UVI-6976 from Dow Chemical.

The amount of the cation curing catalyst (C) with respect to the total amount of the resin component is, for example, in the range of 0.05 to 3% by mass.

The composition (X) may contain a hygroscopic agent as described above. The hygroscopic agent is preferably an inorganic particle having hygroscopicity, and preferably contains at least one component selected from the group consisting of, for example, zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles.

The composition (X) may contain a hygroscopic agent (D) having an average particle size of 100 nm or less. That is, the hygroscopic agent in the composition (X) may contain the hygroscopic agent (D) having an average particle size of 100 nm or less.

The hygroscopic agent (D) is preferably an inorganic particle having hygroscopicity, and contains at least one component selected from the group consisting of, for example, zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. Is preferable. It is particularly preferable that the hygroscopic agent (D) contains zeolite particles.

Zeolite particles having an average particle size of 100 nm or less can be produced, for example, by pulverizing general industrial zeolite. Zeolites may be pulverized and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Methods for producing such zeolite particles are known from JP-A-2016-69266, JP-A-2013-049602, and the like.

A specific example of a method for producing zeolite particles having an average particle size of 100 nm or less is shown. First, prepare zeolite powder. The zeolite powder is preferably a zeolite containing sodium such as LTA type (A type zeolite), but is not limited to this. This zeolite powder is physically crushed. For example, zeolite powder can be physically pulverized by mixing zeolite powder with water to prepare a slurry and subjecting the slurry to a bead mill crusher.

Subsequently, the zeolite powder is crystallized by hydrothermal synthesis. For example, hydrothermal synthesis can be performed by heating a slurry containing zeolite powder after physical pulverization in an autoclave. The conditions for hydrothermal synthesis are, for example, a heating temperature in the range of 150 to 200 ° C. and a heating time in the range of 15 to 24 hours.

Subsequently, the zeolite powder is dried. The drying temperature is, for example, in the range of 150 to 200 ° C., and the drying time is, for example, in the range of 2 to 3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or pestle and then sieved to adjust the particle size.

Subsequently, if necessary, the zeolite powder is subjected to an ion exchange treatment. In particular, when the zeolite powder is a zeolite containing sodium such as LTA, it is preferable to perform an ion exchange treatment for exchanging sodium in the zeolite powder with magnesium.

The ion exchange treatment is carried out, for example, by dispersing zeolite powder in an aqueous solution containing magnesium ions to prepare a mixture, and heating the mixture. More specifically, the ion exchange treatment is performed, for example, as follows. First, the zeolite powder is mixed with magnesium chloride and water, and the obtained mixture is heated and stirred. During this process, it is preferable to repeat the operation of temporarily stopping the stirring, discarding the supernatant of the mixture, then replenishing the mixture with water, and then restarting the stirring a plurality of times at appropriate intervals. .. The heating temperature in this treatment is preferably in the range of 40 to 80 ° C., and the treatment time is preferably in the range of 6 to 8 hours.

When the ion exchange treatment is performed, the zeolite powder is subsequently dried. The drying temperature is, for example, in the range of 150 to 200 ° C., and the drying time is, for example, in the range of 2 to 3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or pestle and then sieved to adjust the particle size.

As a result, zeolite particles having an average particle size of 100 nm or less can be obtained.

Crystallization of zeolite powder can also be carried out in the presence of silicates and alkali metal oxides. A specific example of a method for producing zeolite particles having an average particle size of 100 nm or less in that case is shown. First, prepare zeolite powder. The zeolite powder preferably has a composition of aM12O, bSiO2, Al2O3, and cMe. M1 is an alkali metal, proton, or ammonium ion (NH4 +), Me is an alkaline earth metal, a is a number in the range 0.01-1 and b is a number in the range 20-80. And c is a number in the range 0 to 1. The zeolite powder may be, for example, FAU type, CHA type, BEA type, MFI type, MOR type, or FER type.

This zeolite powder is physically crushed. For example, the zeolite powder can be physically crushed by subjecting it to a bead mill crusher.

The zeolite powder after physical pulverization is dispersed in a solution containing M2 ₂ O, SiO ₂ and H ₂ O to prepare a slurry. M2 is an alkali metal, preferably K or Na. The molar ratio of M2 ₂ O / H ₂ O is, for example, in the range of 0.003 to 0.01, and the molar ratio of SiO ₂ / H ₂ O is, for example, 0.006 to 0.025. The amount of zeolite powder is, for example, 0.5 to 10 g with respect to 100 ml of the solution.

By heating this slurry in an autoclave, zeolite powder can be crystallized. The conditions are, for example, a heating temperature in the range of 100 to 230 ° C. and a heating time in the range of 1 to 24 hours. Subsequently, the zeolite powder is washed and then dried.

As a result, zeolite particles having an average particle size of 100 nm or less can be obtained.

The pH of the zeolite particles is preferably in the range of 6-9. When the pH of the zeolite particles is 6 or more, the crystals of the zeolite particles are less likely to be destroyed, so that the encapsulant prepared from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. Further, when the pH of the zeolite particles is 9 or less, the zeolite particles are less likely to inhibit the curing when the composition (X) is cured. It is more preferable that the pH of the zeolite particles is in the range of 6 to 8, and further preferably in the range of 6.5 to 8.

The pH of the zeolite particles is determined by heating a dispersion obtained by adding 0.05 g of zeolite particles to 99.95 g of ion-exchanged water at 90 ° C. for 24 hours, and then measuring the pH of the supernatant of the dispersion with a pH meter. It is a value obtained by measuring with. As the pH measuring device, for example, a compact pH meter <LAQUAtwin> B-711 manufactured by HORIBA, Ltd. can be used.

In order for the pH of the zeolite particles to be in the range of 6 to 9, it is preferable that the zeolite particles are composed of FAUY type zeolite having a proton as a counter cation.

In the process of producing zeolite particles, when hydrothermal synthesis of zeolite is performed, a treatment for adjusting the pH may be performed. The treatment for adjusting the pH is carried out, for example, before heating the slurry containing the zeolite powder prepared for hydrothermal synthesis, during heating of the slurry, or after heating the slurry. The pH is adjusted, for example, by adding an acid to the slurry. The acid contains at least one component selected from the group consisting of, for example, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid and organic acids such as formic acid, acetic acid and oxalic acid.

The average particle size of the hygroscopic agent (D) is preferably in the range of 10 to 100 nm. When the average particle size is 100 nm or less, the cured product can have particularly high transparency. Further, when the average particle size is 10 nm or more, good hygroscopicity of the hygroscopic agent (D) can be maintained. The average particle size is the median diameter calculated from the measurement result by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As the measuring device, the Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

It is particularly preferable that the average particle size of the hygroscopic agent (D) is in the range of 5 to 70 nm. In this case, the cured product can have particularly good transparency and hygroscopicity.

It is also preferable that the cumulative 90% diameter (D90) of the hygroscopic agent (D) is 100 nm or less. In this case, the cured product can have particularly high transparency.

The amount of the hygroscopic agent with respect to the total amount of the composition (X) is preferably in the range of 1 to 20% by mass. When the amount of the hygroscopic agent is 1% by mass or more, the cured product can have particularly high hygroscopicity. Further, when the amount of the hygroscopic agent is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) can have a sufficiently low viscosity so that it can be applied by an inkjet method. The amount of the hygroscopic agent is more preferably in the range of 1 to 20% by mass, further preferably in the range of 5 to 15% by mass.

When the hygroscopic agent contains the hygroscopic agent (D) having an average particle size in the range of 10 to 100 nm, the amount of the hygroscopic agent (D) with respect to the total amount of the composition (X) is in the range of 1 to 20% by mass. It is preferably inside. When the amount of the hygroscopic agent (D) is 1% by mass or more, the cured product can have particularly high hygroscopicity. Further, when the amount of the hygroscopic agent (D) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) has a sufficiently low viscosity so that it can be applied by an inkjet method. You can also. The amount of the hygroscopic agent (D) is more preferably in the range of 1 to 20% by mass, and even more preferably in the range of 5 to 15% by mass.

As described above, the composition (X) contains the monofunctional cationically polymerizable compound (E) having a viscosity at 25 ° C. of 8 mPa · s or less. When the composition (X) contains the monofunctional cationically polymerizable compound (E), the monofunctional cationically polymerizable compound (E) has the viscosity of the composition (X) even if the composition (X) does not contain a solvent. Can be reduced. In particular, the viscosity of the monofunctional cationically polymerizable compound (E) at 25 ° C. is preferably in the range of 0.1 to 8 mPa · s.

The monofunctional cationically polymerizable compound (E) has only one cationically polymerizable functional group per molecule. The cationically polymerizable functional group is at least one group selected from the group consisting of, for example, an epoxy group, an oxetane group and a vinyl ether group.

The monofunctional cationically polymerizable compound (E) can contain, for example, at least one compound selected from the group consisting of the compounds represented by the following formulas (13) to (15), (9) and (16).

The monofunctional cationically polymerizable compound (E) preferably contains the compound represented by the above formula (16). In this case, the viscosity of the composition (X) can be reduced. Further, since the compound represented by the formula (16) has a high boiling point and low volatility among the components that can be contained in the monofunctional cationically polymerizable compound (E), the viscosity of the composition (X) with time is changed. Can effectively suppress the rise. Therefore, the composition (X) can have good coatability even when stored for a long period of time, and can maintain good inkjet coatability.

The amount of the monofunctional cationically polymerizable compound (E) with respect to the total amount of the resin component is preferably in the range of 5 to 50% by mass. When the amount of the monofunctional cationically polymerizable compound (E) is 5% by mass or more, the viscosity of the composition (X) can be particularly reduced. Further, when the amount of the monofunctional cationically polymerizable compound (E) is 50% by mass or less, the composition (X) can have particularly excellent reactivity at the time of the photocationic polymerization reaction, and thereby the cured product. Can have high strength. The amount of the monofunctional cationically polymerizable compound (E) is more preferably 10% by mass or more, and further preferably 15% by mass or more. The amount of the monofunctional cationically polymerizable compound (E) is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. When the amount of the monofunctional cationically polymerizable compound (E) is particularly 35% by mass or less, the volatile amount of the components in the composition (X) can be effectively reduced while the composition (X) is stored. Therefore, even if the composition (X) is stored for a long period of time, the characteristics of the composition (X) are not easily impaired. Further, it is possible to particularly suppress the occurrence of tack on the cured product. For example, the amount of the monofunctional cationically polymerizable compound (E) is preferably in the range of 10 to 35% by mass.

The composition (X) preferably contains a dispersant (F). In this case, the dispersibility of the hygroscopic agent (D) in the composition (X) can be further improved, and the viscosity of the composition (X) can be further reduced.

The dispersant (F) can contain, for example, at least one of a metal soap and a silane coupling agent.

The silane coupling agent can contain at least one component selected from the group consisting of vinylsilane, epoxysilane, methacrylicsilane, aminesilane, and alkoxysilane.

The dispersant (F) is preferably non-amine type. This is because amine-based dispersants may inhibit photocationic polymerization. Therefore, it is more preferable that the dispersant (F) does not contain the above-mentioned amine silane.

The silane coupling agent preferably contains an epoxy silane, and more preferably contains at least one of 3-glycidoxypropyltrimethoxysilane and 8-glycidoxyoctyltrimethoxysilane.

The amount of the dispersant (F) is preferably 20% by mass or more based on the total amount of the filler. In this case, the dispersibility of the hygroscopic agent (D) can be particularly improved, and the viscosity of the composition (X) can be particularly reduced. It is also preferable that the amount of the dispersant (F) is 40% by mass or less with respect to the amount of the filler. In this case, the generation of outgas from the composition (X) can be suppressed, and the adhesion between the cured product and the glass substrate or the like can be improved. The amount of the dispersant (F) is more preferably in the range of 20 to 40% by mass and further preferably in the range of 25 to 35% by mass with respect to the total amount of the filler. The filler is an inorganic particle in the composition (X) and contains a hygroscopic agent (D). When the composition (X) contains an inorganic filler other than the hygroscopic agent (D) described later, the filler also contains the inorganic filler.

The composition (X) may contain an inorganic filler other than the hygroscopic agent (D). In particular, the composition (X) preferably contains nano-sized high refractive index particles. Examples of high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the cured product can have a high refractive index while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, it is possible to improve the extraction efficiency of the light transmitted through the sealing material 5 and emitted to the outside. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

The amount of high refractive index fine particles in the composition (X) is appropriately designed so that the cured product has a desired refractive index. In particular, the high refractive index particles are preferably contained in the composition (X) so that the refractive index of the cured product is in the range of 1.5 to 1.7. In this case, the light extraction efficiency of the organic EL light emitting device 1 is particularly improved.

The composition (X) may contain various additives other than the above. For example, the composition (X) may contain a sensitizer.

The composition (X) preferably does not contain a solvent. In this case, it is not necessary to dry the composition (X) to volatilize the solvent when preparing the cured product from the composition (X).

The composition (X) can be prepared by mixing the above-mentioned components. The composition (X) is preferably liquid at 25 ° C.

When the thickness dimension of the cured product of the composition (X) is 10 μm, the total light transmittance of the cured product is preferably 90% or more. In this case, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, the efficiency of extracting light that passes through the sealing material 5 and is emitted to the outside can be particularly improved. High light transmittance of such a cured product can be achieved by containing the composition of the composition (X) described above, particularly the hygroscopic agent (D) having an average particle size of 100 nm or less. ..

The hygroscopicity of the cured product is preferably 0.5% by mass or more, more preferably 1% by mass or more, and most preferably 2% by mass or more. The hygroscopicity is determined by the following method. A film having a thickness of 10 μm is produced by applying the composition (X) in an Ar atmosphere and then irradiating with ultraviolet rays. The ultraviolet irradiation conditions are, for example, an ultraviolet peak wavelength of 365 nm, an ultraviolet intensity of 3000 mW / cm2, and an ultraviolet irradiation time of 10 seconds. This film is vacuum dried using, for example, a vacuum dryer under the conditions of a heating temperature of 120 ° C. and a heating time of 3 hours. The mass of the film after drying is measured. Let this measurement result be the initial mass (M0). Subsequently, the film is sufficiently absorbed with moisture. To that end, for example, the film is exposed for 24 hours under conditions of 85 ° C. and 85% RH. Measure the mass of the film after absorbing moisture. This measurement result is called the mass (M) after absorbing moisture. From these initial mass (M ₀ ) and post-moisture absorption mass (M), the hygroscopicity can be calculated by the formula (M-M ₀ ) / M ₀ × 100 (mass%).

The cured product can have high adhesion to silicon nitride and silicon oxide. Silicon nitride and silicon oxide may be used as materials for the passivation layer 6 in the organic EL light emitting device 1. Therefore, when the passivation layer 6 is made of silicon nitride or silicon oxide, the adhesion between the sealing material 5 and the passivation layer 6 can be improved, and thus the reliability of the organic EL light emitting device 1 is improved. To do. When the polyfunctional cationically polymerizable compound has an epoxy group, the cured product can have particularly high adhesion to silicon nitride and silicon oxide.

[Method of manufacturing encapsulant and method of manufacturing organic EL light emitting device]
A method for producing the sealing material 5 and a method for producing the organic EL light emitting device 1 will be described.

First, the support substrate 2 is prepared. An organic EL element 4 is provided on one surface of the support substrate 2. The organic EL element 4 can be manufactured by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable to manufacture the organic EL element 4 by a coating method such as an inkjet method.

Next, the passivation layer 6 is provided. The passivation layer 6 can be produced, for example, by a vapor deposition method.

Next, the composition (X) is applied so as to cover one surface of the support substrate 2 and the organic EL element 4. When the passivation layer 6 is provided, the composition (X) is applied so as to cover the passivation layer 6. The method of applying the composition (X) is, for example, a casting method or an inkjet method. Since the viscosity of the composition (X) can be reduced in the present embodiment, the composition (X) can be applied by an inkjet method. If the inkjet method is applied to both the formation of the organic EL element 4 and the coating of the composition (X), the production efficiency of the organic EL light emitting device 1 can be particularly improved.

Next, the transparent substrate 3 is superposed on the composition (X). The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

Next, ultraviolet rays are irradiated from the outside toward the transparent substrate 3. Ultraviolet rays pass through the transparent substrate 3 and reach the composition (X). As a result, the cationic polymerization reaction proceeds in the composition (X) to cure the composition (X), and a sealing material 5 made of the cured product is produced. The thickness of the sealing material 5 is, for example, in the range of 5 to 50 μm.

Hereinafter, specific examples of the present invention will be presented. However, the present invention is not limited to the examples.

1. 1. Preparation of Composition The compositions of Examples and Comparative Examples were prepared by mixing the components shown in the “Composition” column of the table.

The details of the components shown in the table are as follows. The viscosities of the following components are values measured using a rheometer (manufactured by Anton Paar Japan K.K., model number DHR-2) under the conditions of a temperature of 25 ° C. and a shear rate of 100 s ^-1 .

(1) Polyfunctional cation-polymerizable compound having no siloxane skeleton, celloxide 8010: manufactured by Daicel, trade name celloxide 8010, compound represented by formula (1a), viscosity 60 mPa · s.
-OXT-221: manufactured by Toagosei, product number OXT-221, compound represented by formula (3), viscosity 10 mPa · s.
-Selokiside 2021P: Made by Daicel, product name Selokiside 2021P, compound represented by formula (1b), viscosity 250 mPa · s.
-TEPIC-FL: manufactured by Nissan Chemical Industries, Ltd., product name TEPIC-FL, compound represented by formula (2), viscosity 700 mPa · s.

(2) Polyfunctional cation-polymerizable compound having a siloxane skeleton-X-40-2669: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-40-2669, compound represented by formula (10a-1), viscosity 55 mPa · s.
X-40-2732: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-40-2732, a compound represented by the formula (10a) (mixture of n = 1 to 4, R = C ₂ H ₄ ), viscosity 20 mPa · s.
· X-22-169AS: manufactured by Shin-Etsu Chemical Co., No. X-22-169AS, compounds represented by the formula (10a) (n = 8, R = C 2 H 4), viscosity 25 mPa · s.
X-22-2046: Shin-Etsu Chemical Co., Ltd., product number X-22-2046, compound represented by formula (10d), viscosity 45 mPa · s.
X-40-2715: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-40-2715, linear trifunctional compound, viscosity 190 mPa · s.

(3) Monofunctional cation-polymerizable compound-OXT-212: 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane.
Epogosei 2EH: manufactured by Yokkaichi Chemical Company Limited, product name Epogosei 2EH, compound represented by formula (13), viscosity 2 mPa · s.
-AL-OX: manufactured by Yokkaichi Chemical Company Limited, product name AL-OX, compound represented by formula (9), viscosity 1 mPa · s.
3-allyloxymethyl-3-ethyloxetane: manufactured by Yokkaichi Chemical Company Limited, compound represented by formula (16), viscosity 2 mPa · s.

(4) Catalyst ・ DTS-200: Made by Midori Chemical Co., Ltd., Part No. DTS-200, C ₆ H _5- SC ₆ H _4- S ⁺ (C ₆ H ₅ ) ₂・ B (C ₆ F ₅ ) ^4- .

(5) Dispersant-KBM403: Shin-Etsu Chemical Co., Ltd., product number KBM403, 3-glycidoxypropyltrimethoxysilane.
-KBM4803: Shin-Etsu Chemical Co., Ltd., product number KBM4803, 8-glycidoxyoctyltrimethoxysilane.

(6) Hygroscopic agent (6-1) Zeolite particles 1
Zeolite particles 1 are produced by the following method, and have a D50 of 20 nm, a D90 of 50 nm, and a pH of 11.

A 4A-type zeolite / sodium ion having an average particle size of 5 μm was prepared as a starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry.

After adding 400 g of zirconia beads having a particle size of 100 μm to this slurry, the zeolite powder in the slurry was pulverized for 3 hours with a bead mill crusher to bring the average particle size of the Na-based zeolite to 120 nm. At this time, the slurry flow rate is 10 kg / h and the slurry viscosity is 10 mPa · s.

Subsequently, zirconia beads having a particle size of 100 μm are removed from the slurry, 400 g of zirconia beads having a particle size of 50 μm are added instead, and then the Na-based zeolite in the slurry is pulverized for 1 hour with a bead mill crusher to obtain the zeolite powder. The average particle size was 70 nm. At this time, the slurry flow rate is 10 kg / h and the slurry viscosity is 6 mPa · s.

Subsequently, zirconia beads having a particle size of 50 μm are removed from the slurry, 450 g of zirconia beads having a particle size of 30 μm are added instead, and then the zeolite powder in the slurry is pulverized for 1 hour with a bead mill crusher to obtain an average of the zeolite powder. The particle size was 20 nm. At this time, the slurry flow rate is 10 kg / h and the slurry viscosity is 4 mPa · s.

The zeolite powder in the slurry treated by the bead mill crusher was hydrothermally synthesized by the following method. 50 g of the slurry was placed in a fluororesin container, and the fluororesin container was placed in an autoclave stainless steel (SUS316) container. The stainless steel container has a capacity of 100 cc, a heat resistant temperature of 200 ° C., and a pressure resistant pressure of 50 MPa, and has a closed structure sealed by a lid provided with a safety valve. The stainless steel container was placed in a dryer, sealed, and heated at 180 ° C. for 24 hours. Next, the stainless steel container was taken out from the dryer and rapidly cooled by putting it in water at room temperature.

The fluororesin container was taken out from the stainless steel container, placed in a bat, and left at a temperature of 180 ° C. for 2 to 3 hours to dry the slurry in the fluororesin container. As a result, finely pulverized zeolite powder was obtained. The zeolite powder was taken out from a fluororesin container, crushed in a mortar, and then passed through a mesh to adjust the particle size to obtain zeolite particles 1.

The pH of the zeolite particles was measured by the following method. After putting 0.05 g of zeolite particles and 99.95 g of ion-exchanged water in a polyethylene bottle, the bottle was placed in a constant temperature bath and heated at 90 ° C. for 24 hours. Subsequently, the pH of the supernatant of the liquid in the bottle was measured using a compact pH meter <LAQUAtwin> B-711 manufactured by HORIBA, Ltd.

(6-2) Zeolite particles 2
Zeolite particles 2 are produced by the following methods, the D50 of which is 60 nm, the D90 of which is 100 nm, and the pH of which is 11.

A 4A-type zeolite / sodium ion having an average particle size of 5 μm was prepared as a starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized by a method similar to that for zeolite particles 1 so that the average particle size was 60 nm. Subsequently, the zeolite particles 2 were obtained by subjecting the zeolite particles 1 to a hydrothermal synthesis treatment in the same manner as in the case of the zeolite particles 1 and then crushing the zeolite particles 1 to further adjust the particle size.

(6-3) Zeolite particles 3
Zeolite particles 3 are produced by the following methods, the D50 of which is 150 nm, the D90 of which is 250 nm, and the pH of which is 11.

A 4A-type zeolite / sodium ion having an average particle size of 5 μm was prepared as a starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized by a method similar to that for zeolite particles 1 so that the average particle size was 150 nm. Subsequently, a hydrothermal synthesis treatment was performed in the same manner as in the case of the zeolite particles 1, and then the particles were crushed to further adjust the particle size to obtain the zeolite particles 3.

(6-4) Zeolite particles 4
The zeolite particles 4 are Tosoh's product numbers Zeolite 4A, 100 mesh pass products, which are powder products that have not been surface-treated, and have a D50 of 13 μm, a D90 of 30 μm, and a pH of 10.

(7) High-refractive index particles / nanoparticles: manufactured by Daiichi Rare Element Co., Ltd., product number UEP-100, primary average particle size 10 to 15 nm.

2. 2. Evaluation test The following evaluation test was carried out for Examples and Comparative Examples. The results are shown in the table.

(1) Inkjet The composition is put into a cartridge of an inkjet printer (manufactured by Seiko Epson Corporation, type PX-B700), and after confirming that the composition in the cartridge can be ejected from the nozzle of the inkjet printer, the composition is discharged from the nozzle. The composition was ejected and the test pattern was printed continuously. As a result, "A" indicates that the composition can be discharged for 1 hour and the discharge operation is stable, and "B" indicates that the composition can be discharged for 1 hour but the discharge operation becomes unstable intermittently. The case where the nozzle was clogged and the composition could not be discharged 1 hour before the start of discharge was evaluated as "C".

(2) Dispensability Using an air dispenser (Musashi Engineering Co., Ltd., "SHOTMASTER300"), the dispense nozzle is set to 400 μm, the nozzle gap is set to 30 μm, and the discharge pressure is set to 300 kPa. I drew. As a result, it was evaluated as "B" when at least one of the poor coating shape of the cross pattern and the stringing at the time of coating occurred, and "A" when none of them occurred.

(3) Transmittance A coating film is prepared by applying the composition, and the coating film is applied to the coating film using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. under the condition of about 3000 mW / cm2. A film having a thickness of 10 μm was prepared by irradiating with ultraviolet rays for seconds and photocuring. The total light transmittance of this film according to JIS K7361-1 was measured.

(4) 1 g of the volatile composition was placed in a petri dish having a diameter of 30 mm, and this was placed in a dry box with an Ar atmosphere and left for 1 hour. As a result, the case where the weight loss amount of the composition was 1% or more was evaluated as "B", and the case where the weight loss amount was less than 1% was evaluated as "A".

(5) Pencil hardness A film having a thickness of 10 μm was prepared by the same method as in the above-mentioned evaluation of transmittance. The pencil hardness of this film was measured according to JIS K5600-5-4.

(6) 25 ° C. Viscosity The composition is placed in a resin bottle having a capacity of 200 cc, and the viscosity of this composition at 25 ° C. is measured by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV-25, cone plate: CP1). The mold) was used for measurement under the conditions of 25 ° C. and 50 rpm.

(7) 50 ° C. Viscosity The viscosity at the time when the composition was placed in a resin bottle having a capacity of 200 cc and the composition was held at a temperature of 50 ° C. for 1 hour was measured by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV). -25, cone plate: CP1 type) was used for measurement at 50 ° C. and 50 rpm.

(8) Tackiness (curability)
After applying the composition on a smooth table, it is irradiated with ultraviolet rays for 10 seconds under the conditions of a peak wavelength of 365 nm and an output of 300 mW / cm2 using an LED-UV irradiator manufactured by Panasonic Electric Works, Ltd. It was cured. As a result, a film having a thickness of 10 μm was produced.

The tester touched the surface of the film with a finger to determine the presence or absence of tack. As a result, the case where the examiner did not feel the tack was evaluated as "A", and the case where the examiner felt the tack was evaluated as "B".

(9) Adhesion Strength A composition is applied on the surface of a quartz glass piece (dimensions 76 mm × 52 mm × 1 mm) to form a coating film having a thickness of 50 μm, and another quartz glass piece (dimensions 76 mm) is formed on the coating film. × 52 mm × 1 mm) were overlapped. Subsequently, the coating film was cured by irradiating it with ultraviolet rays for 10 seconds under the condition of about 3000 mW / cm2 using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works, Ltd. Next, the adhesion strength between the two quartz glass pieces was evaluated by performing a T-shaped peel test based on JIS K6854.

(10) Refractive index A coating film is prepared by applying the composition, and the coating film is applied to the coating film using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. under the condition of about 3000 mW / cm2. A film having a thickness of 10 μm was prepared by irradiating with ultraviolet rays for seconds and photocuring.

The total light transmittance and the refractive index of this film were measured with an ellipsometer (manufactured by SCI, "Filmtek 3000").

(11) Moisture Absorption A coating film is prepared by applying a composition in a glove box under an Ar atmosphere, and this coating film is applied using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. A film having a thickness of 10 μm was prepared by irradiating with ultraviolet rays for 10 seconds under the condition of about 3000 mW / cm ² and photocuring.

This film was vacuum dried using a vacuum dryer under the conditions of a heating temperature of 120 ° C. and a heating time of 3 hours, and then the mass of this film was measured. Let this measurement result be the initial mass (M ₀ ). Subsequently, the film was exposed under the conditions of 85 ° C. and 85% RH for 24 hours, and then the mass of the film was measured. This measurement result is called the mass (M) after absorbing moisture. From these initial mass (M ₀ ) and mass after moisture absorption (M), the hygroscopicity was calculated by the formula (M-M ₀ ) / M ₀ × 100 (mass%).

As a result, when the moisture absorption rate is 2% by mass or more, it is "AA", when it is 1% by mass or more and less than 2% by mass, it is "A", when it is 0.5% by mass or more and less than 1% by mass, it is "B", 0 The case of 1% by mass or more and less than 0.5% by mass was evaluated as "C", and the case of less than 0.1% by mass was evaluated as "D".

(12) Storability The composition was placed in a glass container having a capacity of 50 ml with the lid open, and the container was left in a glove box in an Ar atmosphere for one month. Subsequently, the ink property of the composition was confirmed by the same method as in (1).

Claims (20)

Polyfunctional cationically polymerizable compound,
It contains a cationic curing catalyst (C) and a monofunctional cationically polymerizable compound (E) having a viscosity of 8 mPa · s or less.
The monofunctional cationically polymerizable compound (E) contains 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and contains.
The monofunctional cationically polymerizable compound (E) further contains at least one compound selected from the group consisting of the compounds represented by the following formulas (14) to (16), respectively.
The amount of the monofunctional cationically polymerizable compound (E) with respect to the total amount of the resin component is in the range of 5 to 50% by mass.
Used to make encapsulants for organic EL devices,
UV curable resin composition. It is used to prepare the encapsulant for the organic EL element by molding by an inkjet method and then curing with ultraviolet rays.
The ultraviolet curable resin composition according to claim 1. Polyfunctional cationically polymerizable compound,
It contains a cationic curing catalyst (C) and a monofunctional cationically polymerizable compound (E) having a viscosity of 8 mPa · s or less.
The monofunctional cationically polymerizable compound (E) is selected from at least a group consisting of 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and compounds represented by the following formulas (13) to (16), respectively. Contains a kind of compound,
The amount of the monofunctional cationically polymerizable compound (E) with respect to the total amount of the resin component is in the range of 5 to 50% by mass.
It is used to produce a sealing material for organic EL devices by molding by an inkjet method and then curing with ultraviolet rays.
UV curable resin composition. The monofunctional cationically polymerizable compound (E) contains the compound represented by the formula (16).
The ultraviolet curable resin composition according to claim 3. Polyfunctional cationically polymerizable compound,
It contains a cationic curing catalyst (C) and a monofunctional cationically polymerizable compound (E) having a viscosity of 8 mPa · s or less.
The polyfunctional cationically polymerizable compound contains a polyfunctional cationically polymerizable compound (B) having a siloxane skeleton and contains.
The monofunctional cationically polymerizable compound (E) contains 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and contains.
The amount of the monofunctional cationically polymerizable compound (E) with respect to the total amount of the resin component is in the range of 5 to 50% by mass.
It is used to produce a sealing material for organic EL devices by molding by an inkjet method and then curing with ultraviolet rays.
UV curable resin composition. The polyfunctional cationically polymerizable compound contains a polyfunctional cationically polymerizable compound (B) having a siloxane skeleton.
The ultraviolet curable resin composition according to any one of claims 1 to 4. The ultraviolet curable resin composition according to claim 5 or 6, wherein the number of Si atoms in the siloxane skeleton in the polyfunctional cationically polymerizable compound (B) is in the range of 2 to 15. The polyfunctional cationically polymerizable compound (B) contains a compound represented by the following formula (100).
In the above equation (100), n is an integer of 0 or more.
The ultraviolet curable resin composition according to any one of claims 5 to 7. In the above equation (100), n is an integer in the range of 0 to 8.
The ultraviolet curable resin composition according to claim 8. The amount of the polyfunctional cationically polymerizable compound (B) with respect to the total amount of the resin component is in the range of 5 to 95% by mass.
The ultraviolet curable resin composition according to any one of claims 5 to 9. Polyfunctional cationically polymerizable compound,
Cationic curing catalyst (C),
It contains a monofunctional cationically polymerizable compound (E) having a viscosity of 8 mPa · s or less and a hygroscopic agent (D).
The monofunctional cationically polymerizable compound (E) contains 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and contains.
The amount of the monofunctional cationically polymerizable compound (E) with respect to the total amount of the resin component is in the range of 5 to 50% by mass.
It is used to produce a sealing material for organic EL devices by molding by an inkjet method and then curing with ultraviolet rays.
UV curable resin composition. The monofunctional cationically polymerizable compound (E) further contains at least one compound selected from the group consisting of the compounds represented by the following formulas (13) to (16), respectively.
The UV curable resin composition according to claim 5 or 11.
Further containing a hygroscopic agent (D),
The ultraviolet curable resin composition according to any one of claims 1 to 10. Does not contain polyfunctional vinyl ether,
The ultraviolet curable resin composition according to any one of claims 1 to 13. The polyfunctional cationically polymerizable compound contains a polyfunctional cationically polymerizable compound (A) having no siloxane skeleton.
The ultraviolet curable resin composition according to any one of claims 1 to 14. The polyfunctional cationically polymerizable compound (A) contains a compound represented by the following structural formula (1) and contains.
In the formula (1), R ^{1 to} R ¹⁸ are independently hydrogen atoms, halogen atoms, or hydrocarbon groups, and the hydrocarbon group may contain an oxygen atom or a halogen atom, and X is a single bond. The ultraviolet curable resin composition according to claim 15, which is a divalent organic group. The ultraviolet curable resin composition according to any one of claims 1 to 16, which does not contain a solvent. It is a method of manufacturing an organic EL light emitting device including an organic EL element and a sealing material covering the organic EL element.
This includes producing the encapsulant by molding the ultraviolet curable resin composition by an inkjet method and then irradiating the ultraviolet curable resin composition with ultraviolet rays to cure the composition.
The ultraviolet curable resin composition is the ultraviolet curable resin composition according to any one of claims 1 to 17.
A method for manufacturing an organic EL light emitting device. It comprises an organic EL element and a sealing material that covers the organic EL element, and the sealing material is a cured product of an ultraviolet curable resin composition.
The ultraviolet curable resin composition is the ultraviolet curable resin composition according to claim 1 or 2 .
Organic EL light emitting device. The encapsulant was produced by molding the ultraviolet curable resin composition by an inkjet method and then irradiating the ultraviolet curable resin composition with ultraviolet rays to cure it.
The organic EL light emitting device according to claim 19.